Revisiting Stress Corrosion Cracking of Steel in Caustic Solutions for Developing Cracking Susceptibility Diagrams for Improved Applicability

SARVESH PAL, R.K. SINGH RAMAN, and R.N. IBRAHIM Stress corrosion cracking tests were conducted using Bayer solutions of dierent chemistry at dierent temperatures for extraction of alumina from bauxite ores. The validity of the commonly used caustic cracking susceptibility (CS) diagram for steels exposed to plain caustic solutions was assessed by testing the notched and precracked specimens. This study presents rst results toward the development of a model susceptibility diagram for actual Bayer solutions, and for improved applicability of the traditional plain caustic diagram. For mechanistic understanding of caustic cracking, tests were also carried out under imposed electrochemical conditions. DOI: 10.1007/s11661-011-1024-1 The Minerals, Metals & Materials Society and ASM International 2012

I.

INTRODUCTION

IN the Bayer process, steel is the commonly used material for construction of reaction vessels and pipes for dierent processing components for extraction of alumina from bauxite ores, such as digesters, decomposers, and precipitators.[111] Caustic embrittlement continues to be a concern for steel pipes and vessels in hot caustic service; however, low carbon steels is still the most frequently used material.[12] Berk and Waldeck[13] and Mazille and Uhlig[14] investigated the limits of caustic concentrations and temperatures that can cause embrittlement. For example, steels were found to show immunity to caustic embrittlement at 5 wt pct NaOH when temperatures were below 368 K (95 C), whereas this temperature limit was 313 K (40 C) at 50 wt pct NaOH. A caustic cracking susceptibility (CS) diagram (Figure 1)[12] is a plot of caustic concentration against temperature, based on industrial as well as laboratory tests for a maximum of 62 days. This diagram identies dierent regions of CS. The upper hatched area is the severe cracking zone, whereas in the regime immediately below this area, the cracking may or may not take place. For example, the CS diagram suggests that the caustic concentration between 15 and 40 wt pct is most likely to
SARVESH PAL, formerly Postdoctoral Student with the Department of Mechanical and Aerospace Engineering, Monash University, Clayton, VIC 3800, Australia, is now a Postdoctoral Fellow with the Department of Mechanical and Mining Engineering, The University of Queensland, Brisbane, OLD 4072, Australia, and is also with the CRC for Rail Innovation, Brisbane, OLD 4072, Australia. R.K. SINGH RAMAN, Professor, is with the Department of Mechanical and Aerospace Engineering, Monash University, and is also with the Department of Chemical Engineering, Monash University, Clayton, VIC 3800, Australia. Contact e-mail: raman.singh@monash.edu R.N. IBRAHIM, Associate Professor, is with the Department of Mechanical and Aerospace Engineering, Monash University. Manuscript submitted July 15, 2011. Article published online January 27, 2012
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cause caustic cracking at 373 K (100 C), whereas for the same concentration range, the caustic cracking may or may not take place if the temperature is below 353 K (80 C). The upper hatched area was developed in the laboratories,[12] whereas the lower curve is based on the information from eld experience.[15] Understanding of CS is less clear in the regions between the upper hatched area and the lower curve. By developing an improved understanding of the eect of caustic concentration and temperature on caustic cracking, it may be possible to expand the limits for safe application of carbon steel in various steps of the Bayer process.[16] Caustic cracking of in-service components is highly likely to be inuenced by the sharp notches and other stress raisers that are often present in the fabricated components. Therefore, to investigate the validity of the CS diagram, it may be more practical to test the notched and precracked specimens. Impurities in caustic solutions also change CS. For example, aluminate ions (AlO2) increase the CS of steel,[17] because these ions decrease the stability of the passive lm that develops on steels in plain NaOH solution. On the other hand, some oxidizing agents, such as KMnO4 and NaNO3, assist the formation of c-Fe2O3 lms, thereby favorably shifting the electrochemical potential and retarding caustic cracking.[18] The dissolution repassivation theory is the most accepted mechanism for the caustic cracking of mild/ carbon steels.[6,8,19,20] The dissolution-repassivation mechanism[21] involves the rupture of the freshly formed passive lm at the crack tip under a high local stress intensity under tensile stress. This rupture creates a narrow anodic area of very high current density at the crack tip, causing rapid dissolution and subsequent repassivation. Rapid reiterations of the cycle of dissolution and repassivation result in accelerated crack propagation. Hence, establishment and sustenance of favorable crack-tip chemistry under simultaneous electrochemical and mechanical actions is essential for
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caustic crack propagation. For the alloy-environment systems susceptible to caustic cracking by the dissolution-repassivation mechanism, the cracking is expected to be accelerated when electrochemical potential at the crack tip lies within the regime of transition from an active dissolution to repassivation. On the other hand, formation of a robust passive lm at the crack tip that does not crack at the available stress intensity may retard/stop caustic crack propagation. The determination of the threshold value of the stress intensity factor (KI) necessary for propagation of an existing crack in a corrosive environment, i.e., KISCC, is important for material selection and life extension for any mechanical engineering design. Specimens for the determination of KISCC by traditional techniques, viz. compact tension (CT) and double cantilever beam (DCB),[22] are required to be large in order for them to comply with the plane strain conditions for the linear elastic fracture mechanics approach. CT and DCB specimens are also expensive to manufacture/test and require long testing time. The determination of KISCC using a circumferential notched tensile (CNT) specimen is a rapid and accurate approach, which overcomes the aforementioned disadvantages of the traditional techniques. This article builds on revisiting the existing CS diagram that relates only to the plain caustic solutions
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and presents a case for developing new diagrams for actual Bayer solutions. A model CS diagram for typical Bayer solutions was generated using the CNT technique. This diagram will serve as a new guideline for addressing the ongoing concerns of caustic cracking in the alumina processing industry. Imposed potential tests in passive and active-passive transition regions were conducted to ensure that the established mechanistic understanding of caustic cracking in the Bayer solution holds good during CNT testing.

II.

MATERIALS AND METHODS

A. Test Material and Solutions The test material used in this study was AS/NZ 3678(grade 250) steel plates, which is a common material for fabrication of the components for alumina extraction. The chemical composition of this steel is listed in Table I. The mechanical properties of the steel were as follows: yield strength: 338 MPa, ultimate tensile strength: 492 MPa, and elongation: 35 pct. CNT specimens (Figure 2) were machined out of these plates. Dierent test solutions were prepared from a typical Bayer solution. The typical composition of the Bayer solution is given Table II. This Bayer solution was modied by addition of dierent amounts of the reagent grade NaOH pellets, as given in Table III, to make 10, 20, 30, and 40 wt pct free caustic concentrations. The caustic concentration of the supplied Bayer solution was 11.6 wt pct. CS tests were carried out within the temperature range of 318 to 373 K (45 to 100 C), and the free caustic concentrations were in the range of 10 to 40 wt pct.
Table II. Ingredient Chemical Composition of Bayer Solution Content (Wt Pct) 11 3 42 37 3 4

Boiling Point Curve

Cracking area

Temperature, C

100

Severe cracking Above this curve

70

Cracking reported above curve

40 0 10 20 30 40 50 60

Concentration of NaOH,%
Fig. 1CS diagram,[12] superimposed with some recent CS data generated using CNT specimens. New data: the stars represent the denite cracking region, the squares represent the potential cracking, and the circles represent the denite absence of cracking.

NaOH Na2CO3 H2O Al2O33H2O NaCl Na2SO4

Table I. C 0.17 Si 0.27 Mn 1.19 P 0.019

Chemical Composition of Grade 250 Steel (Weight Percent) S 0.009 Cu 0.02 Cr 0.02 Ni 0.01 Mo 0.002 V 0.003 Al 0.028 Ti 0.003

Fig. 2CNT specimen (all dimensions are in millimeters).

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The term equivalent free caustic (FC) concentration is dened as the freely available NaOH concentration in the Bayer solution. As shown in Table II, the Bayer solution consists of NaOH and impurities. The impurities of alumina (in dierent hydrate forms, viz. Al2O33H2O and Al2O3H2O) react with NaOH and form sodium aluminates per the following equations: 2NaOH Al2 O3 3H2 O ! 2N aAlO2 4H2 O 2NaOH Al2 O3 H2 O ! 2NaAlO2 2H2 O 1 2

remaining NaOH in Bayer solution is freely available to take part in the corrosion and caustic cracking. B. Electrochemical Experiments For investigating the role of imposed electrochemical potential on CS, rst, polarization behavior of the carbon steel in a given caustic solution was established. Anodic polarization sweeps were performed using a corrosion cell (autoclave), and the plots of current (i) vs potential (E) were generated. Electrochemical experiments were carried out using cylindrical specimens, a potentiostat, and the autoclave (the schematic diagram is shown in Figure 3). Part of the cylindrical surface was wrapped with Teon tape to ensure that a known surface is exposed to solution. The cylindrical specimen that works as the working electrode was polished up to 2000 grit paper before testing. An Hg/HgO reference electrode that was constructed in-house was connected to the electrochemical cell externally through a solution bridge in such a way that the reference electrode is always in contact with the solution and at room temperature (Figure 3). The Hg/HgO reference electrode was successfully used earlier[23,24] in electrochemical testing using hot caustic solutions. A spiral of Monel wire (1.65-mm diameter), which acted as a counter

Part of the added NaOH reacts with alumina present in the Bayer solution and forms sodium aluminate. The
Table III. Addition of NaOH (g/L) 87 174 359 539 Amount of NaOH Pellet Additions to Bayer Solution FC Concentration in Bayer Solution (Wt Pct) 10 20 30 40

Gas Outlet

Potentiostat

Specimen Thermocouple

Counter Electrode
Reference Electrode Autoclave

Fig. 3Schematic diagram of the potentiodynamic polarization test.

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electrode, was placed around the working electrode. This arrangement ensured homogeneous distribution of current over the exposed area of the working electrode. The test solution temperature was controlled with 1 K (1 C) using a thermocouple and a temperature controller. Anodic polarization tests were carried out using a PAR Versastat II potentiostat. The polarization scans were carried out at the recommended scan rate of 0.1666 mV/s (ASTM G5-87). The polarization sweep identied the regimes of active-passive transition and passivity. A few CNT tests were carried out employing a constant imposed potential in the active-passive transition and passive regimes. C. Tests Using Notched + Precracked CNT Specimens Notched and precracked specimens of dierent geometries (viz. CT and DCB) are generally used in investigations requiring determination of stress intensity (KI). Plots of KI vs parameters such as time to failure or crack growth rate are useful for the life prediction of cracked components that are exposed to the corrosive environment. Such plots also provide the thresholds of KI for stress corrosion crack propagation (KISCC), which is useful data for any decision on the continued operation with an existing crack. Traditional CT or DCB specimens that have been commonly used for the determination of KI and KISCC may require prohibitively expensive machining and a relatively large amount of test material. A relatively simple testing technique, viz. CNT testing, was developed by Ibrahim and Stark[25] for the determination of KI and has lately been extended by Raman and co-workers[2629] for determination of KISCC. Details of this technique and experimental setup are described in the literature.[27,30] This technique simplies and speeds up the testing procedure. The CNT specimen (shown in Figure 2) is also less expensive to produce because of its cylindrical shape, which reduces the cost of specimen fabrication by a factor of up to 10 (cf. CT specimen).[30] The small cross section of the specimen makes it possible to apply quite high stress levels using moderate loads. All these advantages make CNT testing an ideal choice for a relatively large number of tests using precracked specimens that may be required for the investigation of CS of carbon steel in Bayer solution. 1. Determination of KI by CNT testing and associated intricacies CNT specimens were subjected to fatigue precracking, using a rotating bending machine. The precracked specimens were washed with ethanol and dried before being installed into the CNT testing rig. The corrosion cell was lled with plain caustic or Bayer solution. The test rig was heated to the test temperature before applying tensile load to the specimen. This procedure ensured that the applied load did not change as a result of expansion of the specimen and surrounding ttings. The loading was carried out using an INSTRON*
*INSTRON is a trademark of Instron, Canton, MA.

tensile testing machine. The specimens were held in the Bayer solution at an applied load until they failed (or for a considerable length of time, and then examined for the features of caustic cracking). Failed specimens were cleaned with water and acetone. It has been observed that the specimens after fracture were found to have eccentric nal ligaments. When the ligament is ocenter, the fracture of the specimen will not only result from tension forces but will also have a contribution of bending moments. Those specimens having such eccentric ligaments gave underestimated KI results. Therefore, the specimens with eccentric ligaments might yield correct results only if the bending stresses induced by the eccentricity were included in the calculation of KI.[25,31] Therefore, the eect of eccentricity must be taken into account in calculating KI. The KI, following a well-established and documented method,[31] was determined from the fractured specimen, using the following equation for specimens of cylindrical geometry[25,31]: p 3 KI rt rb apFO where rt and rb are the tensile and bending stress terms, respectively; a is the fatigue crack depth; and Fo is the geometrical parameter taking into account the eccentricity of the fatigue crack. The detailed calculation can be found in another publication by the authors.[31,32] D. Fractography The fracture surface was ultrasonically cleaned using a cleaning solution that contained 6 mL conc. HCl + 10 mL of 30 gpl 2 Butyne 1,4 diol + 100 mL distilled water. The cleaned surface was observed under JEOL**
**JEOL is a trademark of Japan Electron Optics Ltd., Tokyo.

840 scanning electron microscopy (SEM) in order to investigate the presence of the well-established fractographic evidence of the caustic cracking of steel.

III.

RESULTS

A. Stress Corrosion Cracking Behavior of Grade 250 Steel To investigate the applicability of the CS diagram, four concentrations at various temperatures were chosen. It is not possible to precisely control the precrack depth, and hence the stress intensity (KI). Therefore, it is practical to select a range of applied loads. The loads were chosen in the range between the fracture toughness (KIC) and the threshold stress intensity for caustic cracking (KISCC) in the test solution in which mild steel in most susceptible to caustic cracking, per Figure 1 (i.e., 30 wt pct NaOH at 373 K (100 C)).[12] Thus, it became necessary to determine KISCC in this solution. The KISCC of grade 250 steel in 30 wt pct NaOH at 373 K (100 C) was determined to be ~24 MPa m1/2 by the same authors using the CNT technique.[29]
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1. Investigation of caustic cracking in plain caustic solutions Although the SCC behavior of steel in plain NaOH was studied recently by the same authors,[26] a detailed study of SCC would relate with electrochemical behavior. In addition, this study compares the SCC behavior of steel in plain NaOH with the Bayer solution. Therefore, it became necessary to present the results of the earlier investigation on plain caustic solution. Test temperatures and caustic concentrations for these tests were selected such that their combinations would fall in the regimes of denitely no cracking, denitely cracking, and may be cracking in the susceptibility diagram (Figure 1). The distinctive fractographic features for caustic cracking of the precracked specimens

was the presence of intergranular cracking immediately adjacent to the fatigue precrack. The representative overall fracture surface of such specimens (shown in Figure 4(a)) has four regions that are located in the following order (moving from edge to center): the machined notch at the specimen edge, fatigue precrack, caustic cracking, and exclusively mechanical fracture. The distinctive features of these regions are established at higher magnications. In light of the features for the presence and absence of intergranular cracking (clearly identied in Figures 4(a) and (b)), the fractographic features of the CNT specimens tested using the chosen combinations of caustic concentrations and temperatures were examined. The specimen that did not fail in stipulated time had an absence of intergranular features

Fig. 4SEM fracture surface of CNT specimens tested in caustic solutions: (a) overall fracture surface showing dierent regions: machined notch, fatigue crack, and mechanical failure zone; (b) samples with caustic cracking showing intergranular cracking at a higher magnication; and (c) samples without caustic cracking having dimples (in the lower half) immediately adjacent to the beach marks (in the upper half) and the absence of intergranular features in between.
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(Figure 4(c)). The results are summarized in Table IV. Based on the test results presented in Table IV, a CS diagram of steel in plain NaOH is presented in Figure 5(a). This is largely consistent with the common CS diagram (Figure 1). 2. Investigation of caustic cracking in Bayer solutions Similar to those in plain NaOH, caustic cracking tests were conducted in dierent Bayer solutions having dierent caustic concentrations. The results are summarized in Table V. The CS diagram of the steel in Bayer solution, as presented in Figure 5(b), was developed on the basis of the data in Table V. It was observed that in the 30 wt pct FC Bayer solution, steel was highly susceptible to caustic cracking even at a considerably low temperature (328 K (55 C)). However, as the FC concentration increased to 40 wt pct, the CS decreased drastically. The caustic cracking at this concentration was observed only at a considerably high temperature (373 K (100 C)), as shown in Figure 5(b). B. Electrochemical Behavior Electrochemical behavior of grade 250 steel in dierent caustic solutions was studied. Figure 6 presents the anodic polarization plots at dierent temperatures and concentrations, and the corresponding ECorr data are presented in Table VI. Typical regions of active-passive potentials and passivation potentials in plain NaOH solutions were selected on the basis of Figure 6. Similar data for the steel in dierent Bayer solutions are presented in Figure 7 and Table VII. C. CS Under Imposed Electrochemical Potentials

imposed potentials were either in the passive region or in the active-passive region. For the test at an active-passive potential, a fatigue precracked CNT specimen was loaded in 30 wt pct NaOH solution at 373 K (100 C), and a potential of 750 mV was imposed. A comparison of data in Figure 8
120 100

Temperature (C)

80 60 40 20 0 0 5 10 15 20 25 30 35 40 45

Free Caustic Concentration of Plain NaOH (%)

(a)
120 100

Temperature (C)

80 60 40 20

A few CNT tests under imposed potentials were carried out at active-passive potentials and passive potentials identied in Figure 6. The anodic polarization curve in 30 wt pct NaOH at 373 K (100 C) suggests that the active-passive regime lies within the range of 830 to 600 mV, after which passive regime starts (Figure 6(c)). In order to study the caustic cracking behavior under imposed potential, CNT specimens were subjected to stressing while the
Table IV. Caustic Concentration (Wt Pct) 10 20 Caustic Solution Temperature (C) 100 70 100 80 80 65 100 70 55 100 70 45

0 0 5 10 15 20 25 30 35 40 45

Free Caustic Concentration of Bayer Solution (%)

(b)
Fig. 5Caustic cracking susceptibility regions in (a) plain NaOH and (b) Bayer solution. The hatched area is the caustic cracking prone area and the points identify the actual test conditions.

Caustic Cracking Tests in Plain NaOH Solutions Applied Stress Intensity (MPa m1/2) 35.8 32.9 39.4 35.7 29.5 49.7 27 39.9 32.6 27.8 33.7 32.5 Evidence of Intergranular Fractographic Features no (forced no (forced yes yes yes no (forced yes no (forced no (forced yes no (forced no (forced to fractured) to fractured)

Time to Failure (h) did not did not 134 h 408 h 950 h did not 815 h did not did not 184 h did not did not fail (in 3192 h) fail (in 6960 h)

CS no no yes yes yes no yes no no yes no no

fail (in 2064 h) fail (in 2000 h) fail (in 5520 h) fail (in 6219 h) fail (in 3192 h)

to fractured) to fractured) to fractured) to fractured) to fractured)

30 40

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Table V. Caustic Cracking Tests in Bayer Solutions Free Caustic Concentration (Wt Pct) 10 20 Caustic Solution Temperature (C) 100 70 100 80 80 65 100 70 55 100 70 45 Applied Stress Intensity (MPa m1/2) 37.3 33.1 31.7 27.3 32.3 62.9 27.3 42.2 53.2 75.1 41.2 30 Evidence of Intergranular Fractographic Features yes no (forced yes yes yes no (forced yes yes yes yes no (forced no (forced to fractured)

Time to Failure (h) 2088 h did not fail (in 2323 h) 241 h 2280 h 950 h Did not fail (in 4000 h) 1801 h 87 h 210.3 h 192 h did not fail (in 2112 h) did not fail (in 1632 h)

CS yes no yes yes yes no yes yes yes yes no no

to fractured)

30 40

to fractured) to fractured)

Fig. 6Potentiodynamic polarization plots of steel at dierent temperatures in plain NaOH solutions (wt pct): (a) 10 pct, (b) 20 pct, (c) 30 pct, and (d) 40 pct.

suggests that at the applied stress intensity of ~24 MPa m1/2, the specimen with the imposed potential failed in 74.8 hours, whereas for similar stress intensities but without imposed potential, it took a minimum of 250 hours for the specimen to fail. This suggests that
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by imposing the potential in the active-passive region, caustic crack propagation was accelerated. The observation of a considerable deterioration in caustic cracking resistance as a result of imposed potential in the active-passive regime is consistent with the literature.[2,23]
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While this observation suggests a considerable increase in cracking susceptibility under the condition, where a component that is susceptible to caustic cracking could fall within the active-passive regime, it also provides a guideline for avoiding such electrochemical conditions in the industry.
Table VI. Ecorr at Dierent Temperatures and Plain Caustic Concentrations Caustic Concentration (Wt Pct) 10 10 20 20 20 30 30 30 40 40 40 Temperature (C) 100 70 100 80 65 100 70 55 100 70 45 ECorr (mV) 190 47.5 249 47.5 9.5 830 207 177 595 341 241

The fracture surface of the failed specimen shows four zones: machine notch, fatigue crack, caustic cracking, and mechanical failure zone (Figures 9(a) and (b)). Each of these features is similar to the reported fractographic features of a carbon steel exposed to 30 wt pct NaOH at free corrosion potential.[26] The caustic cracking zone
Table VII. ECorr at Dierent Temperatures in Bayer Solutions of Dierent Free Caustic Contents Free Caustic Concentration (Wt Pct) 10 10 20 20 20 30 30 30 40 40 40 Temperature (C) 100 70 100 80 65 100 70 55 100 70 45 ECorr (mV) +60 +227 503 39 26 133 84 59 124 102 92

Fig. 7Potentiodynamic polarization plots of steel at dierent temperatures in various Bayer solutions with FC (wt pct): (a) 10 pct, (b) 20 pct, (c) 30 pct, and (d) 40 pct.
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Fig. 8KI vs time to failure plot for the steel in 30 wt pct NaOH at 373 K (100 C): the diamonds represent data for free corrosion potential (Pal and Raman[29]), and the triangle represents the data for imposed potential in the active to passive transition region (750 mV).

(Figures 9(b) and (d)) is sandwiched between the fatigue cracking zone (Figures 9(b) and (c)) and the mechanical failure zone (Figure 9(b)). However, the intergranular features (Figure 9(d)) occupied a considerably larger area of the fracture surface in this specimen (as compared to the sample tested without imposed potential), even though the time of exposure to the caustic solution was shorter (74 hours) in the case of the specimen tested at the imposed active-passive potential (750 mV). This observation further emphasizes the damaging role of imposed electrochemical potential in the active-passive regime. For tests under the imposed potential in the passive region, a potential of 400 mV was selected. Figure 10 compares KI and tf data of specimens tested with and without the imposed passive potential (Ep = 400 mV) at two dierent KI (34.88 and 24.23 MPa m1/2). Neither specimen failed even after ~1800 hours of testing, whereas the specimen tested at a similar KI but without any imposed potential would be expected to fail within ~250 hours (according to the plot). While the observation of considerable improvement of caustic cracking

Fig. 9Fractographs of steel exposed to 30 wt pct NaOH at 373 K (100 C) and imposed potential in the active-passive transition region (750 mV): (a) overall fracture surface; (b) three zones: fatigue crack, caustic cracking, and mechanical failure zones; (c) beach marks suggesting the fatigue cracking zone; and (d) intergranular features conrming CS.
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resistance as a result of imposed passive potential is consistent with the literature,[23,24] this observation also provides a guideline for electrochemical measures for retardation of caustic crack propagation in industrial situations. The fracture surface of the specimen tested in the passive region did not show any feature of caustic cracking. The ductile dimples were observed immediately after the beach mark (shown in Figures 11(a) and (b)), and no regions with intergranular cracking were observed.

IV.

DISCUSSION

A. Effect of Imposed Potentials on CS It is important to note the strong inuence of electrochemical conditions on the caustic cracking. However, as the results of CNT testing under impose passive potential (Figure 10) would suggest, a suitable electrochemical condition can overpower the eect of stress intensity. It is well known that the susceptibility to caustic cracking is greatly increased when the electrochemical potential is in the active-passive regime,

Fig. 10KI vs time to failure plot for the base metal in 30 wt pct NaOH solution at 373 K (100 C) at a free corrosion potential and at imposed potential in the passive region (400 mV). Diamonds are at free corrosion potential (Pal and Raman[29]) and triangles are at the imposed potential.

Fig. 12Potential-pH diagram at 373 K (100 C) for iron.[21]

Fig. 11Fracture surface of carbon steel exposed to 30 wt pct NaOH at 373 K (100 C) under an imposed potential in passive region (400 mV): (a) overall fracture surface and (b) dimple features immediately after beach marks. Absence of intergranular features suggests that the formation of passive lm by imposing the potential in the passive region subsides the susceptibility to caustic cracking.
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whereas the susceptibility is hugely decreased when the potential is in the passive regime.[24] This can be explained on the basis of the chemical reactions described below.[10,23,33,34] Fe 3OH ! HFeO H2 O 2e 2 Fe 2OH ! FeOH2 3FeOH3 2OH ! Fe3 O4 4H2 O 2e 2Fe3 O4 2OH ! 3Fe2 O3 H2 O 2e 2HFeO ! Fe2 O3 H2 O 2e 2 4 5 6 7 8

It was reported in the literature that the formation of di-hypo ferrate (HFeO2) ions promotes the caustic cracking, whereas the formation of stable oxide such as Fe3O4 disfavors this type of cracking.[24] Low carbon steels undergo several oxidation stages during anodic polarization in highly concentrated NaOH solution. Hydroxyl ions (OH) play a predominant part in anodic behavior and accelerate the rate of iron dissolutions at these active potentials. At higher temperatures, these hydroxyl ions promote chemical dissolution of the passive Fe2O3 lm and cause oxidation of iron to FeO2 at high anodic potentials. In the active-passive region, iron dissolves as HFeO2 and these di-hypo ferrate ions (HFeO2) favor caustic cracking. In the active-passive transition potential regime, oxidation of HFeO2 to FeO2 is not thermodynamically possible at these temperatures and caustic concentrations.[34] Application of potential in the active passive region will promote the formation of HFeO2 ions and in the passive region will promote the formation of protective lm of magnetite (Fe3O4), as shown in the pH-potential diagram (Pourbaix diagram in Figure 12). The activepassive peak seen at 0.83 to 0.6 VSCE (Figure 6(c)) corresponds to the dissolution of iron as HFeO2 and the ultimate formation of a Fe3O4 lm, as indicated by the Pourbaix diagram. B. Effect of Temperature and Caustic Concentrations on CS Caustic cracking was observed at each of the four concentrations at 373 K (100 C) in the plain caustic as well as the Bayer solution (Figures 5(a) and (b)). An increase in processing temperature increased the CS, and this eect was more prevalent in the high-temperature regime. However, in the lower temperature regime, the CS was signicantly greater in the Bayer solution than in the plain NaOH solution. This can be attributed to the role of impurities and additives in the Bayer solution. Consistent with the very recent work on pure NaOH by the same authors,[26] CS in 30 wt pct NaOH was limited to 373 K (100 C) (Figure 5(a)), whereas in Bayer solutions, the CS in the present study was observed at much lower temperatures (328 K (55 C)). Among the
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impurities dissolved in the Bayer solutions, aluminate ions have the greatest damaging inuence on the susceptibility of steel.[9] The detrimental eect of aluminate ions is attributed to the formation of an amorphous lm of Fe 3xAlxO4, where x 2, which is less stable (i.e., it is more likely to create an active-passive regime). Sriram and Tromans[35] conducted caustic cracking tests in a Bayer solution (overall concentration: 14.4 wt pct, free caustic concentration: 9 wt pct) at 365 K (92 C) using notched specimens and observed that the presence of AlO2 species moves KISCC toward a lower regime of stress intensities (i.e., the cracking susceptibility increases). Le and Ghali[9] and Raman[36] conducted the experiment in Bayer solutions and dierent caustic aluminate solution in conjunction with tests in plain NaOH at 373 K (100 C) and reported the steel to be more susceptible to caustic cracking in the Bayer solutions.

V.

CONCLUSIONS

1. Experimental work carried out using precracked CNT specimens of carbon steel suggested caustic cracking under conditions in which tests using a smooth specimen reported in the literature did not show caustic cracking (e.g., 30 wt pct caustic solution at 373 K (100 C)). The caustic cracks propagate intergranularly. 2. CS of steel in a Bayer solution extends to a lower temperature regime than in a plain caustic solution. 3. CNT testing with imposed electrochemical potentials provides a simple means to characterize electrochemical mechanistic aspects of caustic cracking, using precracked specimens.

ACKNOWLEDGMENTS The authors appreciate Australian Research Council Linkage Grant No. LP0669622 for nancial support. The authors record a special word of appreciation to Alcoa World Alumina for providing a Bayer solution for testing.

REFERENCES
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