Corrosion Science 46 (2004) 591612 www.elsevier.

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Eect of the strain rate on stress corrosion crack velocities in face-centred cubic alloys. A mechanistic interpretation
S.A. Serebrinsky, J.R. Galvele
*
Comisin Nacional de Energa Atmica, Departamento Materiales, Instituto de Tecnologia, Avda. o o Libertador 8250, 1429 Buenos Aires, Argentina Received 28 August 2002; accepted 2 July 2003

Abstract Constant extension rate tests on smooth samples, with strain rate (SR) values from 106 s1 up to 20 s1 , were used to study stress corrosion cracking (SCC) systems in face-centred cubic alloys. It was found that by increasing the SR a monotonic increase of the log CPR (crack propagation rate) takes place. It was also observed that the slope a in log CPR vs. log SR plots had dierent values for dierent SCC morphologies. Intergranular SCC is more steeply accelerated by SR, aIG 0:50.7, than transgranular SCC, aTG 0:20.3. The dierences found between intergranular SCC and transgranular SCC were analysed under the light of the available SCC mechanisms. 2003 Elsevier Ltd. All rights reserved.
Keywords: A. Stainless steel; Silver; Brass; C. Stress corrosion; Eects of strain

1. Introduction Numerous variables have a strong eect on the stress corrosion cracking (SCC) process in metals and alloys, the strain rate (SR) being one of them [1,2]. In a recent publication Serebrinsky et al. [3] studied the eect of SR on the crack propagation rate (CPR) for a variety of alloyenvironment systems. In their study the authors covered a wide range of SR values, going from 106 s1 up to 20 s1 . They found that, while an increase in the SR produced an increase in the CPR, the eect was

Corresponding author. Tel.: +54-11-6772-7390; fax: +54-11-6772-7404. E-mail address: galvele@cnea.gov.ar (J.R. Galvele).

0010-938X/$ - see front matter 2003 Elsevier Ltd. All rights reserved. doi:10.1016/S0010-938X(03)00172-0

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more signicant for intergranular SCC than for transgranular SCC. The results showed that the slope a in log CPR vs. log SR plots was aIG 0:50.7 for intergranular cracking, while it only reached values of aTG 0:20.3 for transgranular cracking. This dierence in behaviour between transgranular cracking and intergranular cracking, was conrmed by Alvarez et al. [4]. Alvarez et al. compared single crystals of Ag10Au alloy with polycrystalline samples of the same alloy. These authors strained the samples in both a 1 M HClO4 solution and a 1 M KCl solution, and found slopes similar to those reported by Serebrinsky et al. [3]. In the present work a systematic study was made of all the cases studied by Serebrinsky et al. [3] in their preliminary work. Only homogeneous face-centred cubic (fcc) alloys were considered in this study, assuming that similar plastic behaviour would be found when straining the dierent fcc alloys. The previously reported slopes for both intergranular and transgranular SCC were conrmed. An analysis was made of the experimental results, under the scope of the available SCC mechanisms [5,6], and it was concluded that the surface mobility SCC mechanism accounted for the experimental observations.

2. Experimental method 2.1. Materials Only homogeneous alloys, with an fcc structure, were used in the present work. The samples were 0.8 mm diameter wires. All the samples were degreased in acetone and subjected to a thermal treatment, as described below. Before each test, the samples were again degreased with acetone. The alloys used were identied by their commercial name, except for the silver alloys, which were identied by their nominal atomic % composition. The analytical composition of the alloys used, in wt.%, were: type AISI 304 stainless steel (Cr 16.9, Ni 8.0, Si 0.7, Mo 0.4, C 0.08, S 0.03, Fe balance), Ag15Pd (Pd 15.5, Pb < 0.01, Cd < 0.01, Cu 0.030.1, Al 0.003, Si 0.001, Fe 0.01, Mg 0.01, Pt < 0.005, Au < 0.005, Rh < 0.15, Ir < 0.015, Ag balance), and yellow brass (Al 0.002, Si < 0.02, Fe 0.05, Ti 0.02, Mg 0.0002, Mn 0.0005, Sn 0.02, Pb 0.02, Cr 0.0050.02, Ni 0.050.2, Zn 34.8 0.1, Cu balance). The composition of the alloys AgxAu, where x 2, 5 and 15 at.% is given in Table 1. In the present work these alloys are referred to as AISI 304, AgPd, AgAu and brass, respectively.

Table 1 Chemical composition of the AgAu alloys used Alloy (at.%) Ag2Au Ag5Au Ag15Au Element (wt.%) Au 3.99 8.63 23.1 Al Cu <0.2 <0.2 0.050.2 Pt <0.01 <0.01 Si 0.005 0.005 <0.002 Fe 0.002 <0.002 0.002 Mg 0.0002 <0.0002 <0.0002 Ag Balance Balance Balance

S.A. Serebrinsky, J.R. Galvele / Corrosion Science 46 (2004) 591612 Table 2 Mechanical properties of the alloys used, at 105 s1 Alloy AISI 304 Ag15Pd Ag2Au Ag5Au Ag15Au Brass r0:2 (MPa) 206 113 55 55 53 95 UTS (MPa) 885 321 182 178 180 495 er (%) 34.5 26.6 18.8 15.9 16.4 40.0

593

No signicant dierences were observed when varying the strain rate.

All the thermal treatments were carried out in argon atmospheres. The AISI 304 was annealed for 30 min at 1100 C, and water quenched. The AgPd and AgAu alloys were annealed at 800 C for 1 h, and air-cooled. Brass was annealed for 24 h at 454 C and water-quenched. No traces of b phase were detectable in the annealed brass samples. The mechanical properties of all the alloys were measured at strain rates ranging from 105 s1 up to 1 s1 . The properties measured were: the conventional ow stress for 0.2% plastic strain (r0:2 ), the ultimate tensile strength (UTS) and the true strain to rupture (er ). For all the alloys the three parameters either increased slightly with SR, or remained constant. In general the variation of UTS with SR was slightly higher than that of r0:2 . No measurements of mechanical properties were made in the range 120 s1 . Since the change of the mechanical properties with SR, in the measured range was small and smooth, it was assumed that the same should be expected for the SR values not covered during the mechanical properties measurements. Table 2 shows the mechanical property values found at 105 s1 . 2.2. Environments All the solutions used were prepared with analytical grade reagents and triply distilled water with a minimum resistivity of 18.2 MX cm. AISI 304 was tested in an 11.8 M LiCl solution at 130 C. In this case the temperature was kept constant within 1 C. All the other systems were tested at room temperature. The AgPd alloy was tested in aqueous 1 M KCl and 1 M KI solutions. The AgAu alloys were tested in aqueous 1 M HClO4 solution. Brass was tested in 1 M NaNO2 solution and in a solution with the following composition: 0.05 M CuSO4 + 1 M (NH4 )2 SO4 , the pH of the solution was adjusted to 6.5 with NH4 OH. In the text this last solution is referred to as Mattsons solution. 2.3. Polarization curves Anodic polarization curves were measured in a conventional three-electrode glass cell, with a potential scanning rate of 0.5 mV s1 . The solutions were deaerated with prepuried nitrogen [7], in a scrubber connected to the cell. After a 60 min deaeration, the solution was transferred to the cell. The samples were allowed to reach a

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steady potential, and then the potential was scanned, beginning at a potential 100 mV below the corrosion potential. The reference electrodes used were: for AISI 304 in the LiCl solution a calomel saturated reference electrode, for brass in aqueous NaNO2 solution, as well as for AgPd alloy in KI solution and for AgAu alloys in HClO4 solution a mercurous sulphate reference electrode, for AgPd in KCl, a silver chloride reference electrode, prepared according to [8]. In the case of brass in Mattsons solution a pure copper wire was used as a reference electrode. All the potentials are reported in the standard hydrogen electrode (SHE) scale, with the only exception of brass in Mattsons solution, where the potential applied in the straining experiments was the equilibrium potential of copper in the solution. 2.4. Stress corrosion tests The SCC tests were carried out at constant strain rate. For convenience, the experiments were divided in three strain rate ranges: slow strain rate tests (SSRT) for SR values in the range of 106 104 s1 , intermediate strain rate tests (ISRT) for SR values in the range of 104 1 s1 , and ultrafast strain rate tests (UFSRT) for SR values higher than 1 s1 . For SSRT and ISRT the machines used were conventional constant crosshead speed straining machines, and the cell used was described in [9]. The total length of the sample, between grips, was 120 mm, and the part of the samples exposed to the corrosive solutions had an initial area of 0.8 mm2 . The UFSRT were performed in a drop weight apparatus described in [10], and the cell was similar to that for SSRT, but arranged for vertical straining. In the UFSRT the failure time tr was calculated by detecting the starting point and the end of the test with two switches wired to a Tektronix TDS-210 digital oscilloscope. With the xed image in the oscilloscope tr ttot DLr =DLtot was calculated, ttot and DLtot being the total time and length of the mobile grip displacement, and DLr the elongation to rupture. The electrode potentials were measured through a Luggin capillary and were kept constant with a LYP M7 potentiostatgalvanostat. The procedure for loading the solution into the cell as well as the reference electrodes used were those described for the polarization curves. After the samples reached a steady potential, the chosen potential was applied. The samples were kept at constant potential for a short time, and then the straining of the samples was started. The exposure at constant potential pointed to obtaining a reproducible initial surface, but without allowing for excessive surface corrosion. Typical exposure time values, at constant potential, were the following: for AISI 304 and AgPd, 10 min, for AgAu, between 15 s and 10 min, depending on the current density and for brass in Mattsons solution, 3 min. The potentials applied for each experiment, are described in the next section. The samples were strained to fracture. Afterwards the fracture surface and lateral surfaces of the samples were observed with a Phillips 500 scanning electron microscope (SEM). Then the samples were mounted for metallographic sectioning and observation. The crack propagation rate was calculated by dividing the crack length Lf by the failure time tf . The former was found either by measuring the maximum radial length of the brittle part on the fracture surface observed by SEM, or by

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measuring the maximum crack length on the mounted section. In those cases where both measurements were taken into consideration, the former observations were identied as SEM values, and the latter ones as MET values.

3. Experimental results 3.1. Polarization curves 3.1.1. AISI 304 in LiCl The polarization curve of AISI 304 in 11.8 M LiCl solution at 130 C shows a passive range was observed between the corrosion potential, Ecorr 0:5 VSHE , and )0.1 VSHE . The passive current density was of the order of 105 A/cm2 . At potentials above Ep 0:1 VSHE , pitting corrosion started, and the current density rose until ohmic drop limitations appeared. The results obtained were similar to those reported by Wilde [11], and by Du et al. [12]. o 3.1.2. AgPd in halides Fig. 1 shows the polarization curves for pure silver and for Ag15Pd in a 1 M KCl solution. The arrows indicate the potential values used in the present work for the stress corrosion tests. The curves found were similar to those reported by Du and o Galvele [13]. A detailed analysis of the polarization curves was reported by these authors. According to Du and Galvele, for Ag15Pd, in 1 M KCl solution, beo tween 0.2 and 0.4 VSHE selective dissolution of silver was taking place. No traces of Pd were detected by them in the solution after exposing the alloy for 22 h at 0.4 VSHE . On the other hand, above 0.45 VSHE the increase in the current density was
10 10 10
3

I (A/m )

10 10 10 10

-1

1M KCl
Ag 99.99% Ag - 15 Pd

-2

-3

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

E (V/SHE)
Fig. 1. Polarization curves of Ag15Pd and Ag 99.99% in 1 M KCl solution. The arrows show the potentials applied in stress corrosion tests.

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accompanied by simultaneous dissolution of Ag and Pd. At 0.6 VSHE the amount of Pd found by them in the solution indicated a quasi-stoichiometric dissolution of the alloy. 3.1.3. AgAu in HClO4 The polarization curves for pure silver and for AgxAu (x 2; 5; and 15 at.%) alloys in a 1 M HClO4 solution were similar to those reported by Maier et al. [14]. These authors measured the dissolution rate of the alloys in 1 M HClO4 solution, at constant potential, and calculated the rate of formation of dealloyed lms on the metal surface. 3.1.4. Brass in Mattsons solution No measurements were made for the polarization curve in this system. The SCC tests in this system were made at the equilibrium potential of pure copper in the corrosive solution. This choice was based on the observations published by Montoto et al. [15]. 3.1.5. Brass in NaNO2 For the SCC tests in this system the polarization curves published by Alvarez et al. [16] were used. 3.2. Stress corrosion tests 3.2.1. AISI 304 in LiCl Under the experimental conditions chosen, the fracture surface of AISI 304 was always transgranular (TG). The experimental conditions were selected to disfavour intergranular (IG) cracking. In this way the complications in the interpretation of the results due to mixed cracking morphology were avoided. As shown by Galvele et al. for hot MgCl2 [17] and LiCl [12] solutions, when increasing the potential the TG fraction in the cracks increased. The fracture surfaces of the samples strained in the present work showed typical features of TG cracking, such as river patterns and fanshaped marks starting from the initiation points. The longest cracks were usually observed to initiate at large pits. For the lowest SR (2.4 106 s1 ), usually there was only one, passing-through, crack. Sometimes, tiny cracks appeared in the region close to the main crack. When SR increased, up to about 5 103 s1 , a higher number of cracks, with a length similar to the longest one, was found. For higher SR the number of cracks decreased again, but this fact should be associated to a limitation in the detection of cracks rather than to their absence. For example, for the highest SR value in the ISRT (0.044 s1 ) pitting was still eective in inducing cracking, but no cracks were detectable in the UFSRT, at 18 s1 . Scanning electron microscopy (SEM) and metallographic mounting (MET) usually gave comparable values of CPR. Fig. 2 shows crack propagation rates versus strain rate. In the same gure the lower detection limit of the constant strain rate technique is shown. This limit is dened as the length of the smallest detectable crack Lfis;min (here taken conservatively as 4 lm) divided by the largest cracking time tr;max .

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597

10 10 10

-1 -2 -3 -4 -5 -6 -7 -8 -9

AISI 304 in 11.8M LiCl

SEM MET

CPR (m/s)

10 10 10 10 10 10

NF 2 tests

Lower Det. Lim.

-6

10

10

-5

10

-4

10 10 10 Strain Rate (s-1)

-3

-2

-1

10

10

Fig. 2. Eect of strain rate on crack propagation rates of AISI 304 strained in a 11.8 M LiCl solution at )0.1 VSHE and 130 C. The lower detection limit expected for the experimental technique used is shown. NF indicates that no cracks were detected at the end of the experiment.

As mentioned in a previous publication [3] and conrmed in the present work, there is a signicant dierence in the slope, a, of the loglog plot when intergranular SCC is compared with transgranular SCC. The slope a of the loglog plot is dened as a o log CPR ; o log SR 1

and in the case of AISI 304 in LiCl it was 0.31. An extrapolation of this linear relationship to a SR of 18 s1 showed that the expected crack propagation rate was below the detection limit, even when the expected CPR was as high as 2 105 m s1 . If cleavage cracks, longer than 4 lm were produced, they should have been detectable. Nevertheless, in the present work no such cracks were found for transgranular SCC of AISI 304 in LiCl solution. 3.2.2. AgPd in halides This system has been previously studied with SSRT [13]. It was found that the CPR generally increased with the potential, from the potential of formation of the silver halide up to an overpotential of %300 mV. For higher potentials the CPR reached a plateau [13]. As reported by Du and Galvele [13], fracture morphology was always IG in o both KI and KCl solutions, with no traces of TG cracking. The fracture surfaces were covered with AgI and AgCl, respectively, as identied by EDAX. For low potentials in KCl, the coverage was incipient, and only a small number of crystals were observed. On the other hand, for high potentials a dense coverage with many silver halide crystals was found. Similarly as in AISI 304, for low SR there was only one, passing-through, crack. Small number of cracks were also observed for high

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10 10 10

-1

1M KCl
-2 -3 -4 -5 -6 -7 -8 -9

1M KI

0.322VSHE 0.372VSHE 0.422VSHE 0.472VSHE -0.15VSHE

0.522VSHE 0.572VSHE 0.622VSHE

CPR (m/s)

10 10 10 10 10 10

Lower Det. Lim.

-6

Ag-15Pd
-2 -1

10

10

-5

10

-4

10 10 10 Strain Rate (s-1)

-3

10

10

Fig. 3. Eect of strain rate on crack propagation rates of Ag15Pd in 1 M KI and KCl solutions.

potentials. When SR increased, or the potential decreased, a larger number of cracks with similar length appeared. A characteristic feature, quite common in intergranular stress corrosion fracture surfaces, was the presence of shallow pits or vacancy clusters, as previously reported by Maier et al. [14]. Unlike to what was observed with AISI 304 in LiCl, AgPd alloy in halide solutions gave measurable cracks for UFSRT. The cracks in a sample strained in 1 M KI at 5 s1 were about 100 lm in size. The samples strained in KCl showed shorter cracks, but still above the detection limit of the experimental technique. The slopes a in the logarithmic plot of Fig. 3 were clearly steeper than those found for AISI 304 in LiCl solution. The values measured for a were between 0.5 and 0.65, and were listed in Table 3. One important observation was that, as shown in Fig. 4, in the UFSRT, the cracks measured at 5 s1 were always longer than those measured at 18 s1 . This observation was important because if the cracks produced at 5 s1 were due to a single pseudo-cleavage type event, the same crack length should have been expected for the experiments at 18 s1 . Fig. 5 shows the eect of electrode potential on the crack propagation rate at various strain rate values, for Ag15Pd in 1 M KCl solution. It was observed that an increase in the potential (E) produced an increase in CPR, up to an overpotential of about 300 mV, where a plateau was reached. The shape of the curves of CPR in function of E was similar for all strain rates tested, but the curves were shifted to higher CPR values as the SR increased. The present results could lead to introduce in Eq. (1) the eect of the potential: log CPRSR; E f E a log SR 2 suggesting that the eects of the electrochemical variable (E) and the mechanical variable (SR) could be independent. The slope a remained fairly independent of E. According to the measurements of Yu and Parkins, Eq. (2) is also valid for brass in nitrites [18]. The inverse slopes p of the ascending part of the CPRE curves were

S.A. Serebrinsky, J.R. Galvele / Corrosion Science 46 (2004) 591612 Table 3 Compilation of the slopes in log CPRlog SR plots from the present work Alloy AISI 304 Ag15Pd Ag15Pd Ag15Pd Ag15Pd Ag15Pd Ag15Pd Ag15Au Ag15Au Ag15Au Ag5Au Ag2Au a-brass a-brass Environment 11.8 M LiCl, 130 C 1 M KI 1 M KCl 1 M KCl 1 M KCl 1 M KCl 1 M KCl 1 M HClO4 1 M HClO4 1 M HClO4 1 M HClO4 1 M HClO4 Mattsons sol.a 1 M NaNO2 Potential (VSHE ) )0.10 0.15 0.32 0.37 0.42 0.47 0.52 0.90 1.00 1.15 0.90 0.90 (0.0 VCu0=Cu ) 0.20 Morph. TG IG IG IG IG IG IG IG IG IG IG IG IG TG a 0.31 0.65 0.63 0.53 0.55 0.59 0.57 0.62 0.54 0.19 a0 0.31 0.52 0.59 0.58 0.53 0.51 0.47 0.50 0.48 0.45 0.40 0.44 0.19

599

The a0 values were calculated excluding the measurements for SR higher than 1 s1 . a 0.05 M CuSO4 + 1 M (NH4 )2 SO4 + NH4 OH adjusted to pH 6.5.

60 50 40
0.372VSHE 0.472VSHE 0.522VSHE 0.572VSHE 0.622VSHE

Ag-15Pd in 1M KCl

L fis (m)

30 20 10
Lower Det. Lim.

0 0 10

10

Strain Rate (s-1)

Fig. 4. Crack lengths measured at 5 s1 and at 18 s1 for Ag15Pd in 1 M KCl solutions. By increasing the SR, in the UFSRT region, the crack lengths were found to decrease.

approximately 75 mV/decade, close to the value of 100 mV/decade reported by Galvele et al. for low-gold AgAu alloys in 1 M potassium halide solutions at SSRT [19]. 3.2.3. AgAu in HClO4 This system has been previously studied by Maier et al. [14] at SSRT, and by Du and Galvele [20] and by Kelly et al. [21] at UFSRT. The experimental results o from the present work are shown in Figs. 6 and 7.

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10 10 10
-1

-2

Ag-15Pd in 1M KCl

-3

CPR (m/s)

10 10 10 10 10

-4

Strain Rate:
2.3 E-6 1/s 8.8 E-6 1/s 7.3 E-5 1/s 1.8 E-3 1/s 4.4 E-2 1/s 5.0 1/s 18 1/s

-5

-6

-7

-8

10 300

-9

350

400

450

500

550

600

650

E (mV/SHE)
Fig. 5. Eect of potential on the crack propagation rate at various strain rate values, for Ag15Pd in 1 M KCl solution.

10 10 10

-1

-2

Ag-xAu in 1M HClO4, 0.9VSHE

Ag-2Au Ag-5Au Ag-15Au

-3

CPR (m /s)

10 10 10 10 10 10

-4

-5

-6

-7

-8

Lower Det. Lim.

-6 -5 -4 -3 -2 -1 0 1

-9

10

10

10

10

10

10
-1

10

10

Strain Rate (s )
Fig. 6. Eect of strain rate on crack propagation rates of AgAu alloys in 1 M HClO4 , at one potential 0.9 VSHE .

The fracture surfaces found were always intergranular, though small isolated transgranular patches were also detected. Vacancy clusters or shallow pits, as described by Maier et al. [14], were also present in this system. The eect of the potential and strain rate on the number and length of the cracks was the same as for Ag15Pd in KCl, i.e. few and long cracks, with one much longer than the others, was the situation favoured by high potentials and low SR. In this system a comparison was made on the eect of SR on CPR as a function of alloy composition, Fig. 6, and also for one alloy at dierent potentials,

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601

10 10 10

-1

-2

Ag-15Au in 1M HClO4
0.9VSHE 1VSHE 1.1VSHE 1.15VSHE

-3

CPR (m/s)

10 10 10 10 10 10

-4

-5

-6

-7

-8

Lower Det. Lim.

-9

10

-6

10

-5

10

-4

10

-3

10

-2

10

-1

10

10

Strain Rate (s-1)

Fig. 7. Eect of the electrode potential on the SR versus CPR for Ag15Au in 1 M HClO4 .

Fig. 7. The eect of SR was the same as found with AgPd alloy, the slopes a were higher than those found with AISI 304. The a values found were between 0.4 and 0.65. Fig. 7 shows the eect of the electrode potential on the SR versus CPR for Ag 15Au in 1 M HClO4 . When the potential was increased it was found that the CPR also increased. The inverse slopes p were about 230 mV/decade, for SSRT, ISRT and UFSRT. These results were very close to the value of ca. 200 mV/decade for Ag 2Au, Ag5Au, Ag10Au and Ag15Au at SSRT reported by Galvele et al. [19]. In the present system no plateau velocity was reached, possibly due to the very high dissolution rate at high potentials. The eect of increasing SR was again to shift the CPRE curves upwards, while keeping the shape of the curves. Here again Eq. (2) was applicable. 3.2.4. Brass in Mattsons solution This system showed intergranular stress corrosion cracks on the fracture surfaces, with occasional transgranular patches. The variation of the number and distribution of the length of cracks with strain rate was similar to that described in the previous systems, including the decrease in the number of cracks at UFSRT observed in AISI 304. Fig. 8 shows the logarithmic plot of CPRSR, where a slope a of 0.54 was found. 3.2.5. Brass in 1 M NaNO2 solution The fracture surfaces in this system were transgranular, as described by Alvarez et al. [16] and by Rebak et al. [22]. The results of the straining experiments are shown in Fig. 9, and the slope for a was 0.19 [3].

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10 10 10

-1 -2 -3 -4 -5 -6 -7 -8 -9

Brass in Mattson's solution

CPR (m/s)

10 10 10 10 10 10

Lower Det. Lim.

10

-6

10

-5

10

-4

10

-3

10

-2

10

-1

10

10

Strain Rate (s-1)

Fig. 8. Eect of strain rate on crack propagation rates of brass in Mattsons solution (0.05 M CuSO4 + 1 M (NH4 )2 SO4 + pH 6.5 adjusted with NH4 OH) at 0 VCu .

10 10 10

-1 -2 -3 -4 -5 -6 -7 -8

Brass in 1M NaNO2 solution

CPR - UTS CPR - 0.2

CPR (m/s)

10 10 10 10 10 10

Lower Det. Lim.

-9

10

-6

10

-5

10

-4

10 10 10 Strain Rate (s-1)

-3

-2

-1

10

10

Fig. 9. Eect of strain rate on crack propagation rates of brass in 1 M NaNO2 solution at 25 C and 0.2 VSHE . The meaning of the CPR lines will be considered in Section 4.

4. Discussion 4.1. Dierence between IG and TG cracking The analysis of the experimental results described above indicates that there is a clear and consistent dierence in the values of the logarithmic slope a, Eq. (1), when intergranular SCC systems are compared with transgranular SCC systems. It was

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603

always found that the slope for intergranular SCC was higher than that for transgranular SCC: aIG > aTG : 3 Table 3 shows the values for a found in the present work. Since the values of CPR could not be measured in some systems for UFSRT, Table 3 also includes the values for a0 , dened by the same Eq. (1) but taking into account the measurement for SR up to 1 s1 (i.e. neglecting UFSR tests). The data in Table 3 shows that Eq. (3), either for a or a0 , is satised in all the systems studied. One objection that could be raised is that dierent systems were compared. In support of the conclusion reached in Eq. (3) the following facts should be taken into account. (a) Only fcc alloys were considered. Thus systems with similar deformation mechanisms were compared. (b) One same alloy, from the same batch (brass), was subjected in the present work to IGSCC (Mattsons solution) and TGSCC (1 M NaNO2 solution) and the results were compared. The values found, for the same alloy in two dierent environments, were aIG 0:54 and aTG 0:19, which conrms Eq. (3). (c) Alvarez et al. [4] studied one single alloy system (AgAu alloy) in the same environment, and produced IGSCC and TGSCC. For this purpose these authors compared AgAu single crystals with AgAu poly-crystals. The studies were made in 1 M HClO4 solution and in 1 M KCl solution. As shown in Table 4, and discussed below, Alvarez et al. were able to conrm the validity of Eq. (3). To further conrm the validity of Eq. (3), values of a published in previous publications were collected in Table 4. As mentioned above, a major point in the analysis of the present results is provided by the work of Alvarez et al. [4]. These authors strained single crystals of Ag10Au in 1 M HClO4 and 1 M KCl solutions. As for the gold contents x, Maier et al. [14] showed that for x between 2.2 and 15 at.% Au there was no noticeable eect of the alloy composition on CPR, in experiments made at a slow strain rate. In the present work it was found that this observation is correct also when measurements are made with the ISRT. As a consequence, the measurements made by Alvarez et al. [4] can be compared with those reported in the present work. Alvarez et al. found for TGSCC aTG 0:22, while for IGSCC they found aIG 0:48. In the present work the lowest value for
Table 4 Compilation of the slopes a in log CPRlog SR plots from previous publications Alloy Ag20Au Ag20Au Ag15Au Ag15Au Ag10Au single crystal Ag10Au single crystal Environment 1 1 1 1 1 M M M M M HClO4 KCl KCl HClO4 KCl Reference [20] [20] [4] [4] [4] [4] Potential (VSHE ) 1.20 0.70 0.50 0.90 0.50 0.90 Morph. IG IG IG IG TG TG a 0.60 0.63 a0 0.69 0.68 0.48 0.30 0.22

1 M HClO4

IG: Intergranular SCC; TG: Transgranular SCC. The a0 values exclude measurements for SR higher than 1 s1 .

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IGSCC (a0 for Ag2Au) was aIG 0:4, all the other a values being higher. When the measurements were made in KCl solution, the dierence between IGSCC and TGSCC was maintained. Alvarez et al. measured for TGSCC aTG 0:30 and for IGSCC aIG 0:68. Du and Galvele [20] reported for IGSCC of Ag20Au in 1 M o KCl aIG 0:63 and in 1 M HClO4 aIG 0:60. Finally, it is important to point out that in the present work, in the case of TGSCC of stainless steels in hot concentrated chloride solutions, as well as brass in nitrite solutions, no cracks were detected after UFSRT. On the other hand, no reference was found in the literature of detection of any incipient transgranular cracks after an UFSRT. If there were any cracks, they were smaller than the detection limit of the technique used in the present work. 4.2. Mechanistic interpretation The above results will be analysed within the scope of the surface mobility SCC mechanism. When appropriate, references to the lm induced cleavage SCC mechanism [5], and the anodic dissolution SCC mechanism [5] will be made. Since the above analysis involves the use of the equations developed for the surface mobility SCC mechanism, a brief review of those equations will be made. The surface mobility mechanism [5,23,24] is based on the assumption that the environment acts by increasing the surface mobility of the alloy, and that the cracks propagate by capture of vacancies at the tip of the stressed crack. This mechanism was used to quantitatively explain numerous cases of SCC [5,6,10,24,25]. The following equation was developed for the crack propagation rate [23,24]:     DS r T a3 CPR exp 1 ; 4 L kT DS being the surface self-diusion coecient at the crack walls, L the diusion distance of the vacancies, rT the elastic stress at the tip of the crack, a the atomic size, k the Boltzmann constant, and T the temperature in K. Since measured DS values, for the conditions of interest for SCC, are very scarce two dierent approaches can be used to calculate the value of DS . When a solid lm, with a known melting point, contaminates the crack surface, an empirical equation, based on the work of Gjostein [26] and Rhead [27,28] can be used to calculate DS [23]: DS m2 s1 740 104 exp126Tm =RT 0:014 104 exp54Tm =RT ; 5 R being the molar gas constant (R 8:314 J mol1 K1 ), T the absolute temperature in K, and Tm the melting point of the surface lm in K. On the other hand, when no surface lms are formed, but the SCC process is specically aected by the concentration of cations of the noble metal of the alloy, as in the case of AgCd alloy in AgNO3 solution, Galvele and Du [29] developed an o

S.A. Serebrinsky, J.R. Galvele / Corrosion Science 46 (2004) 591612

605

equation for the calculation of DS , based on the alloy composition and the exchange current density of the noble metal. 4.3. Transgranular stress corrosion cracking 4.3.1. AISI 304 in LiCl The crack propagation rate values measured with SSRT for AISI 304 in LiCl solution at 130 C, Fig. 2, are very close to those found by Speidel [30] using fracture mechanics techniques. This coincidence in the measured CPR values proved that the SSRT is a valid technique for measuring crack propagation rates in the present system. As mentioned by Du et al. [12] for this SCC system, assuming that the surface o mobility SCC mechanism was operative, the analysis of the temperature dependence of CPR showed that DS at 130 C was approximately 3 1015 m2 s1 . For SSRT the predicted CPR values, with the stress rT equal to r0:2 (206 MPa, Table 2), agreed very well with the present experimental results. When increasing the strain rate, the samples fractured with noticeable plastic deformation. Then it is reasonable to assume that the value of rT will increase, eventually reaching the UTS value (885 MPa, Table 2). As shown in Fig. 10, using these two rT values (Table 2) the extreme CPR values predicted by the surface mobility mechanism contain the experimentally measured values. There is no information about the exact values rT will have at dierent strain rates. Nevertheless, in SSRT the samples fracture with very small plastic deformation; consequently it is reasonable to assume that the stress at the tip of the crack will be close to r0:2 . On the other hand, under high strain rates, where cracks propagate while the samples are undergoing strong plastic deformation, the rst assumption would be that the maximum value reached by the stress at the tip of the crack would be that given by the UTS. The results in Fig. 10 suggest that the surface mobility SCC mechanism could give a good account for the correlation found between CPR and SR for transgranular SCC. No equations were found in the literature for a similar analysis from the point of view of the lm induced cleavage SCC mechanism, or the anodic dissolution SCC mechanism. Consequently, from Fig. 10 no conclusions can be drawn either supporting or disqualifying these two mechanisms. 4.3.2. Brass in NaNO2 The reactions taking place at the tip of the crack, during SCC of brass in NaNO2 solutions are only ambiguously known. Newman and Burstein [31] suggested that decomposition of nitrite ions could lead to the formation of ammonia, with subsequent stability of copper ions by complex formation. On the other hand Rebak et al. [22] concluded that passivity breakdown was the step previous to SCC of brass in NaNO2 solution. For any of these alternatives, the environment at the crack tip would be a solution with a high concentration of copper ions, providing a high exchange current density i0 of Cu $ Cu . In this case, surface diusion would be associated with the exchange current density, as in the model of Galvele and Du o

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10 10 10

-1

-2

AISI 304 in 11.8M LiCl

SEM MET CPR - 0.2 CPR - UTS
NF 2 tests

-3

CPR (m/s)

10 10 10 10 10 10

-4

-5

-6

-7

-8

Lower Det. Lim.

-6

-9

10

10

-5

10

-4

10

-3

10

-2

10

-1

10

10

Strain Rate

(s-1)

Fig. 10. Crack propagation rates of AISI 304 in 11.8 M LiCl at 130 C. Comparison of measured values with the predicted range of the surface mobility SCC mechanism.

[29]. Giordano et al. [32] and Montoto et al. [15] conrmed the validity of this hypothesis. When the value of DS is not known, but experimental CPR values are available for a given experimental condition, Eqs. (4) and (5) can be used to predict the CPR value at a dierent condition. This was done, for example, to predict CPR values for alloy 600 at dierent temperatures [25]. In the present case it will be assumed that in a SSRT the value of rT is equal to r0:2 and with the CPR value measured at SSRT, plus Eqs. (4) and (5), a DS value tting these results can be calculated. Assuming that this value does not change with the SR, and also assuming, as done above, that the maximum stress value at the tip of the crack will be the UTS, the maximum CPR expected can be calculated. Fig. 9 shows that, as it was the case with AISI 304 in LiCl solution, the CPR values measured at dierent SR for SCC of brass in NaNO2 solutions fall between the extreme values predicted by the surface mobility SCC mechanism. 4.4. Intergranular stress corrosion cracking 4.4.1. Brass in Mattsons solution Speidel [33], using fracture mechanics techniques, for brass, of a composition equal to that used in the present work and exposed to a NH4 OH solution, reported CPR values very close to those found in the present work, with SSRT (Fig. 8). As mentioned above for AISI 304, this observation gives support to the validity of the CPR values measured with SSRT. The same procedure used for brass in NaNO2 solutions, was applied to the CPR results measured for brass in Mattsons solution. As before, the value of DS tting the SSRT results was calculated. Then with the DS value found, the CPR for rT equal

S.A. Serebrinsky, J.R. Galvele / Corrosion Science 46 (2004) 591612

607

10 10 10

-1 -2 -3 -4 -5 -6 -7 -8 -9

Brass in Mattsons solution

CPR - UTS CPR - 0.2

CPR (m/s)

10 10 10 10 10 10

10

-6

10

-5

10

-4

10

-3

10

-2

10

-1

10

10

Strain Rate (s-1)

Fig. 11. Comparison of crack propagation rates of brass in Mattsons solution (0.05 M CuSO4 + 1 M (NH4 )2 SO4 + pH 6.5 adjusted with NH4 OH) at 0 VCu , measured and predicted by surface mobility.

to the UTS was calculated. As shown in Fig. 11, contrary to what was found for transgranular SCC, Figs. 9 and 10, the extreme values of CPR predicted by the surface mobility SCC mechanism were not the limits for the experimentally found CPR for intergranular SCC. As shown in Fig. 11, when the strain rate increased, the measured crack propagation rates exceeded the values predicted by surface mobility, if as done before, the maximum stress rT acting at the tip of the crack was considered to be the UTS. A calculation of the maximum stress rT required by Eq. (4) to t the CPR measured in UFSRT gave a value of 2.7 GPa, which was about ve times larger than the UTS. The stress values required by Eq. (4) to t the experimental CPR values are shown in Fig. 12. One possible reason for the dierent eect on SR, between intergranular and transgranular SCC, could be the fact that grain boundaries act as barriers for the free movement of dislocations, leading to dislocation pileups [34]. At an atomic level, at the tip of the crack, this process will lead to an increase in the value of rT well above the externally applied stress. As discussed below, the dislocation pileups could account for the required stress values mentioned in Fig. 12. A very crude calculation of the formation rate of dislocations, at dierent strain rates, can be attempted by using the equations developed by Van Bueren [35]. Fig. 13 shows the results of such calculations for copper. It is interesting to point out the similarity between Fig. 13 and Figs. 7 and 8. If the role of dislocations was to produce a surface slip step, where corrosion would be localised, as it is assumed in the slip-step anodic dissolution SCC mechanism [5], an increase in the strain rate should produce an increase in the crack propagation rate, as found in the present work. Nevertheless, the anodic dissolution SCC mechanism does not predict a dierence in behaviour between IGSCC and TGSCC. On the other hand, any mechanism based on the elastic stresses at the tip of the crack will be able to explain the dierence between IGSCC and TGSCC, because of the higher stress values induced by the dislocation pileups at the grain boundaries.

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3000 Brass in Mattson's solution 2500

0.2
Stress (MPa)

2000 1500 1000 500 0 -6 10

UTS required

10

-5

10

-4

10 10 10 Strain Rate (s-1)

-3

-2

-1

10

10

Fig. 12. Stresses rT of Eq. (4) required to t the measured crack propagation rates of brass in Mattsons solution (0.05 M CuSO4 + 1 M (NH4 )2 SO4 + pH 6.5 adjusted with NH4 OH) at 0 VCu .

10

12 11 10 9 8 7 6 5 4

Disloc. Density (cm -2 s -1)

10 10 10 10 10 10 10 10

10

-6

10

-5

10

-4

10

-3

10

-2

10 (s-1)

-1

10

10

Strain Rate

Fig. 13. Rough estimate of the rate of production of dislocations, in copper, at various strain rates, based on Van Buerens equations [35].

4.4.2. AgPd in halides The same procedure used above was applied to the CPR results measured for Ag Pd in halide solutions. As before, the values of DS tting the SSRT were calculated. Then, with the DS values found, the CPR for values rT equal to the UTS were calculated. For potassium iodide environment, with the calculated value of DS , results similar to those in Fig. 11 were found. The relation of rT =UTS required to t the measured CPR had a maximum value of 4.5, very close to the value %5 indicated in Fig. 12. This observation supports the same assumptions made above for IGSCC.

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For potassium chloride environment a range of potentials was applied, and more data is available. The polarization curve, Fig. 1, shows a noticeable discontinuity at about 0.45 VSHE , related to the change in the mode of dissolution of the alloy. Nevertheless, as reported by Du and Galvele for SSRT [13], and conrmed in the o present work with dierent SR values, no discontinuities were observed in CPR at any SR, Figs. 3 and 5. These observations suggest that, at least for IGSCC of Ag 15Pd in 1 M KCl solution, the dissolution mode of the alloy had no eect on the SCC process. As regards Eq. (2), and following the predictions of the surface mobility SCC mechanism, the present results suggest the following: apparently, if Eq. (4) is taken into account, the eect of SR is concentrated mainly on the mechanical variable rT , while the potential E acts mainly by changing the value of DS (and possibly to some extent L). 4.4.3. AgAu in HClO4 Due to the high solubility of AgClO4 in water, 26.9 moles per litre of water [36], it is probable that during dissolution, an acid concentrated AgClO4 solution will be present next to the alloy interface, but no surface compounds will be expected. No measurements are available at present of the DS value expected in this system. Vela et al. [37] reported that the rate of step movement on pure Ag surfaces, in 1 M HClO4 solution, was an order of magnitude higher than in vacuum. On the other hand, Du and Galvele [20] reported that SCC of Ag20Au alloy was faster in 1 M o AgClO4 solution than in 1 M HClO4 solution. While the operating mechanism is still not clear, it is safe to assume that the DS value in this system is high. Using the same approach applied in the above discussed SCC systems, it was found again that with the calculated value of DS , results similar to those in Fig. 11 were found. The relation rT =UTS required to t the measured CPR was very close to that shown in Fig. 12. These are two facts that should be pointed out. The rst one is that the eect of potential and SR on the CPR can be described by Eq. (2), as it was the case with Ag Pd in halides. The second one is that Alvarez et al. [4] found that the inverse slope p from a log CPRE plot is the same for both IGSCC and TGSCC. These observations indicate that there is an association between SR and rT , as well as for a with the SCC morphology and also an association between E and DS , if the surface mobility mechanism is considered, Eq. (4). As a further contribution to this point, Alvarez et al. [38] have recently found that the activation energy for IGSCC of AgAu alloy was equal to that for TGSCC for the same alloy, and that there was a coincidence between the activation energy predicted by the surface mobility SCC mechanism and the experimental results. As for the lm induced cleavage (FIC) mechanism, Maier et al. [14] showed that there was no relation between the rate of dealloyed lm formation and the CPR, as should be expected if the FIC mechanism was operative. The supporters of the FIC [39] attributed particular importance to the critical potential for selective dissolution (Ec ) in alloys like AgAu. Maier et al. [14] found that changes in the nature of the selective dissolution process had no eect on the CPR. This observation was

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particularly evident for Ag15Au, Ag25Au and Ag40Au alloys 1 M HClO4 solution [14]. No breaks were found in the CPR vs. E curve when the potential crossed the critical potential value. These results showed that SCC of AgAu alloys in HClO4 solution was independent of the Ec value, and that there was no experimental evidence correlating the SCC with that critical potential value. A similar observation regarding Ec was reported by Lichter et al. [40] for CuAu alloys. 4.5. Mechanistic considerations The above observations indicate that the slope in Eq. (1) is higher for IGSCC than for TGSCC, Eq. (3). Besides the numerous considerations made above, the involvement of SCC mechanisms, other than the surface mobility mechanism, will be further considered. In the case of the lm rupture, or slip step anodic dissolution mechanism, it should be expected that, as found in the present work, an increase in the strain rate will lead to an increase in the SCC rate. Nevertheless, as mentioned above, the eect should be the same for IGSCC and for TGSCC. In the literature of slip step anodic dissolution mechanism no explanation was found for the observation indicated by Eq. (3). As for the FIC SCC mechanism, as mentioned above, numerous contradictions were found by various authors between the predictions of this mechanism and the experimental results. On the other hand, the literature published on this mechanism does not give, so far, any clue for the observation indicated by Eq. (3). Besides, in the present work, Fig. 4, longer cracks were found for 5 s1 than for 18 s1 . From the descriptions given for the FIC mechanism, a single event of crack propagation should be expected at both strain rates, and no dierence in the crack length should be observed. Unfortunately no further quantitative comparisons can be made for this mechanism at the present state of development of the FIC model.

5. Conclusions The following conclusions can be drawn from the present work: An increase of the strain rate generally accelerates the crack propagation process according to the relation (1), or equivalently log CPR / alog SR: 6

The slope a is dierent for transgranular and intergranular cracking. The values are aTG 0:20.3 and aIG 0:40.7. The eect of potential can be incorporated as an additional term f E in Eq. (6), not having a noticeable eect on the SR-dependent term. No information was found in the anodic slip step dissolution mechanism, that could explain the present experimental results. The FIC mechanism requires further development to account for the dierences found between IGSCC and TGSCC.

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The surface mobility SCC mechanism can account for the dependence of crack propagation rate on strain rate. With an increasing strain rate, the stress at the crack tip zone will increase due to the formation of dislocation pileups, which is equivalent to say that the driving force for the movement of surface vacancies increases. The surface mobility SCC mechanism can account for the separate eect of strain rate and potential on crack propagation rates, according to Eq. (2). The strain rate aects the stress at the tip of the crack, as indicated above, and the potential aects the surface diusion coecient. The absence of transgranular cracks, when very high strain rates are used, favours a continuous crack propagation model and sheds doubts on any mechanism based on very fast and discontinuous crack propagation events.

Acknowledgements The present research has been supported by the Consejo Nacional de Investigaciones Cientcas y Tcnicas, Argentina, and by the FONCYT, Secretara de e Ciencia y Tecnologa, Argentina.

References
[1] J.C. Scully, D.T. Powell, Corros. Sci. 10 (1970) 719. [2] R.H. Jones, R.E. Eicker, in: R.H Jones (Ed.), Stress Corrosion Cracking, ASM International, Ohio, 1992, p. 4. [3] S.A. Serebrinsky, G.S. Du, J.R. Galvele, Corros. Sci. 41 (1999) 191. o [4] M.G. Alvarez, S.A. Fernndez, J.R. Galvele, Corros. Sci. 42 (2000) 739. a [5] J.R. Galvele, in: R.E. White, J.OM. Bockris, B.E. Conway (Eds.), Modern Aspects of Electrochemistry, vol. 27, Plenum Press, New York, 1995, p. 233. [6] J.R. Galvele, in: R.H. Jones (Ed.), Chemistry and Electrochemistry of Stress Corrosion Cracking, TMS, Warrendale, PA, 2001, p. 27. [7] D. Gilroy, J.E.O. Mayne, J. Appl. Chem. 12 (1962) 382. [8] G.J. Janz, in: D.J.G. Ives, G.J. Janz (Eds.), Reference electrodesTheory and practice, Academic Press, New York, NY, 1961, p. 179. [9] J.R. Galvele, S.M. de De Micheli, I.L. Muller, S.B. de Wexler, I.L. Alanis, in: R.W. Staehle, B.F. Brown, J. Kruger, A. Agrawal (Eds.), Localized Corrosion, NACE, Houston, 1974, p. 580. [10] J.R. Galvele, in: S.M. Bruemmer, E.I. Meletis, R.H. Jones, W.W. Gerberich, F.P. Ford, R.W. Staehle (Eds.), Parkins Symposium on Fundamental Aspects of Stress Corrosion Cracking, The Minerals, Metals & Materials Society, Warrendale, PA, 1992, p. 85. [11] B.E. Wilde, J. Electrochem. Soc. 118 (1971) 1717. [12] G.S. Du , I.A. Maier, J.R. Galvele, Corros. Sci. 28 (1988) 1003. o [13] G.S. Du , J.R. Galvele, Corros. Sci. 30 (1990) 249. o [14] I.A. Maier, S.A. Fernndez, J.R. Galvele, Corros. Sci. 37 (1995) 1. a [15] M.L. Montoto, G.S. Du, J.R. Galvele, Corros. Sci. 43 (2001) 755. o [16] M.G. Alvarez, C. Manfredi, M. Giordano, J.R. Galvele, Corros. Sci. 24 (1984) 769. [17] C. Manfredi, I.A. Maier, J.R. Galvele, Corros. Sci. 27 (1987) 887. [18] J. Yu, R.N. Parkins, Corros. Sci. 27 (1987) 159. [19] J.R. Galvele, I.A. Maier, S.A. Fernndez, Corrosion 52 (1996) 326. a [20] G.S. Du , J.R. Galvele, Metall. Trans. A 24 (1993) 425. o

612 [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] [37] [38] [39] [40]

S.A. Serebrinsky, J.R. Galvele / Corrosion Science 46 (2004) 591612 R.G. Kelly, A.J. Frost, T. Shahrabi, R.C. Newman, Metall. Trans. A 22 (1991) 531. R.B. Rebak, R.M. Carranza, J.R. Galvele, Corros. Sci. 28 (1988) 1089. J.R. Galvele, Corros. Sci. 27 (1987) 1. J.R. Galvele, Corros. Sci. 35 (1993) 419. J.R. Galvele, J. Nucl. Mat. 229 (1996) 139. N.A. Gjostein, in: J.J. Burke, N.L. Reed, V. Weis (Eds.), Surfaces and Interfaces-I, Syracuse University Press, 1967, p. 271. G.E. Rhead, Surf. Sci. 15 (1969) 353. G.E. Rhead, Surf. Sci. 22 (1970) 223. J.R. Galvele, G.S. Du, Corros. Sci. 39 (1997) 605. o M.O. Speidel, Metall. Trans. A 12 (1981) 779. R.C. Newman, G.T. Burstein, J. Electrochem. Soc. 127 (1980) 2527. C.M. Giordano, G.S. Du, J.R. Galvele, Corros. Sci. 39 (1997) 1915. o M.O. Speidel, in: M.O. Speidel, A. Atrens (Eds.), Corrosion in Power Generating Equipment, Plenum Press, New York, 1984, p. 85. J.P. Hirth, J. Lothe, in: Theory of Dislocations, Krieger Publishing Co., Malabar, FL, 1992, p. 764. H.G. Van Bueren, in: Imperfections in Crystals, North-Holland Publishing Co, Amsterdam, 1960, p. 156. R.C. Weast (Ed.), CRC Handbook on Chemistry and Physics, 54th ed., CRC Press, Cleveland, 1973, p. B-134. M.E. Vela, G. Andreasen, R.C. Salvarezza, A. Hernndez-Creus, A.J. Arvia, Phys. Rev. B 53 (1996) a 10217. M.G. Alvarez, S.A. Fernndez, J.R. Galvele, Corros. Sci. 44 (2002) 2831. a F. Friedersdorf, K. Sieradzki, Corrosion 52 (1996) 331. B.D. Lichter, W.F. Flanagan, J.B. Lee, M. Zhu, in: R.P. Ganglo, M.B. Ives (Eds.), EnvironmentInduced Cracking of Metals (NACE-10), NACE, Houston, TX, 1990, p. 251.