CORROSION SCIENCE SECTION

Application of Electrochemical Impedance Spectroscopy for Monitoring Stress Corrosion Cracking

R.W. Bosch, F. Moons,* J.H. Zheng, and W.F. Bogaerts**

ABSTRACT
The present study investigated whether electrochemical impedance spectroscopy (EIS) could be used to monitor stress corrosion cracking (SCC). First, a model was developed that interpreted the impedance response of a cracked surface (i.e., the model could distinguish between a flat electrode surface and a surface with cracks). Experiments on stainless steel (SS) electrodes with artificial cracks (electrically drilled small holes) in 0.1 M sodium sulfate (Na2SO4) showed that the influence of the artificial cracks on the impedance response was reflected mainly in the phase shift at frequencies between 100 Hz and 1 Hz. To generate real stress corrosion cracks, slow strain rate tests (SSRT) were performed with a sensitized Type 304 SS (UNS S30400) specimen in a 5-N sulfuric acid (H2SO4) + 0.1-M sodium chloride (NaCl) solution at room temperature. Analysis of the fracture surface clearly showed intergranular attack, suggesting that stress corrosion cracks were formed. Impedance measurements were performed twice an hour during experiments with stress (SSRT) and without stress. Phase shifts at frequencies 100 Hz and 10 Hz showed a clear difference between the results with stress and without stress, suggesting that stress corrosion cracks were detected by the impedance measurements. KEY WORDS: electrochemical impedance spectroscopy, slow strain rate test, stainless steel, stress corrosion cracking

INTRODUCTION
With electrochemical impedance spectroscopy (EIS), a small sinusoidal (potential) perturbation of a certain frequency is used to distort an electrochemical system. The (current) response is measured, and the modulus (|E|/|i|, where |E| is the absolute value of the potential and |i| is the absolute value of the current) and phase shift of the impedance are determined.1-3 Proper experimental data can be obtained from a corrosion system when three requirements are fulfilled: linearity, causality, and stability.3 The first requirement is obtained using a small potential perturbation so that the system stays in the linear region. The second requirement is generally not problematic as long as the background noise is small. The third requirement is more difficult since a corrosion system is always changing with time. If these changes are small, the system is assumed to be quasi-stable and good experimental data can be obtained. A stress corrosion process is, however, always evolving with time and therefore not really stable. This is probably why EIS rarely has been used to investigate corroding systems subjected to stress corrosion cracking (SCC). A particular characteristic of EIS is that a reference electrode is not needed to perform the measurements. This makes possible application under severe conditions (aqueous solutions at high temperatures and pressure, as in nuclear power plants), where a reference electrode is difficult to use. Also, few techniques suited for stress corrosion detection are available. Therefore, it seems worthwhile to investigate

Submitted for publication July 1999; in revised form, December 2000. Presented as paper no. 151 at CORROSION/99, April 1999, San Antonio, TX. * SCKCEN, Nuclear Research Centre Belgium, Boeretang 200, B-2400 Mol, Belgium. ** KU Leuven, Department of Metallurgy and Materials Engineering, De Croylaan 2, B-3001 Heverlee (Leuven), Belgium.

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whether EIS can be used for SCC monitoring. To avoid problems caused by an unstable corrosion system, measurement time should be as small as possible. EIS has been used only occasionally to investigate SCC phenomena. Armstrong, et al., used EIS on nonstressed samples to investigate SCC.4-5 They measured relaxation times for passivation and tried to correlate this with the susceptibility to SCC of lowcarbon steel in carbonate/bicarbonate solutions at 70C. Oltra and Keddam used a transmission line,6 similar to the cylindrical pore model developed for the potential distribution in porous electrodes of de Levie,7 to model stress corrosion crack impedance. Petit, et al., used EIS during slow strain rate tests (SSRT) of Type 304 stainless steel (SS) (UNS S30400)(1) in boiling 44% magnesium chloride (MgCl2) solution.8 They measured the phase shift at a particular frequency during tests and tried to correlate crack initiation with changes in this phase shift. The present study attempted to combine the ideas of Oltra and Keddam6 and Petit, et al.8 First, the transmission line model was used and extended to model the crack impedance. This resulted in a crack model that incorporated the geometry of the crack, an active or passive crack tip, and the influence of the ratio between the electrode surface area and the crack surface area. The latter aspect is important for the sensitivity of the impedance technique for detecting stress corrosion cracks. Experimental results with SS electrodes with artificial cracks (electrically drilled small holes) were compared to simulations from the crack model, showing good agreement with each other. SSRT were performed with a sensitized Type 304 SS specimen in a 5-N sulfuric acid (H2SO4) + 0.1-M sodium chloride (NaCl) solution at room temperature. This material/solution combination resulted in intergranular SCC at room temperature.9 This system was chosen because, for the first experiments, it was desirable to avoid the possible influence of an electric heater (electric noise) on impedance measurements. In a later phase, other systems at elevated temperatures will be investigated. EIS measurements were performed continuously during the SSRT tests. Phase shifts at particular frequencies showed a clear difference between the stressed and nonstressed specimens. This suggests the possibility of using EIS to monitor stress corrosion cracks.

1) of de Levie,7 used for the cylindrical pore model to describe the impedance of porous electrodes.10-11 This transmission line model represents a single crack. From the transmission line model, the following principal equations are derived:

de = iR sol dz i =

1 de R sol dz

(1)

di =

e dz Z wall

(2)

where e is the potential, i the current, Rsol the solution resistance in the crack, Zwall the crack wall impedance, and z the distance along the crack. Notice that Rsol and Zwall depend on the crack length (i.e., Rsol and Zwall have units of -mm). Combining both equations results in the following differential equation:

d 2e R e sol = 0 Z wall dz 2

(3)

This differential equation is solved with the following boundary conditions: At the crack opening (z = 0), the potential e is equal to the potential at the electrode surface Eo: z = 0, e = Eo (4)

At the crack tip, the potential is equal to EL, which is dependent on the impedance on the crack tip (Zcracktip):

E L = i.Z cracktip , with Equation (1): E L =

Z cracktip de (5) R sol dz

The differential Equation (3) is solved with these boundary conditions:

R sol Z wall R sol + coth L Z cracktip Z wall (6) R sol Z wall R sol coth L + R sol Z cracktip Z wall

Z crack = R sol Z wall

IMPEDANCE MODELING OF A STRESS CORROSION CRACK

The mathematical modeling of a stress corrosion crack starts with the transmission line model (Figure
(1)

This equation still includes the impedance of a porous electrode. When the crack impedance Zcracktip , Equation (6) changes to: R sol Z crack = R sol Z wall coth L Z wall which is the equation for a pore impedance.7-8,11

(7)

UNS numbers are listed in Metals and Alloys in the Unified Numbering System, published by the Society of Automotive Engineers (SAE) and cosponsored by ASTM.

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FIGURE 1. Transmission line model describing the impedance of a cylindrical pore or crack.

crack wall. Using the above-described impedances, an equivalent circuit of the crack model can be constructed, as shown in Figure 3. In this equivalent circuit, Rsurface is the polarization resistance of the outer surface of the working electrode, Csurface the capacity of the electrochemical double layer of the outer surface of the working electrode, and Rohm the ohmic resistance between the reference electrode and the outer surface of the working electrode. Zcrack is given by Equation (6). Assuming that the polarization resistance of a passive SS surface is Rpassive in -mm2 and the electrochemical double layer is Cdl in F/mm2, R R passive then R crack = passive in , Ccrack = Cdlr2 in F, R wall = 2 in r r 2 -mm, and Cwall = Cdl2r in F/mm. In case the crack tip is in the active state, the polarization resistance of an active surface can be used instead of Rpassive.

SIMULATIONS WITH THE CRACK MODEL

The just-developed crack model was used to investigate two phenomena important to the application of EIS during a SCC process. First, the influence of the corrosion rate at the crack tip on the impedance response was investigated. Second, the influence of the total surface area of an electrode on the impedance response for a fixed crack surface area was investigated. Depending on the SCC mechanism, the crack tip can be passive or active. When the crack tip is passive, the corrosion rate at the crack tip is very small and the value of Rcrack is large. When the crack tip is active, the corrosion rate at the crack tip is larger and the value of Rcrack is small. For various values of Rcrack, the impedance is calculated with Equation (6) and shown in Figure 4. The Nyquist diagram shows clearly that, with decreasing Rcrack, the vertical line is turned off to the real axis. The lines with slopes of 45 to the real axis are typical for a transmission line impedance and are found with porous electrodes.4-5 In such cases, the transmission line impedance represents the Zcrack described by Equation (7). When the SCC mechanism cycles between the passive and active status of the crack tip, the stability requirement for the impedance measurements is not fulfilled. Therefore, impedance data should be treated carefully when used for mechanistic modeling. Verification of the experimental data with a Kramers-Kronig transform is then recommended.10-11 The influence of the Zcrack on the whole impedance of an electrode can be so small that the crack is not noticed. Especially for small stress corrosion cracks on a large electrode surface area, this might be a problem. Therefore, some simulations were performed with the crack model shown in Figure 3. For a small crack of fixed dimensions on an electrode surface with varying diameter, the impedance was calculated. The phase shift of the impedance vs the frequency for various electrode diameters is shown in

FIGURE 2. Cylindrical crack filled with electrolyte solution: r is radius, L is crack length, and z is the coordinate along the crack.

In this study, the cracks were represented by cylindrical holes, as shown in Figure 2. Rsol of this cylinder is then as follows:

R sol =

1 r 2

(8)

where r is the crack radius and the conductivity of the electrolyte solution. The Zcracktip consists of a charge-transfer resistance at the crack tip (Rcrack) and the crack tip capacity (Ccrack), as a result of the electrochemical double layer. The crack tip impedance is then as follows:

Z cracktip =

R crack 1 + jCcrack R crack

(9)

Zwall follows from an analogue treatment:

Z wall =

R wall 1 + jC wall R wall

(10)

where Cwall is the double-layer capacity of the crack wall and Rwall is the polarization resistance of the

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FIGURE 3. Equivalent circuit of a crack with a transmission line and the surface impedance.

Figure 5. Figure 5 shows that the influence of the Zcrack on the phase shift decreased with increasing surface area (or sample diameter D) of the electrode. However, the influence of a small crack on the phase shift was still noticeable even when the surface area of the electrode was 100 times larger than the surface area of the cross section of the crack (i.e., 22 4 = 100 ). This can be explained by the much 2 = 0.04 0.2 smaller ratio between the surface area of the electrode and the surface area of the crack wall, which is D2 = 5 . In the previous calculations, only a factor 5 2 rL the cracks were cylindrical, as shown in Figure 2.

EXPERIMENTAL PROCEDURES

Experiments with Artificial Cracks

The working electrodes for the experiments with artificial cracks were made from commercial Type 316 SS (UNS S31600). A cylindrical electrode with a diameter of 8 mm was embedded in epoxy. A small hole (d = 2 mm) was drilled in the center of the electrode. Figure 6 is a picture of the electrode and the working electrode holder. Experiments were performed in a glass corrosion cell with a three-electrode configuration. The counter electrode was made of the same material as the working electrode and was the same size. The working electrode and counter electrode were placed parallel to each other (facing each other). To fill the holes with electrolyte solution, a small plastic tube was used to inject the solution. Experiments were performed in a 0.1-M sodium sulfate (Na2SO4) solution open to the air. EIS experiments were performed with an amplitude of 10 mV root mean square (rms) over a frequency range of 10 kHz to 0.1 Hz.
FIGURE 4. Nyquist diagram for different values of Rcrack (), with Ccrack = 4.7 108 F, Rsol = 3.5 104 -mm, Cwall = 9.4 107 F/mm, Rwall = , L = 1 mm, and r = 0.1 mm. ReZ is the real part of the impedance and lmZ is the imaginary part of the impedance.

Slow Strain Rate Tests

Commercial Type 304 SS was used in the experiments. The material was first solution-annealed at 1,050C in a protective argon atmosphere for 15 min

and water-quenched, and then it was sensitized at 650C. The exposure surface of the specimens was mechanically polished with 600-grit silicon carbide (SiC) paper before testing. The gauge length of the specimen was 10 mm and the diameter was 3 mm. Polytetrafluoroethylene (PTFE) tape was used to seal the specimen, resulting in an exposed surface area of 0.94 cm2. SSRT were conducted using a tensile test machine operated at a crosshead speed of 0.001 mm/min, which corresponds to an initial strain rate of 1.5 106/s of the tested samples. Details about the experimental installation are described elsewhere.12 All tests continued until the specimen was pulled completely apart, and the elongation of the tested sample was recorded. After each test, the fracture surfaces of the tensile sample were examined using scanning electron microscopy (SEM).

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FIGURE 5. Phase shift vs frequency for various sample diameters: L = 1 mm, r = 0.1 mm, Rwall = , Cdl = 30 108 F/mm2, Rpassive = 108 -mm2, Rohm = 3,000 , and = 0.1799 103 s/mm.

FIGURE 6. Drawing of SS samples with a small hole in the surface.

tion at room temperature. The solution was prepared with reagent-grade chemical and double-distilled water. All experiments were duplicated to check their reproducibility. During the tests, EIS measurements were performed as described previously. Three different tests were performed to distinguish between the influences of stress, corrosion, and the synergetic effect of stress and corrosion: (1) an experiment without stress and with a corrosive environment (corrosion test), (2) an experiment with stress and without a corrosive environment (tensile test), and (3) an experiment with stress and a corrosive environment (SSRT). When the results of Tests 1 and 3 are compared, the influence of the corrosion can be separated by analyzing the microstructure. When the results of Tests 2 and 3 are compared, the influence of the stress can be separated by analyzing the stressstrain curves. With the results of these three tests, it is possible to prove the presence or absence of SCC.

RESULTS AND DISCUSSION

SS Electrodes with Artificial Cracks

Experiments on SS electrodes with different crack length were performed in 0.1 M Na2SO4 open to the air. Notice that these artificial cracks did not have a bare surface at the bottom, which is one major difference from an actively cracking specimen. After stabilization of the corrosion potential, impedance measurements were performed. The phase shift and modulus were plotted against the frequency. The results with crack length of 0, 5, and 10 mm were plotted in the same graph. Figure 8 shows the simulated and experimental results. The simulated and experimental curves have the same characteristics, indicating that the crack model is capable of reproducing impedance responses dependent on the geometry of the crack that are close to the experimental results. The influence of the crack length on the phase shift was more pronounced than on the modulus of the impedance. The effect of the increasing crack length is also noticeable at higher frequencies.

FIGURE 7. Experimental setup of SSRT. F is force.

A conventional electrochemical cell was used with three electrodes (i.e., a silver-silver chloride [Ag-AgCl] reference electrode, a platinum auxiliary electrode, and the tested specimen). Figure 7 shows a schematic of the electrochemical cell with the test sample and electrodes. All the potentials mentioned in the following text are vs the Ag-AgCl scale (207 mV vs standard hydrogen electrode [SHE]). Experiments were carried out in a 5-N H2SO4 + 0.1-M NaCl solu-

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(a)

(b)

(c)

(d)

FIGURE 8. Simulated and experimental Bode diagrams for SS samples in 0.1 M Na2SO4 with various crack lengths: r = 1 mm, D = 8 mm (diameter of the specimen), CdI = 30 108 F/mm2, Rpassive = 108 -mm2, Rohm = 3,000 , and = 0.1799 103 s/mm.

Although the artificial cracks have dimensions much larger than real cracks, clearly the phase shift at a particular frequency can be used to distinguish between a flat and a cracked surface.

SSRT with Type 304 SS

During SSRT, impedance and corrosion potential were measured every 30 min. Figure 9 shows the corrosion potentials during a SSRT experiment (with stress) and a corrosion experiment (without stress). A clear difference can be noticed between the results with and without stress. The corrosion potential for the test without stress stabilized after a few hours, while the corrosion potential of the test with stress shows a clear shift after 7 h. The latter phenomena is most likely related to the beginning of the SCC process. Phase shifts of four different frequencies (1,000, 100, 10, and 1 Hz) were analyzed and plotted against time. Figure 10 shows a graph for each frequency with results of a test with and without stress (or load). The phase shifts at 1,000 Hz were almost equal to the tests with and without stress. At 100 Hz, a clear difference between the phase shifts of the tests

FIGURE 9. Corrosion potentials with and without stress vs time for sensitized Type 304 SS in a 5-N H2SO4 + 0.1-M NaCl solution.

with and without stress can be seen from 7 h. At 10 Hz, this difference is even clearer, also starting from 7 h. At 1 Hz, a clear difference between both conditions can be noticed, but the link with SCC is not as evident. For applying EIS to monitor SCC under these circumstances, a frequency between 100 Hz and 10 Hz seems the most appropriate

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(a)

(b)

(c)

(d)

FIGURE 10. Phase shifts with and without stress (load) vs time at frequencies: (a) 1,000, (b) 100, (c) 10, and (d) 1 Hz for sensitized Type 304 SS in a 5-N H2SO4 + 0.1-M NaCl solution.

(a)

(b)

FIGURE 11. SEM photographs after SSRT: (a) magnification = 20X and (b) magnification = 1,500X.

choice. The phase shifts of the specimens with stress were smaller than those of the specimens without stress. This is in agreement with the results of the SS electrodes with artificial cracks. For instance, the first picture of Figure 8 shows that at 1 Hz the flat specimen had a phase shift of 90, while the cracked specimens had a phase shift of 50.

To prove that SCC indeed took place, the fracture surface was examined using SEM. Figure 11 shows a picture of the fracture surface at two different magnifications. The photographs show clearly the intergranular fracture related to the SCC process. Because of the severe conditions of the test solutions, localized attack along the grain surfaces is evident.

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SSRT also were performed with specimens not subjected to a corrosive environment. Figure 12 shows the stress/strain curves of two tests, with and without the corrosive environment. The difference in strain clearly reflects the significant reduction in elongation caused by the SCC process. The total strain of the specimen without SCC was 83%, while the total strain of the specimen with SCC was 11%.

CONCLUSIONS
A crack model was developed that described the impedance of a stress corrosion crack. This crack model showed that a change in the phase shift of the impedance at particular frequencies is related to the length of a stress corrosion crack. Experimental results obtained by EIS with SS electrodes containing artificial cracks in a 0.1-M Na2SO4 solution showed good agreement with the simulated results of the crack model. It was shown that intergranular SCC occurred during SSRT experiments with sensitized Type 304 SS specimens in a 5-N H2SO4 + 0.1-M NaCl solution. Impedance measurements showed that a change in phase shift could be related to the SCC process. This suggests that EIS can be used to monitor SCC cracks.
REFERENCES
1. D.D. Macdonald, M.C.H. McKubre, ASTM STP 727, Electrochemical Impedance Techniques in Corrosion Science, in

FIGURE 12. Stress-strain curves for sensitized Type 304 SS with and without a corrosive environment.

2.

3.

4. 5. 6. 7.

8. 9. 10. 11. 12.

Electrochemical Corrosion Testing, eds. F. Mansfeld, U. Bertocci (West Conshohocken, PA: ASTM, 1981), p. 110. C. Gabrielli, Use and Applications of Electrochemical Impedance Techniques, Solartron Instruments, Technical Report 24 (1994), p. 4. J.R. Macdonald, Impedance Spectroscopy: Emphasizing Solid Materials and Systems (New York, NY:, John Wiley and Sons, 1987), p. 5. R.D. Armstrong, A.C. Coates, Corros. Sci. 16 (1976): p. 423. R.D. Armstrong, M.F. Bell, J.P. Holmes, Corros. Sci. 19 (1979): p. 297. R. Oltra, M. Keddam, Corros. Sci. 28 (1988): p. 1. R. de Levie, Advances in Electrochemistry and Electrochemical Engineering, vol. 6 (New York, NY: Wiley-Interscience, 1967), p. 329. M.C. Petit, M. Cid, M. Puiggali, Z. Amor, Corros. Sci. 31 (1990): p. 491. G. Cragnolino, D.D. Macdonald, Corrosion 38, 8 (1982): p. 406. I.D. Raistrick, Electrochim. Acta 35, 10 (1990): p. 1,579. H. Keiser, K.D. Beccu, M.A. Gutjahr, Electrochim. Acta 21 (1976): p. 539. J.H. Zheng, W.F. Bogaerts, M.J. Brabers, Corrosion 48, 4 (1992): p. 320-331.

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