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EIS Testing of New Aluminium Sacrificial Anode
EIS Testing of New Aluminium Sacrificial Anode
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Key words: aluminium alloys, anode corrosion efficiency, EIS, sacrificial anodes
Abstract
Aluminium alloys In/Hg free, suitable as sacrificial anodes for cathodic protection, have been developed. Short-term
electrochemical tests were performed on these new alloys to obtain their electrochemical efficiency and to reveal any
tendencies to passivation. Samples were galvanostatically held at different current densities, which changed every
24 h according to DNV RP 401. Electrochemical impedance spectroscopy (EIS), polarization curves and electrode
potential against time measurements were employed to study the main features of the processes taking place at the
alloy–solution interface.
Fig. 2. Experimental set-up short-term electrochemical test (after DNV RP B401) [9].
potential was determined and electrochemical imped- anode specimen and the corresponding electrochemical
ance spectroscopy (EIS) measurements were made at the equivalent.
beginning and end of each current density level period
(every 24 h). This revealed any tendencies to passiva-
tion. The test solution was aerated substitute ocean 3. Results and discussion
water with an initial pH of 8.3 according to ASTM
D1141 [10]. Electrochemical impedance was conducted The trend of the anode potential (open-circuit potential)
by using a Gamry CMS300 Instrument over a frequency against time when the experimental alloys are immersed
range of 10 kHz to 100 mHz (10 points per decade) in a 3% NaCl is reported in Figure 3. The alloy needs
superimposing a 10 mV a.c. signal and interpreted in time to reach a steady potential. This potential,
terms of equivalent circuit with frequency dependent (1020 mV vs SCE) is very close to the electrode
components. The equipment was controlled with a PC potential reported by Barbucci et al. [5] and Foley and
running EIS software, also from Gamry. EIS measure- Trzaskoma [11], who used an aluminium alloy very
ments were used to monitor the corrosion process on the similar to that used in this study in a chloride containing
aluminium anode daily for the 96 test hours. solution.
At the end of the test, the samples were removed, The calculated electrochemical efficiency [9], e, for the
cleaned and weighed to obtain the weight loss. The as-cast Al anode samples was 61.43%, corresponding to
anode efficiency was obtained by calculating the total 1832 Ah kg)1. The closed-circuit potentials measured
charge passed through the system, the weight loss of the were in the range )1.05 V vs SCE at 0 mA cm)2 to
900
Fig. 3. Anode potential of Al–Zn–Mg–Li alloy versus time of different samples tested. Key: (r) sample A, (j) sample B, (m) sample C, ()
sample D, () sample E and (d) sample F.
)0.86 V vs SCE at 4.0 mA cm)2. An active closed- (lower melting point than aluminium). Under polariza-
circuit potential is desirable because a relatively noble tion, this local composition variation will favour the
potential could indicate the presence of passivation. initiation and propagation of macro- and microlocal
Anodes must also possess high faradaic efficiency to events (galvanic corrosion and pitting for example).
prevent frequent anode replacement. The NACE [12] These events are responsible for lowering anode effi-
and DNV [9] tests specify that an Al anode should have ciency by electrochemical or mechanical mass loss [13].
a closed-circuit potential active to )1.0 V vs SCE and The low efficiencies shown by the studied anodes are
a e between 2300 and 2700 Ah kg)1. Then the anode similar to those obtained by Salinas et al. [13] for Al–
analysed met the potential criterion, but appeared to 5%Zn alloy. A possible explanation is that the main
exhibit only moderate efficiency. Theoretically, uniform efficiency loss can be ascribed to the secondary reac-
anode dissolution will give maximum efficiency. Either tions, since they are produced by the relatively high
secondary cathodic reaction on the same interface and/ content of impurities, particularly Fe and Cu, that cause
or mechanical grain loss due to local macro or micro- local cell action.
corrosion cells will reduce the anode efficiency [13]. In Another possible reason for the low efficiency of the
Al–Zn alloys, Zn tends to be rejected to interdendritic anode alloys tested is the effect of the formation of
zones or grain boundaries. This effect is favoured by the corrosion products on the self-corrosion rate of the
cooling rate and the alloying element characteristics anode. The formation of these corrosion products on
Fig. 4. Corrosion products resistance as a function of current density. Estimated values from corresponding EIS diagrams, at the beginning of
applied current density (r), after 24 h (j) and average (m).
901
Fig. 5. Typical Nyquist diagrams of Al–Zn–Mg–Li alloy obtained at the different current densities applied.
902
the anode surface significantly affects the electrochem- an inductive semicircle, Figure 5, which may be attrib-
ical efficiency of the material, as pointed out by the uted to pitting corrosion. The preferred dissolution
results shown in Figure 4, in which it can be observed morphology is general attack rather than pitting, since
that the electrochemical behaviour (performance) of the pitting attack has been correlated to less than optimal
Al anode alloy is strongly dependent on the formation performance.
of surface corrosion products. Figure 4 summarizes the Galvanostatic polarization was applied to the anode
resistance of the corrosion product film as a function of after the test. Under these conditions, the actual active
applied current density. It is clear that the increase in electrode area had already reached a steady state value.
current density produces a decrease in the resistance The polarization test was performed at the end of the
value of the corrosion products, Rcp, formed on Al short-term electrochemical test to determine the anode
anode. This is probably due to the fact that a heavier behaviour type. The anodic polarization behaviour
and denser corrosion product forms at a higher current showed that the anode efficiency obtained at low current
density, thus promoting the self-corrosion activity [14]. densities would be the same as that obtained at high
This seems to prove the effect of the formation of current densities. These results consolidate the acceler-
corrosion products on the self-corrosion rate of the ated dissolution test performed.
anode. Several authors [15, 16] have shown a relation Formerly an argument against using the short-term
between the electrochemical efficiency of anode materi- electrochemical test stated that in the two-week [9] or
als and the anodic current densities. The anodic current four-day [12] test, only the outer 260 lm is consumed,
density is therefore a test parameter that should be given whereas in the one-year test at least 0.5 cm penetration
due consideration. On specimens without a well-devel- is achieved. Murray et al. [21] have obtained successful
oped corrosion product, the self-corrosion rate will results by showing that the evaluation of both the as-
account for a relatively higher portion of the total cast material simultaneously with the cut surfaces
mass loss at lower anodic current densities. On partly (which are representative of the bulk material) makes
consumed anodes, where corrosion products have set- the short-term test appear representative of the cast
tled, the maintenance and development of the corrosion anode long-term performance.
products will be more efficient at higher current densi-
ties than at lower current densities. Consequently, the
self-corrosion rate due to a more corrosive environment
4. Conclusions
beneath the corrosion product will be correspondingly
higher at high anodic current density [14].
(i) The presence of a secondary phase strongly affects
EIS measurements were performed during the DNV
the electrochemical behaviour of the Al–Zn–Mg–Li
test, Figure 5. The shapes of the diagrams show signif-
alloys studied.
icant differences. At high and medium frequencies two
(ii) A secondary reaction led to significant loss in cur-
depressed capacitive loops are evident, probably due to
rent efficiency and was dependent on the micro-
the oxide and to the aluminium faradaic dissolution. At
structure of the Al anodes.
low frequencies an inductive loop is detected. These
(iii) EIS is a useful tool to study the dissolution behav-
results are in agreement with those obtained by Barbucci
iour of Al-alloy sacrificial anodes when subjected to
et al. [17] and other authors [18–20], although in their
cathodic protection.
research unalloyed aluminium was studied. The capac-
itive behavior at high and medium frequencies might be
due to the oxide passive film and the metal–oxide
interface (the charge transfer processes, Al dissolution Acknowledgement
through the film oxide), whereas for the inductive
behaviour, an oxide–solution interface (oxygen ion This work was supported by a grant from CONACYT
ingress in the oxide film) could be ascribed to the (Mexico), Project NC-204.
faradaic processes.
It is evident from the electrochemical impedance data,
Figure 5, that the current density condition plays a References
critical role on the resistive property of the corrosion
products, suggesting a significant change on the corro- 1. A.R. Despic, J. Appl. Electrochem. 6 (1976) 499.
2. M. Salleh, PhD thesis, UMIST, Manchester, UK (1978).
sion product property formed on the Al anode. Dark
3. J.B. Clark, Trans. Am. Soc. Met. 53 (1961) 295.
grey corrosion products were formed. The surface 4. G.M. Kuznetsov, A.D. Barsukov, Izv. Akad, Nauk, SSSR Met. 4
dissolution morphology exhibited a rough, pitted sur- (1986) 198.
face. The EIS diagrams showed evidence of both 5. A. Barbucci, G. Cerisola, G. Bruzzone and A. Saccone, Electro-
passivation and pitting. The lower electrochemical chim. Acta 42 (1997) 2369.
6. R.J. Kilmer and G.E. Stonere, ‘Light Weight Alloys for Aerospace
activity exhibited by the Al anode samples strongly
Applications II’, TMS (1991), p. 3.
suggests that secondary reactions may be the funda- 7. D.A. Petrov, in G. Petzow and G.E. Effemberg (Eds), ‘Ternary
mental cause of this behavior. In our experiments, the Alloys’, Vol. 8 (VCH Verlagsgesellschaft, Weinheim 1993), p. 57
EIS diagrams obtained at higher current densities show 8. X. Zhand and Y. Wang, Corros. Sci. Prot. Technol. 7(1) (1995) 53.
903
9. DNV Recommended Practice RP B401 (1993): ‘Cathodic Protec- 15. C.F. Schreiber and R. Murray, Mater. Perform. 27 (1988)
tion Design’, Det Norske Veritas Industry AS, Hovik (1993). 70.
10. ‘Standard Specification for Substitute Ocean Water’, ASTM 16. S.L. Wolfson, Mater. Perform. 33 (1994) 22.
D1141–75. 17. A. Barbucci, G. Cerisola, P.L. Cabot and G. Bruzzone, Mater. Sci.
11. R.T. Foley and P.P. Trzaskoma, in R.P. Frankental and J. Kruger Forum 289–292 (1998) 529.
(Eds), ‘Passivity of Metals’ The Electrochemical Society, NJ 18. J.B. Bessone, D.R. Salinas, C.E. Mayer, M. Ebert and W.J.
(1978), p. 337. Lorenz, Electrochim. Acta 37 (1992) 2283.
12. NACE Standard Test Method ‘Impressed Current Laboratory 19. J.B. Bessone, C.E. Mayer, K. Juttner and W.J. Lorenz, Electro-
Testing of Aluminium Alloy Anodes’, NACE Standard TM0190- chim. Acta 28 (1983) 171.
98. NACE International, Houston, TX (1998). 20. J.H.W. DeWitt and H.J.W. Lenderink, Electrochim. Acta 41 (1996)
13. D.R. Salinas, S.G. Garcia and J.B. Bessone, J. Appl. Electrochem. 1111.
29 (1999) 1063. 21. J.N. Murray, R.A. Hays and K.E. Lucas, ‘Testing Indium
14. B. Spelid, B. Schei and T. Sydberger, ‘Characterization of Activated, Aluminium Alloys Using NACE TM0190-90 and Long
sacrificial anode materials through laboratory testing’, Corro- Term Exposures’, Corrosion’93, NACE, Houston, TX (1993),
sion’96. NACE, Houston (1996), Paper 551. Paper 534.