Journal of Electroanalytical Chemistry 622 (2008) 161164

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Journal of Electroanalytical Chemistry

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Effect of rare earth metals addition on the corrosion behaviour of crystalline CoNi alloys in alkaline solution
F. Rosalbino a,*, S. Delsante b, G. Borzone b, E. Angelini a
a b

Politecnico di Torino, Dipartimento di Scienza dei Materiali e Ingegneria Chimica (DICHI), Corso Duca degli Abruzzi 24, I-10129 Torino, Italy Universit degli Studi di Genova, Dipartimento di Chimica e Chimica Industriale (DCCI), INSTM UdR Genova, Via Dodecaneso 31, I-16146 Genova, Italy

a r t i c l e

i n f o

a b s t r a c t
The corrosion performance of two crystalline CoNiPr and CoNiEr alloys (Pr5.5Co58Ni36.5 and Er6.5Co57.5Ni36) in an alkaline solution, like the one used in water electrolysis, was studied and compared with that of a commercially employed binary CoNi alloy (Co57Ni43) in order to assess the inuence of rare earth elements on its corrosion behaviour. Light electron microscopy, scanning electron microscopy and quantitative electron probe microanalysis were used to characterize the samples prior to the electrochemical tests. The experiments were carried out in 1 M KOH solution at 298 K. Potentiodynamic polarization curves and potentiostatic current decay transients revealed that CoNiR alloys signicantly improved resistance to corrosion compared with CoNi alloys, in spite of their two-phase microstructure, as a direct consequence of the presence of the praseodymium and erbium rare earth metals in the anodic layer formation. 2008 Elsevier B.V. All rights reserved.

Article history: Received 14 April 2008 Received in revised form 14 May 2008 Accepted 28 May 2008 Available online 2 June 2008 Keywords: CoNi alloys Rare earth intermetallics Corrosion behaviour Polarization curves Potentiostatic current decay transients

1. Introduction Oxygen evolution reaction (OER) plays an important role in electrochemical science and technology because it is involved in many electrochemical systems like water electrolysers, fuel cells, metal-air batteries, sensors, etc. [110]. At present, due to the high overpotential of the oxygen evolution reaction, alkaline water electrolysis normally exhibits low energy efciency and much effort has been directed to the study of noble metals (Pt, Pd, Ir, Ru, Rh, Au, and Os) and their alloys in order to use them as oxygen-evolving anodes in alkaline media, in an attempt to reduce the overpotential. Noble metals and their alloys constitute a wide class of materials with good electrocatalytic activity for a lot of electrode reactions, for example O2 and Cl2 evolution, O2 reduction, ozone production, and organic electrosynthesis [1115]. However, the criteria for choosing the electrode material for an industrial application, which is mostly based on a compromise between electrocatalytic activity and costs, have led to the development of new anode materials. In this context, CoNi alloys, either amorphous [1619] or crystalline [2023], have been identied as efcient electrocatalysts for alkaline water electrolysis, as their catalytic activity is comparable to that of noble metals. Recently, the elect-

* Corresponding author. Tel.: +39 11 0904641; fax: +39 11 0904699. E-mail address: francesco.rosalbino@polito.it (F. Rosalbino). 0022-0728/$ - see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.jelechem.2008.05.015

rocatalytic properties of crystalline CoNi alloys have been improved by alloying additions of rare earth metals through synergetic effects arising from the intimate electronic interaction of the components [2427]. One of the most important features of a given material for industrial applications is its corrosion resistance over extended periods of service. For this reason, corrosion problems have to be considered at an appropriate stage of material development. Even though it must be said that the unusual physical properties of rare earths and their compounds and alloys with transition metals make them increasingly interesting in a growing number of highly important areas. Rare earth elements are among the most electrochemically active metals, the standard potentials for RE3+/RE systems being 2.6 to 2.0 V [28]. It has been established that transition metal alloys containing relatively high amounts (20 mass %) of rare earth elements suffer strongly from corrosion attack both in acidic and neutral media [2931], but very little information is available for the corrosion behaviour in an alkaline environment [32]. In the present study, the corrosion performance in alkaline solution, as used for example in water electrolysis, of crystalline CoNiPr and CoNiEr alloys was studied and compared with that of binary CoNi alloys in order to assess the inuence of rare earth elements on their corrosion behaviour. Cobalt and Nickel exhibit complete solid solubility for all compositions. Praseodymium and erbium were chosen as representatives of the light and the heavy rare earths, respectively.

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2. Experimental details The alloys were prepared in the composition range up to 7 at% of rare earth (Pr and Er), starting from cobalt (99.98 mass%), nickel (99.9 mass%), and rare earth (99.9 mass%) rods. The alloys were obtained by induction melting of a mixture of weighed and polished small pieces of pure metals in alumina sinterized crucibles under argon atmosphere. The alloys were re-melted twices and shaken during melting in order to reach homogenisation; possible mass losses were generally found to be negligible. The microstructures of the alloys were systematically investigated rst by light optical microscopy (LOM) and then by scanning electron microscopy (SEM), and quantitative data were collected by EPMA (electron probe microanalysis). An electron microscope (Zeiss EVO-40) equipped with an OXFORD INCA Energy 300, which allowed chemical analysis by EDS, was used. Cobalt standard was used for calibration and the X-ray intensities were considered for ZAF effects using pure elements as standards; the compositional values derived were usually accurate to 1 at%. For electrochemical testing the alloy samples were electrically connected to an isolated metallic wire and embedded in epoxy resin. Before every test the electrodes were mechanically polished with diamond paste down to 0.1 lm and nally rinsed with distilled water. The polarization measurements were carried out using an Amel System 5000 potentiostat connected to a conventional three-electrode cell with a platinum net as counter electrode and a saturated calomel electrode (SCE) as reference electrode. The electrolyte was purged with N2 for 1 h before each test. The alloys were investigated in 1 M KOH aqueous solution at 298 K. The geometrical area of all electrodes tested was 0.25 cm2. After monitoring the open circuit potential (OCP) for 1 h, potentiodynamic and potentiostatic polarization measurements in the anodic regime were performed. The dynamic polarization was started from the cathodic regime (about 100 mV versus OCP) and linearly swept in an anodic direction at a scan rate of 0.5 mV/s. Anodic potentiostatic measurements were conducted by performing a potential step from the OCP to a potential of +300 mV/SCE in the passive domain, which was chosen from the potentiodynamic polarization curves, and the changes in anodic current density were recorded as a function of time. In all cases triplicate experiments were performed in order to ensure a high reliability of the results.

Fig. 1. SEM image (BSE mode) of the Er6.5Co57.5Ni36 at% as cast alloy. Co70Ni30 primary crystals (1) surrounded by a ne two-phase mixture of Co70Ni30 and Er10(Co,Ni)90 with 39 at% Ni (2). Notice the divorced appearance of the two-phase mixture.

3. Results and discussion First of all we have compared the corrosion behaviour of a commercially employed binary Co57Ni43 alloy to the ternary ones in which a part of the Ni was replaced by a rare earth element (Er6.5Co57.5Ni36 and Pr5.5Co58Ni36.5). The EDS analysis conrmed the nominal composition of the samples. Fig. 1 shows the micrograph of the Er6.5Co57.5Ni36 at% as cast alloy, where the Co70Ni30 primary crystals are surrounded by a ne two-phase mixture formed by Co70Ni30 and Er10(Co,Ni)90 with 39 at% Ni. The phase with composition Er10(Co,Ni)90 may be the solid solution of Ni in Er2Co17 with a higher solubility than that reported in literature (27 at% Ni) [33]; this can be ascribed to the use of an as cast sample. A divorced behaviour [34] of the two-phase mixture around the Co70Ni30 primary crystals should be noted. Fig. 2 shows the micrograph of the Pr5.5Co58Ni36.5 at% as cast alloy. The appearance is similar to that of the ErCoNi alloy: primary crystals of Co70Ni30 surrounded by a two-phase mixture of Co70Ni30 and Pr15.5(Co,Ni)84.5 with 37 at% Co. Notice the divorced behaviour of the two-phase mixture around the Co70Ni30 primary crystals, which can be considered a typical feature in these alloys. In this case the Pr15.5Co37Ni47.5 phase can be the solid solution of Co in PrNi5, which is also reported in literature to exist in the whole

Fig. 2. SEM image (BSE mode) of the Pr5.5Co58Ni36.5 at% as cast alloy. Primary crystals of Co70Ni30 surrounded by a two-phase mixture of Co70Ni30 and Pr15.5(Co,Ni)84.5 with 37 at% Co.

range of compositions. These micrographic appearances were observed in the ternary RNiCo (R = Y, Ce, and Pr) Ni-rich (67 at% R and Ni content >65 at% Ni) and Co-rich (67 at% R and Co content >55 at% Co) both as cast and in samples annealed for a few days at 800 C and quenched in cold water, as observed in studying binary RNi (R = Y, Ce, Pr, Sm, and Tb) crystalline alloys which showed a divorced eutectic behaviour around the primary Ni crystals [27]. On the basis of these results, we decided to prepare the single phases found in each ternary alloy (Co70Ni30, Er10(Co,Ni)90 with 39 at% Ni and Pr15.5(Co,Ni)84.5 with 37 at% Co) on which the electrochemical measurements have also been carried out. After the synthesis, the Rx(Co,Ni)y samples proved to be nearly single phase showing crystals of Er2(Co,Ni)17 or Pr(Co,Ni)5 with a small quantity of two-phase mixture formed by (Co,Ni) solid solution and the corresponding Er2(Co,Ni)17 or Pr(Co,Ni)5 in the thin grain boundaries, see Fig. 3. Co70Ni30 was a single-phase sample. The potentiodynamic polarization curves of Co57Ni43 and CoNiR (R = Pr, Er) alloys recorded in deaerated 1 M KOH solution at room temperature are shown in Fig. 4. It can be seen that CoNiR alloys exhibit a passive region under the conditions given

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Fig. 5 shows anodic current density transients measured in deaerated 1 M KOH solution at a potential value of +300 mV/SCE, selected from the passive region of the potentiodynamic polarization curves (Fig. 4). The logarithmic anodic current density decreases linearly with the logarithmic anodizing time in the initial stage. The rate of growth of the barrier type anodic lms on metals follows a linear relationship between log j and log t, which can be written as [35]:

j Atn
where j is the anodic current density, t is the time, A is a constant and n is a passivation parameter representing the slope of log jlog t plot. In the double logarithmic plot of the current density versus time all curves exhibit slopes close to n = 0.5, indicating a process of diffusion-controlled surface lm growth [36]. Corresponding to the potentiodynamic polarization curves, the transients for the Co58Ni36.5Pr5.5 and Co57.5Ni36Er6.5 alloys exhibit lower overall current density levels compared to the Co57Ni43 alloy, thereby conrming the formation of a more protective surface lm. As shown by the electrochemical measurements, CoNiR alloys exhibit better passive behaviour in the studied medium compared to the Co57Ni43 alloy. Thus, the presence of a two-phase microstructure does not apparently lead to higher dissolution rate or to instability of the passive state as would be expected. Similar behaviour was observed by Latanision et al. on copperzirconium alloys [37]. A Cu60Zr40 amorphous alloy was prepared by melt spinning and subsequently devitried, yielding a single-phase polycrystalline material. For this composition both structures exhibit very similar corrosion behaviour in acidic solutions. The inuence of inhomogeneity was checked by the same authors in Cu58Zr42 and Cu55Zr45 alloys that form two-phase crystalline microstructures. Both amorphous and crystalline forms of these alloys show identical corrosion behaviour as the homogeneous Cu60Zr40 alloy, suggesting that in this region of copperzirconium compositions the precipitated phases are galvanically similar. Since more protective surface layers are formed on the Co58Ni36.5Pr5.5 and Co57.5Ni36Er6.5 alloys than that of the Co57Ni43, galvanic coupling interactions between Co70Ni30 and Pr15.5(Co,Ni)84.5 and between Co70Ni30 and Er10(Co,Ni)90 phases can be considered to occur to a limited extent. In order to gain a plausible explanation for the better corrosion behaviour exhibited by CoNiR alloys, potentiodynamic polarization curves were recorded on the single phases in deaerated 1 M KOH solution at room temperature and the obtained

Fig. 3. SEM image (BSE mode) of the Pr15.5Co37Ni47.5 at% as cast alloy. Crystals of Pr15.5(Co,Ni)84.5 with 37 at% Co and two-phase mixture of (Co,Ni) solid solution and Pr(Co,Ni)5 in the thin grain boundaries.

10

1 j (mA/cm )
2

0.1

0.01

1E-3

1E-4 -600

Co57Ni43 Co58Ni36.5Pr5.5 Co57.5Ni36Er6.5 -400 -200 0 200 E (mV/SCE) 400 600

Fig. 4. Potentiodynamic polarization curves of CoNi and CoNiR (R = Pr, Er) alloys recorded in deaerated 1 M KOH solution at 298 K.

above and also show rather low anodic current densities. This feature is indicative of a material which has formed a protective passive lm in the studied medium. Moreover, a signicant shift in the positive direction of the corrosion potential, Ecorr, is observed with respect to the Co57Ni43 alloy (Ecorr = 530 mV/SCE; Ecorr (Co58Ni36.5Pr5.5) = 410 mV/SCE; Ecorr (Co57.5Ni36Er6.5) = 330 mV/ SCE). As can be seen in Fig. 4, the Co58Ni36.5Pr5.5 alloy exhibits a passivity range extending from 200 to +450 mV/SCE, where the passive current density value is 0.04 mA cm2. The Co57.5Ni36Er6.5 alloy is characterized by a more noble corrosion potential together with a narrower passivity range (from 150 to +480 mV/SCE) compared to the Co58Ni36.5Pr5.5 alloy. However, the passive current density value is 0.02 mA cm2. The Co57Ni43 alloy also exhibits a passive behaviour in the potential range from 300 to +460 mV/SCE. Nevertheless, the passive current density value is higher than 0.15 mA cm2. The higher passive current density value observed for the binary alloy with respect to the Co58Ni36.5Pr5.5 and Co57.5Ni36Er6.5 alloys is indicative of a surface lm less protective than in the case of CoNiR alloys. For all investigated alloys the sharp rise in anodic current density observed at potential values higher than 450480 mV/SCE (transpassive potentials) is attributable to the oxygen evolution reaction.

Co57Ni43 Co58Ni36.5Pr5.5 Co57.5Ni36Er6.5

j (mA/cm2)

0.1
n = -0.5

0.01 1 10 100

t (s)
Fig. 5. Potentiostatic current decay transients recorded at Eanodic = +300 mV/SCE for CoNi and CoNiR alloys in deaerated 1 M KOH solution at 298 K.

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10 1 0.1 j (mA/cm )
2

0.01 1E-3 1E-4 1E-5 -600 Co70Ni30 Pr15.5(Co,Ni)84.5 Er10(Co,Ni)90 -400 -200 0 200 E (mV/SCE) 400 600

 The two-phase microstructure which characterizes the Co58Ni36.5Pr5.5 and Co57.5Ni36Er6.5 alloys has no inuence on their corrosion behaviour which appears to be dominated by that of Pr15.5(Co,Ni)84.5 and Er10(Co,Ni)90 rare earth-containing phases.  As a direct consequence of the presence of praseodymium and erbium in the anodic layer formation, surface layers formed on ternary CoNiR alloys exhibit improved protective properties compared to the lm grown on the binary Co57Ni43 alloy. The present results show that from the corrosion resistance point of view, it is advantageous to employ CoNi alloys containing rare earth metals in alkaline solutions, e.g. in alkaline water electrolysis. References
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Fig. 6. Potentiodynamic polarization curves of CoNi and CoNiR phases recorded in deaerated 1 M KOH solution at 298 K.

results are reported in Fig. 6. It can be seen that for the Pr15.5(Co, Ni)84.5 and Er10(Co,Ni)90 rare earth-containing phases, spontaneous passivation occurs compared to the binary one. Pr15.5(Co,Ni)84.5 and Er10(Co,Ni)90 phases are characterized by a passive behaviour in wide potential range where the passive current density values never exceed 0.01 mA cm2. This feature is indicative of a material which has formed a protective passive lm in the studied medium. By contrast, the Co70Ni30 phase exhibits higher corrosion rates due to less effective passivation in the studied medium. This phase exhibits a wide active peak characterized by anodic current density values higher than 0.3 mA cm2, followed by active-to-passive transition occurring at a potential of 200 mV/SCE. Moreover, even though the passive range is comparable with that of the Pr15.5(Co,Ni)84.5 and Er10(Co,Ni)90 phases, the passive current density is about one order of magnitude higher. With respect to the Pr15.5(Co,Ni)84.5 and Er10(Co,Ni)90 phases, the slightly higher passive current densities exhibited by CoNiR alloys (Fig. 4) conrms the limited galvanic coupling interactions between Co70Ni30 and Pr15.5(Co,Ni)84.5 and between Co70Ni30 and Er10(Co,Ni)90 phases. Hence, from these results it is reasonable to assume that Pr15.5(Co,Ni)84.5 and Er10(Co,Ni)90 phases dominate the corrosion behaviour of CoNiR alloys. Supposedly, the higher stability and degree of protection conferred by the surface lms of the Co58Ni36.5Pr5.5 and Co57.5Ni36Er6.5 alloys with respect to the Co57Ni43 alloy results from the presence of the alloying rare earth metals praseodymium and erbium in the anodic layer formation. 4. Conclusions  The corrosion behaviour of ternary CoNiR alloys containing praseodymium and erbium is altered compared to the binary Co57Ni43 alloy without rare earth metals. Due to the presence of the alloying rare earth metals praseodymium and erbium, ternary alloys exhibit improved resistance to corrosion in alkaline solution. Indeed, polarization tests show lower anodic current density values of CoNiR alloys in comparison with the Co57Ni43 one.