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Journal of Electroanalytical Chemistry 658 (2011) 18–24

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Journal of Electroanalytical Chemistry
journal homepage: www.elsevier.com/locate/jelechem

Electrodeposition of Co, Sm and SmCo from a Deep Eutectic Solvent
E. Gómez a,⇑, P. Cojocaru b, L. Magagnin b, E. Valles a
a
b

Departament de Química Fısica and Institut de Nanociència i Nanotecnologia (IN2UB), Universitat de Barcelona, 08028 Barcelona, Spain
Dipartimento di Chimica, Materiali e Ingegneria Chimica ‘‘Giulio Natta’’, Politecnico di Milano, 20131 Milano, Italy

a r t i c l e

i n f o

Article history:
Received 1 March 2011
Received in revised form 15 April 2011
Accepted 19 April 2011
Available online 28 April 2011
Keywords:
Electrodeposition
Cobalt
Samarium
Deep Eutectic Solvent

a b s t r a c t
The suitability of 1 choline chloride:2 urea mixture, Deep Eutectic Solvent (DES) for the electrodeposition
of cobalt, samarium and cobalt–samarium system has been studied. Its electrochemical window permits
deposition analysis to be carried out without interference from parallel reactions. Deposition was studied
at 70 °C in order to stimulate mass transfer and to lower solution viscosity.
Cobalt deposits according to a nucleation and three dimensional growth mechanism, all its characteristic features do appear for all cases studied. Samarium deposition takes place through a more complex
process in which a first potential range is found where the species formed limit the conductive character
of the substrate. When potential becomes more negative, normal behaviour is observed. When both
cobalt and samarium are present in the solution, codeposition occurs, at no potential value, any current
diminution of the current was recorded under stirred conditions. Deposits of SmCo show different morphology and composition depending on applied potential. Nodular cobalt-rich deposits are obtained at
low deposition potentials whereas fine grained samarium-rich ones are obtained at more negative deposition potentials.
Ó 2011 Elsevier B.V. All rights reserved.

1. Introduction
Electrodeposition of some metals has been restricted in aqueous
solutions at moderate temperatures to those presenting a standard
potential less negative than that of water reduction. Some of these
metals could be deposited, albeit expensively, using either organic
solvents or more drastic conditions such as molten salts [1–5].
In the last decade research in ionic liquids (ionic materials with
melting point below 100 °C), with a wide electrochemical window,
has made it possible to deposit metals with very negative standard
potentials and their alloys [6–14]. Metallic coatings that up to then
had been impossible to deposit became obtainable. Different generations of ionic liquids have been developed widening the spectrum of depositable metals [15–19]. However, many of them do
require a complex synthesis and a very accurate electrochemical
work, since the majority of the ionic liquids present high sensibility
to water or degradation by oxygen.
It has been shown recently that it is possible to create an ionic
fluid mixing quaternary ammonium halides with an amide, carboxylic acid or alcohol moiety [20–23]. Such mixtures are not,
strictly speaking, room-temperature ionic liquids (RTIL) since in
general contain an uncharged molecular component, so that, the
term Deep Eutectic Solvent (DES) was coined by Abbott [24].
Unlike the ionic liquids these room-temperature eutectic mixtures
⇑ Corresponding author.
E-mail address: e.gomez@ub.edu (E. Gómez).
1572-6657/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jelechem.2011.04.015

are easy to prepare in pure state. They are not water reactive and
their biodegradability is proven. Moreover, the economic investment involved is much lower than that incurred using roomtemperature ionic liquids. However, little information is available
about their physic–chemical properties [25].
The microelectronic industry employs many kinds of coatings in
specific parts of the devices, magnetic materials being the most popular ones. Important advances has been achieved in the preparation
of soft magnetic materials but the electrodeposition of hard magnetic ones is still restricted to a few ones [26–28]. The challenge
in preparing such alloys by electrodeposition is that these alloys
contain metals that have electrocatalytic character to hydrogen
evolution, very negative standard potential, or both. Then, the use
of water-free solvents with a wide electrochemical window is welcome in this field and its possibilities are worthy of study.
In this work we select to study the cobalt–samarium electrodeposition processing possibilities in DES medium, as this alloy is
potentially a hard magnetic material depending on the metal ratio
[29–31]. Few studies of SmCo electrodeposition have been performed in aqueous medium [32] since samarium has a very
negative standard potential leading to simultaneous hydrogen evolution. A study about the preparation of SmCo by electrodeposition
in urea-acetamide-NaBr-MClx melts has been performed by Liu et
al. [33]. Our interest is to analyse the possible electrodeposition of
cobalt, samarium and cobalt–samarium systems using the eutectic
1 choline chloride:2 urea mixture as solvent due to its easy preparation, good working conditions and non aggressive nature.

2A. The solids. curve b). Holding the scan in the potential range of the first reduction peak. A cylindrical three electrode cell of one single compartment was used. 3. curve c). 2B. in the molar proportion 1 choline chloride:2 urea. curve a). Vitreous carbon electrode was polished to a mirror finish using alumina of different grades (3. Work temperature was kept constant at 70 °C to favour low viscosity and high conductivity of the solvent.75 lm and 1. 1) and to ensure reference electrode reproducibility in the DES medium. 3. an increase in the oxidation charge was recorded increasing the hold time (Fig. and cobalt chloride from Fluka both of analytical grade were used as source of electroactive species. Gómez et al. a well defined reduction peak appeared previous to a massive reduction current (Fig. Stable and reproducible values of the potential were obtained with this reference electrode. Samarium nitrate from Aldrich. 2. (b) dashed: after two hours of first scan. cleaned ultrasonically for 2 min in water and dried with air prior to be immersed in the solution. Electrochemical experiments were carried out using an Autolab with PGSTAT30 equipment and GPES software. For all the cathodic limits used. Cyclic voltammograms in DES solvent at: (a) black: immediately after desoxigenation. the electrochemical response of the blank solution (DES solvent) was recorded to establish its electrochemical window (Fig. Prior to dissolution.5 V. and (c) grey: after 50 h of first scan. Solutions were prepared using the DES solvent. A wide electrochemical window in vitreous carbon electrode was observed between the reduction–oxidation processes of the solvent.25 V and (c) t = 30 s at . and (B) with potential holds of: (a) t = 0 s. 2A. cobalt salt was maintained in a stove at 110 °C in order to assure maximum dehydration. 1. 2B. Deposits morphology were observed using Hitachi S-2300 scanning electron microscope. Fig. nucleation loop was observed (Fig. Elemental composition was determined with an X-ray analyser incorporated in Leica Stereoscan S-360 equipment and by X-ray fluorescence (XRF). as corresponds to deposition process. Results Fig. Magnetic stirrer was used when the agitation effect was tested. Experimental Solvent was prepared using choline chloride (from Across Organics) and urea (from Merck) of analytical grade. The reference electrode was an Ag|AgCl/NaCl 3 M mounted in a Luggin Cyclic voltammetry was selected to perform the initial electrochemical study of the deposition processes. For more negative potential limits.87 lm). When the hold was made in the potential range of the massive reduction during the same time. 1. 2. Voltammetric experiments were carried out at 50 mV s 1.1. the oxidation charge increase recorded was less important and a widening of the peak to positive potentials was observed (Fig. Before and during experiments solutions were de-aerated with argon. By reversing the scan at very low negative overpotential. (b) t = 30 s at 1. scanning at first to negative potentials. Fig. / Journal of Electroanalytical Chemistry 658 (2011) 18–24 19 capillary containing the DES solvent. Firstly. Cobalt deposition A basic study of cobalt deposition was made using the habitual electrochemical techniques. were warmed and removed constantly to achieve the liquid state of the deep eutectic solvent (DES).E. curve b). The counter electrode was a platinum spiral.113 M solution (A) at different cathodic limits. Working electrodes were vitreous carbon rods (from Metrohm). a single oxidation peak was recorded during the positive scan. Only one cycle was run in each voltammetric experiment. 1 shows the coincidence between voltammetric scans performed immediate after electrode immersion and those made hours after. Cyclic voltammetric scans were recorded at different negative limits. Cyclic voltammograms from CoCl2 0.

(b) 0.025 M and (c) 0.52 V during 60 s and (C) 1.113 M. the potentiostatic experiments were made stepping the potential from a potential value at which no current was detected to different potentials values. (c) j = 16 mA cm 2 and (d) j = 32 mA cm 2. Fig.34 V during 60 s. the only difference observed being the advance in the appearance of the reduction current and the increase of the current recorded as the Co(II) concentration was increased. the current decay after the maximum was reduced. 3.019 M. / Journal of Electroanalytical Chemistry 658 (2011) 18–24 Fig. For all the solutions tested.036 M and (c) 0. (b) 0. the maximum appeared a short deposition times as the potential applied was made more negative.113 M at the [Co(II)] = 0. (B) E–t transients (a) [Co(II)] = 0.036 M solution curves: (b) j = 8 mA cm 2. Voltammetric potential holds under stirred conditions from the [Sm(III)] = 0.045 M.78 and 2.005 M. Stirring the solutions.025 M solution at: (B) 1. (A) Cyclic voltammograms from different Sm(III) solutions: (a) 0. For a fixed concentration.2 V from different [Co(II)] solutions: (a) 0. Gómez et al. 3A). and from profile decays to attain a quasi stationary value. a displacement of the maximum to low deposition times and an increase in the recorded current was observed increasing the concentration (Fig. This general behaviour was similar using solutions with different Co(II) concentration. (A) j–t transients at 1. (quiescent conditions).20 E. . By comparing the j–t curves obtained at fixed potential from different cobalt (II) concentrations. All the j–t transients recorded evolved to a maximum from which the current 8 mA cm 2 . 4.

curves b–d). . The shape of both voltammetric and potentiostatic curves and the effect of the stirring over the voltammetric. The two reduction peaks were advanced. (c) 1. This result was corroborated by a set of voltammetric experiments holding the scan along the potential range of the first peak: both under quiescent and stirred conditions the reduction current decreased during the hold (Fig. 4C). under stirring. as in aqueous solutions [34]. increasing the number of consecutive scans favours the onset of deposition process when a previous deposit is present. consecutive cyclic voltammetric scans evidenced that as the number of scans increases. Whereas when the potential hold was made in the potential range of the second peak predictable behaviour was recorded: a diminution of current was observed under stationary conditions but important current increase occurred under stirring conditions (Fig. and (f) solvent response at j = 3. (e) j = 9.6 V. This is a rather unexpected behaviour.5 V and (d) 1. maximum in the j–t transient and nucleation spike in the E–t transients evidenced that the characteristic outputs observed in water dissolutions [35–37] continue being valid in the DES solvent demonstrating that nucleation and growth process takes place for cobalt deposition in this eutectic solvent.6 mA cm 2 using: (a) a polished substrate at stationary conditions.5 mA cm 2 under stirring. Fig.3 V. (C) E–t transients from [Sm(III)] = 0.2 mA cm 2 under stirring. (b) 1. nucleation loop.4 mA cm 2 under stirring. During the positive scan no oxidation current was recorded even when very low cathodic limits were used.025 M solution at different potentials: (a) 1. voltammetric experiments revealed similar features in the negative going sweep: at 21 first a peak-band appeared. For all Sm(III) concentrations.2 mA cm 2. although in this type of solvent vigorous agitation was needed to appreciate the effect of the stirring arising difficult ion transport. / Journal of Electroanalytical Chemistry 658 (2011) 18–24 Galvanostatic experiments under stirring conditions revealed that the system initially attained a minimum negative potential value (potential spike) that evolved to less negative values as the deposition time increased (Fig. All the experimental results obtained. (A) j–t transients from the [Sm(III)] = 0. 3B.4 V. Therefore. the reduction process is partially blocked for some reduction products. The stirring of the solution minimises the [Co(II)] depletion near the electrode. (b) j = 6. followed by a second peak developed previous to massive current (Fig. 3B. 5.045 M Sm(III) at j = 1. (b) a polished substrate under agitation and (c) the substrate after experiment b. 4A). As the applied current was made more negative.5 mA cm 2 quiescent solution. curve a).E. In none condition oxidation current was revealed during positive scan. (c) j = 6. the onset of the current appearance occurs at more negative potentials even when the negative potential limit corresponds to low overpotentials.4 mA cm 2 quiescent solution.045 M (a) j = 3.2. In general. at stationary conditions. the first part of the curves recorded under quiescent conditions and from ⁄ symbol. 3. potentiostatic and galvanostatic responses to the Co deposition process in the eutectic 1 choline chloride:2 urea mixture reveals the transport control of the process. By reversing the scan in none condition nucleation loop was recorded. 4B and C). it seems that in the potential range of the first peak. more negative potentials were associated (Fig. (d) j = 9. Samarium process For all the samarium (III) solutions tested. enhanced and better defined as the Sm(III) concentration increased. (B) E–t transients from 0. Gómez et al.

Scanning towards negative potential a peak was detected followed by a close peak that did not clearly developed since a current increase was observed. more evident when the solution was stirred (Fig. At quiescent conditions no clear nucleation spikes were observed.045 M of Sm(III) after: (A) 15 min. the j–t transients recorded showed a previous current peak followed by a smooth current increase. revealed that: low deposition times lead to very fine grained deposits (Fig. As the potential applied was made more negative the current recorded was greater. The agitation effect was also stated in the potentiostatic curves. the potential value achieved was more negative than the corresponding one to the polished substrate (Fig. Nevertheless when the applied currents lead the system to potentials corresponding to the second voltammetric peak. curve b). Low or nor oxidation current was detected in the positive scan. with the stirring of the solution the charge involved in the reduction process was enlarged (Fig. Samarium–cobalt deposition The effect of cobalt (II) in the samarium (III) deposition process was studied using a solution containing 0. Independently of the potential. 6B). 3. The stirring of the solution lead to an increase in the recorded current but was not sufficient to maintain stationary value and especially when the most negative potentials were applied. curves c and d). 6. Galvanostatic experiments were made applying currents sufficiently negative to allow codeposition of both metals. the coating showed different morphology in which flat deposits were observed (Fig. in all applied potentials. to a sudden current increase followed by a current decay. Reversing the scan at the current onset a nucleation loop was recorded followed by an oxidation peak (Fig. and (D) SEM image of a deposit obtained at 1.45 V under stirred conditions from the solution 0. it seems that this feature corresponds to cobalt deposition. curves a and b). 5C. For currents that evolved to potentials corresponding to the first voltammetric peak. 6A). At long deposition times the deposit was cracked (Fig. thus covering stabilization potentials corresponding to the two reduction peaks. Voltammetric scan evidenced a slight advance of the overall deposition process (Fig. 5B. In all potential range where codeposition occurs.045 M Sm(III) + 0. 8A).018 M Co(II). a smooth current diminution was recorded. (B) 25 min and (C) 80 min. In all conditions the potential value at which the solvent reduction takes place was very negative compared to the values where the metallic cation reduced evidencing that in all cases the main process corresponds to deposit formation (Fig. Moreover. Similar results were obtained when deoxygenation of solution was made during 10 h prior to the experiment. stirring of the solution lead the potential to more negative values than that corresponding to quiescent conditions (Fig. although the shape of the curve remembers the typical nucleation feature and with the time the potential dropped smoothly to more negative values. The deposits obtained potentiostatically in this zone present similar morphology. In these experiments low current were flowed and the time consuming to achieve sufficient coverage was important. 7A. 6D). 7B). 7A. 5B. curve f). 7A. Deposits prepared under agitation at different conditions were analysed by scanning electron microscopy. This discards the possible effect of the oxygen presence. 6C). The imaging of deposits obtained after a voltammetric hold at potential values corresponding to the first voltammetric peak. it was not observed in any case the appearance of nucleation loop. the observed behaviour corresponds to a mass control transfer: the potential value achieved under stationary conditions was more negative than the corresponding under agitation (Fig. in both stationary and stirring conditions and applying wide current densities spectrum. Gómez et al.9 V during 30 min under stirred conditions in a potentiostatic experiment. 8A. The j–t transients corresponded. in case that galvanostatic experiment was repeated on a substrate. However when the solution was stirred the potential increased with the increase of deposition time making in evidence the favourable stirring effect over the deposition process. Increasing deposition time the coverage increased and the deposit showed some cracks and a new growth was observed on the first deposit (Fig. which has been maintained into the solution and thus with the deposit already formed present. Enlarging the cathodic limit to more negative limits. 5C).22 E. / Journal of Electroanalytical Chemistry 658 (2011) 18–24 Fig.3. SEM images of Samarium deposits obtained during a voltammetric hold potential at 1. . curve c). curve a) respect to that observed in the free cobalt (II) solution (Fig. Galvanostatic transients were recorded. positive difference in the charge recorded under agitation was observed (Fig. inset as curve c). Whereas if the potential applied corresponds to more negative potential.

3 V during 3600 s. fine grained deposits with homogeneous coverage were obtained (Fig. / Journal of Electroanalytical Chemistry 658 (2011) 18–24 23 Fig. and under stirred conditions at (c) 1.018 M Co(II) solution under quiescent conditions at: (a) 1. Gómez et al. after one hour of deposition no complete coverage was allowed. In order to check the possibilities to deposit on a metallic substrate a Ni/Cu/Au slide was used. These deposits contain 75 wt. (b) 1. Inset of the figure shows the voltammogram recorded reversing the scan at the initio of the deposition and (c) [Co(II)] = 0. 8B shows a detail of the morphology of SmCo deposit obtained in a potential near to the minimal necessary to induce codeposition. or even lower.045 M Sm(III) + 0.018 M. Deposits prepared at different potentials under stirred conditions were imaged and their samarium percentage was evaluated. deposition potentials than those over vitreous carbon.9 V and SEM pictures of deposits obtained over vitreous carbon at: (B) E = 1. (A) Comparison of cyclic voltammograms obtained from 0.018 M Co(II) solution under: (a) quiescent and (b) stirred conditions.018 M and (b) [Co(II)] = 0 M. 8C). Low deposition rate was obtained in this case.8 V and (d) 1. the composition of the deposits corresponded always to 80 wt. Fig. 8. (C) E = 1. . When the potential was made more negative.9 V. By applying similar. 7.% of Sm.045 M Sm(III) + 0.E.% of Sm shows nodular morphology with rounded grains. Increasing the deposition time a new growth over the first deposit was developed (Fig.% of Sm independently of the thickness.045 M Sm(III) solution containing: (a) [Co(II)] = 0. (B) Voltammograms obtained from the 0. Fig. (A) j–t transients from 0. This deposit of 27 wt. 8D).6 V during 900 s and (D) E = 1.6 V during 2500 s.8 V.

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M. samarium deposition in DES solvent shows a less standard behaviour.J. 42 (2010) 1271. Electrochim. the observed behaviour make in evidence that the transport in this kind of systems is another parameter to consider. Chem. Rasheed. D. 144 (1999) 3881.K. N. Physica B 299 (2001) 199. Visan. A. Germany. Electroanalytical Chemistry. D. McKechine. Endress. Fuller. Nobe. 159 (1983) 267. 67. Interface Anal. Müller.Y. When the reduction progresses the recorded current diminishes. Abbott. 650 (1) (2010) 1. [15] T. 99 (1999) 2071. Appl. 20 (2004) 295. 43 (2004) 3447. Acta 54 (22) (2009) 5300–5306. G.C. France. [36] S. SmCo deposits with Sm percentages that exceed 70 wt. [32] J. L.S. de Rango (Eds. [31] A. / Journal of Electroanalytical Chemistry 658 (2011) 18–24 4. ECS Trans. Davies. Magn. R. M. Gibilaro. Abbott. Chem. in: Proceedings of the 18th Int. Soc. Yan. on metallic substrate. Munro. A. Chem. Acta Mater.X. The authors wish to thank the Serveis Cientificotècnics (Universitat de Barcelona) for the use of their equipment. However. Swain. [7] Fei Xiao. Pattanaik. Electrochim. G. p. R.P. Luo. Cobalt deposition analysis in this DES solvent reveals that cobalt deposits through a typical nucleation and three dimensional process. Takeyoshi Okajima. Lwin. Chem. Q. Electrochem.J. Gemming. W. Xu. [18] A. [34] E. 103 (2008) 043911. Irene Montenegro. K.P. during samarium deposition in this DES solvent. Westcott. [35] J. Osteryoung. M. Met. Laure E. From the Sm(III):Co(II) ratio used (around 4:1). A. P. at these low potentials. [17] J. K. 19 (2002) 97– 802. M. Zheludkevich. Section IX ‘‘MAGMAS Materials’’. in: A. Top. Fletcher. W. [25] Tetsuya Tsuda. L. Biosens. All the features related to this process are observed: loop in voltammetric experiments. Having demonstrated the possibility of obtaining CoSm deposits using a DES solvent. H. Proc.). Wei. [8] Jing-Fang Huang. Li. Chai-Liu Kao. Chem. (1992) 965. P. Feng. Davies.J. R. . Abbott. Takeo Onsaka. (2003) 70. K.J. 24 (2009) 3481–3486. Etenko. Mater. W. Masazumi Okido. Soc. S. Electrochem. J. K. Acknowledgements This paper was supported by contract CTQ2010-20726 (subprogram BQU) from the Comisión Interministerial de Ciencia y Tecnología (CICYT). [12] F. Finish. This result confirms also that the nucleation-growth models developed to describe the metal deposition processes could be applied in this kind of solvents. This percentage is higher than that the corresponding to SmCo5 or Sm2Co17 magnetic alloys.L. Wolf. [23] A. 2004. R. Abbott. R. Tong. 2008. Fagiong Zhao. Dempsey. 1971. vol. D.S. 157 (8) (2010) F96. 83 (2005) 51.A. J. since they do not entirely impede samarium deposit formation. [22] A. Capper. Annecy. [20] A. Boland. Capper. Electrochim. T. A. P. Electrochem. J.P. Abbott. Golgovici. A. [28] R. [26] G. P. [4] E. Acta 56 (3) (2011) 1130. 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Although the agitation effect is lesser than the observed in parallel studies at similar Co(II) concentrations in aqueous solutions. Acta 52 (8) (2007) 2746. O. Wiley-VCH Verlag GmbH. Hasegawa. [37] A. Electrochem. Anicai.