You are on page 1of 7

Journal of

Electroanalytical
Chemistry
Journal of Electroanalytical Chemistry 599 (2007) 288–294
www.elsevier.com/locate/jelechem

Electrodeposition of zinc–tin alloys from deep eutectic solvents
based on choline chloride
Andrew P. Abbott *, Glen Capper, Katy J. McKenzie, Karl S. Ryder
Chemistry Department, University of Leicester, Leicester LE1 7RH, UK
Received 18 November 2005; received in revised form 24 March 2006; accepted 3 April 2006
Available online 21 June 2006
Dedicated to David Schiffrin

Abstract
Here we describe the electrolytic deposition of Zn, Sn and Zn/Sn alloys from a solution of the metal chloride salts separately in urea
and ethylene glycol/choline chloride based ionic liquids. We show that the deposition kinetics and thermodynamics differ from the aqueous processes and that qualitatively different phases, compositions and morphologies are obtained for the metal coatings in the different
ionic liquid systems. We have quantified the electrochemical stripping responses using cyclic voltammetry together with compositional
analysis using SEM/EDAX and X-ray diffraction. The differences in electrochemical responses are rationalised in terms of the speciation
of both Zn and Sn chlorides in the ionic liquids that have been identified using FAB mass spectrometry. Also we demonstrate that composite metal coatings, e.g. containing Al2O3 particles, can be obtained from these liquid systems by virtue of the stable liquid suspensions.
This novel feature of these liquids is a function of their relatively high viscosity.
Ó 2006 Elsevier B.V. All rights reserved.
Keywords: Electrodeposition; Zinc; Alloy; Ionic liquid; Eutectic

1. Introduction
Ionic liquids are classed as salts that are liquid at below
100 °C [1]. They have been extensively studied primarily for
synthetic and electrochemical applications [2]. The majority of investigations have concentrated on imidazolium 

cations with discrete anions such as BF
and
4 ; PF6 

(F3CSO2)2N . These ionic liquids have large potential windows and exhibit relatively high conductivities and low viscosities. Two recent reviews by Endres [3,4] cover all
aspects of electrodeposition from these liquids, Compton
and coworkers [5] have reviewed fundamental aspects of
electrochemistry in ionic liquids and a book by Ohno [6]
describes other electrochemical aspects. While ionic liquids
with discrete anions show significant potential for the electrodeposition of electronegative metals such as aluminium
*

Corresponding author. Fax: +44 116 252 3789.
E-mail address: Andrew.abbott@le.ac.uk (A.P. Abbott).

0022-0728/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jelechem.2006.04.024

[3], issues such as toxicity and availability will limit their
practical use for larger scale applications of other metals.
An alternative approach to making ionic liquids is to start
with a simple quaternary ammonium halide and decrease
the freezing point by complexing the anion to effectively
delocalise the charge. These eutectic-based ionic liquids
can be described by the general formula:
R1 R2 R3 R4 Nþ X: z Y
and we have characterised these materials into three types
depending on the complexing agent Y;
Type 1 Y = MClx, M = Zn, Sn, Fe, Al, Ge
Type 2 Y = MClx Æ yH2O
Type 3 Y = RZ, Z = CONH2, COOH, OH
The electrochemistry, physical properties and speciation
occurring in Types 1 and 2 ionic liquids has been reported
for a variety of metals [7–10]. Considerably fewer studies

The tube was a long fine focus Cu anode.g. gluconate [17] and pyrophosphate baths [18]. Ni filtered Ka radiation.62 V. colourless liquid formed. The panel was placed in the Hull Cell with a nickel cathode (also rinsed with water and DCM prior to use).A. Voltammetry was carried out using an Autolab PGSTAT12 potentiostat controlled with GPES software. tin chloride (Aldrich) and zinc chloride (BDH) were used as received. 1B also illustrates the difference in deposition kinetics for Zn and Sn. Results and discussion As with all non-aqueous electrochemistry. in the most part. Fig. at 100 °C until a homogeneous. In the current work we show how DESs formed with choline chloride and either urea or ethylene glycol can be used for the electrodeposition of zinc.5 M Zn:0. With the DESs based on urea and ethylene glycol the latter approach is used for two reasons. We also show that the choice of hydrogen bond donor affects the type of alloy and the electrochemistry of the components in solution. biodegradable and is already used as a common component to numerous household and industrial products. metals can be deposited with high current efficiencies (vide infra) because the reduction kinetics of the eutectic are considerably slower on other metal surfaces e.38 V and 0.02° 2h. 1A and B show the voltammetry of ZnCl2 and SnCl2 in ChCl mixtures with urea and ethylene glycol. rinsed and dried prior to all measurements. in the stated proportions. The potential window of the urea: choline chloride eutectic mixture is relatively small on a platinum electrode (1.2 V to +1. polymer synthesis [14] and metal oxide processing [15]. at a speed of 1°/min.12]. The difference in the metal reduction potentials in the urea-based liquid is exactly the same as that in water. Experimental þ Choline chloride ðHOC2 H4 NðCH3 Þ3 Cl Þ (ChCl) (Aldrich 99%) was recrystallised from absolute ethanol. acids and alcohols as complexing agents makes the liquids very versatile and to distinguish them from other ionic liquids the term deep eutectic solvents (DES) has been coined. 1. It is also evident from Fig.05 M Sn and 3 wt% Al2O3. The peak reduction potentials for tin are very similar in both the urea and glycol based liquids (0. A three-electrode system consisting of a platinum microelectrode (0. Powder X-ray diffraction was carried 289 out using a Philips model PW 1730 X-ray generator. respectively) suggesting firstly that the silver wire does act as a stable reference electrode and secondly that the hydrogen bond donor does not significantly affect the mechanism of tin ion reduction (where this is a combination of thermodynamic and kinetic effects). Zinc–tin alloys have been deposited from a variety of aqueous baths including sulphate [16]. tin.5 mm diameter) (made in-house) a platinum counter electrode and a silver wire reference electrode were used. Abbott et al. / Journal of Electroanalytical Chemistry 599 (2007) 288–294 have been carried out using Type 3 based liquids. Fig. 2. Most of our previous studies have concentrated on choline chloride as the quaternary ammonium salt as it is non-toxic. Hence it can be applied economically to large-scale processes. 3. Angle calibration is by a synthetic Si sintered standard. In aqueous solutions the difference between the standard reduction potentials for the two metals is 0. DESs have been used for electropolishing [13]. The alloys are found to have better corrosion resistance than pure zinc. The magnitude of this ratio can be explained. Most studies in ionic liquids have used either ferrocene as an internal standard or a silver wire quasi-reference electrode. Stainless steel Hull cell panels were prepared by washing with deionised water and dried. then removed and allowed to dry. as the charges associated with deposition and stripping of the metal are approximately equal despite a 10-fold difference in the concentration of the two metal salts. The current density at different positions across the Hull cell was calibrated using a Ni strip 5 mm wide. The reduction potentials for zinc are different in the urea and glycol based liquids (1. which use hydrogen bond donors as the complexing agents [11. However. on Zn no significant decomposition of the eutectic occurs above 2 V. Surface analysis was carried out using scanning electron microscopy (Philips XL30 ESEM) and energy dispersive analysis by X-rays (EDAX). In all the experiments described here the concentration of chloride ion is very much larger than that of any other species in solution. then degreased by placing in dichloromethane (DCM) for 2 min. 0. The use of simple amides. by the . and zinc–tin alloys. filtered and dried under vacuum. Scans are run from 15° to 110° 2h with a step size of 0.25 V vs. The panel was plated at 10 V for 30 min. The cell was filled with 1ChCl:2urea ionic liquid containing 0. Fig. shows a ratio of approximately 15. Firstly: ferrocene along with many of its functionalised derivatives is largely insoluble in the ionic liquids.P. ip(EG)/ip(urea). The normal current operating conditions are 40 kV 30 mA. rinsed with deionised water and allowed to dry. Ethylene glycol (EG) (Aldrich 99+%). particularly in high humidity conditions and are also reported to be superior to cadmium deposits in marine environments. respectively. the reference potential of the silver wire in both IL environments is likely to be dominated by the activity of chloride ion. while that in the ethylene glycol based liquid is only 0. All voltammograms were performed at 40 °C and a scan rate of 20 mV s1.85 V. The eutectic mixtures were formed by stirring the two components together. For example the ratio of the cathodic peak currents. The working electrode was polished with 0. Ag) [15]. Urea (Aldrich > 99%) was dried under vacuum prior to use. observed during Zn deposition.50 V.00 V and 0. with a PW 1716 diffractometer and PW 1050/25 detector. respectively) suggesting that the zinc complexes present in solution may differ in the two liquids. the definition of a reference potential is difficult due to the unknown liquid junction potential. 1 that the currents for reduction and oxidation of zinc are significantly different between the two liquids despite the concentrations being similar.62 V.35 V.3 lm alumina paste. Second.

but this would be expected as the deposition of zinc is now occurring on a fresh tin surface rather than platinum. The difference in the species present will certainly result in a change in reduction potential of the metal. 1 suggests that the mixed zinc species present in 1ChCl:2EG are easier to reduce than ZnCl 3 in urea lending further weight to the idea that the urea is involved in the coordination sphere. EG]. g. D. It is . in part. The most 3 .g. We have previously studied eutectic mixtures between just SnCl2 and ChCl and found  both SnCl 3 and Sn2 Cl5 [9]. Abbott et al. ZnSnCl 5 Þ were observed in either the urea or EG liquids. of reacting species by Walden’s Rule (below) [19]. In urea the only zinc containing species is ZnCl 3 whereas in EG   ZnCl were detected. The two stripping potentials occurring on the anodic sweep occur at approximately the same potentials as the individual metals shown in Fig.13]. It was found that Zn2 Cl 5 was the predominant species. Fig.5 V results in a separate reduction signal for zinc. Fig. Zn2 Cl5 and Zn3 Cl7 probable explanation for the observed differences between zinc chloride in these two liquids is the ligand properties of the two complexing agents. then SnCl2 and finally a mixture of the two metals in a 10:1 ratio. 1 for pure zinc. Urea will act as a far stronger ligand for ZnCl 3 than ethylene glycol.05 M SnCl2 (solid line) and in 1ChCl:2urea containing 0. but none of the di-tin species were detected in either the urea or EG case. The negative ion spectra are considerably more complex due to the isotope splitting of the metal chloride species. The zinc deposition response is not as sharp as that observed in Fig. In the positive ion analysis mode. This indicates that viscosity effects only account for approximately one-third of the observed differences. gEG = 50 cP @ 20 °C) [11.290 A.5 M ZnCl2 (dotted line). 1B suggesting that this is stripping of the pure metals and that this is a two-phase alloy i. (A) Voltammograms (scan rate 20 mV s1) for a Pt microdisc electrode (0. 1 produces a slightly turbid yellow solution suggesting that the solution is actually beyond its saturation limit for tin chloride. 2 shows the response for a solution containing 0.5 M ZnCl2 and 0.05 M SnCl2. which is in contrast to what was found in the ZnCl2/SnCl2/ChCl eutectic where it was the dominant species [7]. and the remaining discrepancy could be accounted for by variations in surface area of the electrode together with differences in the deposition kinetics (since the deposition peaks have qualitatively different shapes). The signals at m/z = 95 and 97 were also observed corresponding to [Cl. Zn2 Cl5 and Zn3 Cl7 . 1. discrete zinc and tin phases. 1). Eutectic mixtures between ChCl and ZnCl2 are   reported to contain ZnCl 3 .5 mm diameter) immersed in 1ChCl:2urea containing 0. Extending the scan potential down to 1. SnCl2 is considerably less soluble in the ChCl:urea systems and at the concentration shown in Fig. Its absence from the FAB-MS spectrum is not unexpected as it is rarely seen as a metal complex with this technique. In the ethylene glycol based ionic liquid separate deposition and stripping signals are observed for tin and zinc. / Journal of Electroanalytical Chemistry 599 (2007) 288–294 Fig. There is a significant difference between the voltammetric behaviour of the two liquids containing both tin and zinc chlorides. (B) Voltammograms (scan rate 20 mV s1) for a Pt microdisc electrode (0. Where just tin is present the only species identified in both liquids is centred at m/z = 225 [SnCl3]. D1 g1  D2 g2 It can easily be shown for a diffusion-controlled process in a linear sweep voltammogram that the corresponding ratio of peak currents for Zn ion reduction in the two media is given by the expression: pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ip ðEGÞ=ip ðureaÞ ¼ DEG =Durea Inserting the ratio of diffusion coefficients derived from the viscosity values (Walden’s Rule) into this expression gives a value for the ratio ip(EG)/ip(urea) of 5. Stopping the reductive scan at 0. peaks of m/z = 104 and 243 were the only signals observed and these are known to correspond to the species Choline+ and [2Choline Cl]+ and shows that no significant cationic metal-containing species are formed. For the zinc containing liquids a significant difference is observed between the urea and EG systems. To elucidate the cause for the different voltammetric responses FAB mass spectra were run of both ChCl:2urea and ChCl:2EG each containing ZnCl2. No mixed metal complexes (e. of the two liquids (gurea = 1072 cP @ 20 °C. The observation that no Zn2 Cl 5 was observed in the urea based liquid suggests that urea acts as a better complexing agent than ZnCl2 for ZnCl 3. difference in viscosity. The relative proportions of each species have been quantified using potentiometry [8]. where the subscripts 1 and 2 denote the viscosities and diffusion coefficients of a reacting species in two differing media.P.e. A signal at 174 is common to all spectra [Choline 2Cl].5 mm diameter) immersed in 1ChCl:2EG containing 0.5 V the deposition of only tin is observed with QC = QA. This may account.5 M ZnCl2 (dotted line). These viscosities are related to the diffusion coefficients.05 M SnCl2 (solid line) and in 1ChCl:2EG containing 0. urea] and [Cl. for the smaller voltammetric response of SnCl2 (in relation to ZnCl2) observed for the urea system (see Fig.

050x10 -4 -0. Fig.050x10-4 0. Bulk deposition of zinc from both EG and urea based liquids leads to zinc deposits with small crystallites that have negligible residual chloride. The stripping of pure zinc and pure tin are clearly discernable and the third oxidative peak increases its relative size depending on the lower reductive limit. This was typical of the morphology in both the EG and urea based liquids and was relatively unaffected by the current density.050x10 -4 -0.5 M ZnCl2.a. Even taking the shift in reference potential into -0. ZnSnCl 5 which are known to exist in the Type 1 systems [7]. 1B. the difference between the reduction potentials of the two metals in the 2ZnCl2/ChCl eutectic is only 0. 10– 25 lm) [20]. The response observed on the anodic sweep is comparable with that observed with ChCl:2EG.500 291 -0.150x10 -4 -1.250 0. The reductive potentials for tin and zinc are shifted to more positive potentials compared to those in Fig.5 M ZnCl2. 4 shows an SEM image of a zinc film grown in 1ChCl:2EG containing 0. The single anodic process occurs at a voltage that is in between those for the zinc and tin processes shown in Fig. Comparing these data to the 2ZnCl2/ChCl eutectic with 3 wt% SnCl2 described previously [10] it is interesting to note that the voltammetry is very similar to that shown in Fig. 3. 3 shows an analogous voltammogram to that shown in Fig.05 M SnCl2 in 1ChCl:2EG at a current density of 10 mA cm2 for 1 h. akin to that observed above.075x10-4 0.250x10 -4 0. only when the reductive limit is extended to more negative potentials that a third stripping peak is observed at +50 mV and this could be due to a third phase consisting of predominantly tin with some zinc.075x10 -4 0 0.350x10 -4 0. Guaus and Torrent-Burgues [17] studied the deposition of tin–zinc alloys from aqueous sulphate–gluconate baths and found a considerably more complex voltammetric response than that shown in Fig. Interestingly no stripping of a tin rich phase is observed. 4. A shift in reference potential is not likely to be a large contributory factor because the reference electrode appears to remain stable (vide supra) as can be seen by comparing Figs.5 M ZnCl2:0.500 -1.250 Fig. / Journal of Electroanalytical Chemistry 599 (2007) 288–294 -4 0 -0. Voltammograms (scan rate 20 mV s1) for a Pt microdisc electrode (0.050x10 i/A i/A A. 2 but using urea as the hydrogen bond donor in place of EG.000 1.150x10 -4 0. We have previously shown that zinc can be deposited as a crack free film with high current efficiency from a 1ChCl:2ZnCl2 liquid [7].025x10-4 0.500 1.5 mm diameter) immersed in a 1:2 ChCl:EG DES containing 0. 4 (c.5 mm diameter) immersed in a 1:2ChCl:urea DES containing 0. Interestingly.250 -0. this could be due to the presence of mixed metal complexes i. 2.250 E/V 0. Voltammograms (scan rate 20 mV s1) for a Pt microdisc electrode (0.341 V which is less than that observed in either of the two solvents seen here and less than the standard aqueous reduction potentials (0. account the difference between the main onset of reduction (0. Fig.5 M ZnCl2/0.750 1. Abbott et al. 1. The relative areas under the oxidation peaks vary with the lower reduction limit. 1. However.55 V) is nevertheless greater than that shown in Fig.e. Scanning electron micrograph obtained by the electrolysis of 0. The deposits are dull and silver coloured in all cases. 2.000 -0.100x10 -4 -1. The morphology is also similar to that obtained from deposition from the 2ZnCl2/ChCl eutectic Fig.05 M SnCl2 and 0.750 -0.05 M SnCl2 and 0. It is probable therefore. The electrochemical response in the two ionic liquids is clearly different and significantly the response is also different to the response of the two individual component voltammograms for SnCl2 and ZnCl2.05 M SnCl2 at a current density of 10 mA cm2 for 1 h. 2.0.450x10 -4 0.025x10 -4 -0. 1 and 2.62 V).P.88 V) and the oxidation peak potential (0. It was shown that the four reduction peaks observed were due to different zinc and tin containing species. These films are white in appearance and are made up of crystallites that are slightly larger than those shown in Fig. .500 E/V Fig. that the use of urea in the ionic liquid tends to lead to less of the separate zinc and tin phases and instead yields a zinc rich phase.

7. Electrolysis of the mixed SnCl2/ZnCl2 solutions produced deposits with different morphologies depending on the hydrogen bond donor used. Scanning electron micrograph of a ca. 3 at a current density of 10 mA cm2 for 60 min (A + 1. Scanning electron micrograph of an alloy deposit grown from the solution of 0. 6.13]. 1600 Intensity / cps EG Urea 1200 800 400 0 20 Fig. Bright areas show high Al2O3 content.05 M Sn in 1ChCl:2urea containing 3 wt% Al2O3 (shown in Fig. Scanning electron micrograph of a deposit grown from the solution shown in Fig.05 M SnCl2 in 1ChCl:2urea + 3 wt% alumina at a current density of 10 mA cm2 for 120 min. produced more dendritic clusters. The dendrites are built up of simple cubic crystals as can be seen from Fig.P.292 A. 6 and 7.5 M ZnCl2/0. Alternatively the deposition of tin. Scanning electron micrograph obtained by the electrolysis of 0. X-ray diffraction (XRD) analysis of the samples shown in Figs. 5. 89%) with the remainder being Fig. 40 60 2θ / degrees 80 100 Fig. 1–2 mm deposit grown from a solution of 0. 9.8 mS cm1 and ChCl:2EG = 11 mS cm1 both at 40 °C) [11. Fig. which look similar to those found in Fig. 4 (not shown). Fig. . plated onto copper substrate at a current density of 10 mA cm2 for 30 min. Energy Dispersive Analysis by X-rays (EDAX) showed that they are predominantly zinc (ca. 8. With urea based liquids the deposit was made up of cubic crystallites. Abbott et al. which is common for the deposition of tin from aqueous solutions. The deposition of whisker-like deposits.05 M SnCl2 in 1ChCl:2urea. The issue associated with the use of these Type 1 zinc eutectics is the low conductivity (36 lS cm1 at 40 °C) whereas the two Type 3 eutectic mixtures used in this work have much higher conductivities (ChCl:2urea = 1. reported here.5 M Zn:0.0 V in situ anodic etch was performed in the solution for 1 min before deposition commenced). 5. 3) at a current density of 10 mA cm2 for 30 min. / Journal of Electroanalytical Chemistry 599 (2007) 288–294 with 3 wt% SnCl2 [10]. was not observed in either ionic liquid when the current density applied was 10 mA cm2.

11. A = 85 mA cm2. 293 Electrolysis of the ethylene glycol based liquid used in Fig. B = 97. 7 but with dendritic growths on the top. 6 and 7 and the results are shown in Fig.05 M SnCl2 in 1ChCl:2urea. These dendritic areas showed higher Sn content than the bulk and we assume that the dendrites are pure tin. 1–2 mm deposit grown from a solution of 0. Signals at 2h = 34° and 36° are largely absent from the sample prepared in the EG based liquid and from those deposited from aqueous solutions [17] and could be due to a homogeneous Zn based alloy. Scanning electron micrograph showing different regions of a hull cell panel coated with an alloy deposit grown from the solution of 0. 8. 3) at various current densities for 30 min. 10. X-ray diffraction (XRD) analysis was carried out on the samples shown in Figs. Cyclic Fig. Hence it can be seen that changes in ionic liquid composition can affect the thermodynamics of metal deposition by changing metal speciation. at a current density of 10 mA cm2 for 120 min. Colloidal dispersions of 1 lm Al2O3 require over 3 h to settle and this is possibly aided by the high ionic strength of the liquids. 2. Regular macroscopic pores of approximately 150 lm diameter are observed with a regular crystalline architecture surrounding them. 6 shows a ca. 64° and 74° being absent from the sample deposited from the urea based liquid. The relatively high viscosity of these solvents allows improved stability of suspensions. Plot of elemental composition as a function of current density for the deposits shown in Fig. The XRD spectra are notably different with the distinct tin signals at 2h = 30°. The overall Sn composition of the underlying metal is higher in tin than that found using urea based liquids (ca.P. Mild agitation was sufficient to retain the alumina as a homogeneous dispersion. A dispersion of 3 wt% Al2O3 was made in the mixture whose voltammetry is shown in Fig. C = 110.05 M Sn in 1ChCl:2urea containing 3 wt% Al2O3 (shown in Fig. Thick deposits (>1 mm) showed unusual morphologies. Abbott et al.5 M ZnCl2:0.A. largely tin with only traces of chloride. D = 148. The two metals seemed evenly distributed throughout the deposit. 11).5 M Zn:0. / Journal of Electroanalytical Chemistry 599 (2007) 288–294 Zn Sn O Al Cl 60 50 Wt % 40 30 20 10 0 80 100 120 -2 Current density / mA cm 140 Fig. 40–45% Sn and 50–55% Zn). 2 at 10 mA cm2 gave a deposit with similar underlying morphology to that shown in Fig. Fig. . 11 (data obtained from the hull cell panel shown in Fig.

11C: I = 110 mA cm2) floral shaped tin deposits are found on the surface and these aggregate at even higher current densities (Fig. Increasing the current density yields a similar underlying deposit with an amorphous surface coating (Fig. G. Surf.L. [19] A. V. Raichevsky. 43 (2004) 3447.P. H. Munro. Bard. Swain. Wheeler. V. Fin. Tambyrajah. New York. Electrochemical Aspects of Ionic Liquids. Torrent-Burgues. Davies. R.K. Inorg.K. ChemPhysChem 3 (2002) 144. V. Germany. Rasheed. H. Soc. Inorg.P. Evans. K. American Chemical Society. Endres. Pushpavanam. B.L. 82 (1996) 226. [3] F. Capper. 11B) that is tin rich (42% Sn and 38% Zn).L. At I = 85 mA cm2 a homogenous deposit is formed as shown in Fig. D. R. Chem. [15] A. Abbott. Inst.C. 4.K. Weinheim. V. Vitkova. [7] A. Commun. Fundamentals and Applications. 11A. D. ChemPhysChem 5 (2004) 1106. Electroanal. 2005. Abbott. Rogers.G. Abbott. Capper.L.). Abbott. R. Abbott. Capper. Muralidharan. T. Ohno (Ed.R. Chem. Fig. 10 (2004) 3769. Capper. Wu.L. Capper. Compton. D. Met. ACS Symposium Series. Eur.R. Rasheed. G. Wiley. [10] A. Capper. Technol. Met. Wiley-VCH Verlag. V. G. [18] V. Falkner. Chem. References [1] T. J. 9. Davies. Buzzeo. R. Davies. Ivanova.L. Capper. [4] F. Commun. G. Rasheed. [14] J. L. D. 11D: I = 148 mA cm2) these coalesce to give nodular deposits. Z. [13] A. 99 (1999) 2071. Abbott et al. Rasheed. Vasantha. (1996) 60. [12] A. in: R. Met. Seddon (Eds. D. T. G. Phys. G. Capper. Shikotra. [16] St. Chem. Davies.P. 218 (2004) 255.H. Chichester. P.G.K. 10 shows the percentage of each component as a function of current density and it can be seen that this is largely unaffected over the current density range studied. It is shown for the first time that the alloy morphology and composition can be changed by judicious choice of the ionic liquid. Liao. [5] M. G. Inorg. Capper. p. Rasheed. Rasheed. 79 (2001) 204. 439. Boothby. [2] P. Davies. Ionic Liquids as Green Solvents: Progress and Prospects.G. It is also demonstrated that composite materials can be deposited and Al2O3 is used as an example. The size of the Al2O3 inclusions appears to suggest that the particles do not aggregate in solution or upon deposition in the film but rather remain as discrete entities.H. [8] A. Abbott. Abbott. Davies. Finish. Abbott.P. John Wiley & Sons.J.C. / Journal of Electroanalytical Chemistry 599 (2007) 288–294 voltammetry of the dispersion showed negligible difference from that shown in Fig.L. It is shown that zinc and tin can be electrodeposited from these liquids both individually and as alloys. Ionic Liquids in Synthesis. 2003. Inst. The Al concentration in the film is approximately 1 wt% which is similar to that in the liquid suggesting that the material is just dragged onto the surface as the metal deposits. This could open a new avenue for the deposition of coatings with improved wear resistance. Rev. 549 (2003) 25.K.P.C. [9] A.P. Sn and Al2O3 composition of the film (determined by EDAX). . At higher current densities (Fig. Davies. R. Abbott. [17] E. R. Welton. Am. [20] A. 126 (2004) 9142. Conclusions This work shows that ionic liquids based on eutectic mixtures of choline chloride and hydrogen bond donors such as ethylene glycol or urea can be used as electrochemical solvents. Wasserscheid. R. Rasheed. 83 (2005) 51. It was however found that the morphology of the surface layer was dependent on the current density. Acknowledgement The authors acknowledge the EU under the FP6 programme for funding this work through the IONMET Project. Munro. Fig. Chem. D. R.D. J. [11] A. EDAX analysis confirms the inclusion of Al2O3 in the films and these can be seen as bright areas in Fig. D. 2. Chem. G. [6] H. Chem. J. P. A Hull cell test was also carried out to determine the effect of current density on the Zn. D. Endres.P. M.S. Chem. G. J.P.A. Fin.P. (2003) 70. Welton. Rasheed. Chem. T. 2003. 44 (2005) 6497. Tambyrajah.P. It is proposed that metal speciation is a cause of metal reduction thermodynamics. V.S. G.L. Y. Electrochemical Methods. Commun. 8 (2005) 390. 9 shows an SEM image of the Zn/Sn alloy deposited from the EG based liquid using a current density of 10 mA cm2 for 30 min. Chem.294 A. D.L. (2001) 2010. Tambyrajah.K. Tambyrajah. R. 1980. D. Coat. Davies. Guaus. R. Bai.).