Journal of

Electroanalytical
Chemistry
Journal of Electroanalytical Chemistry 599 (2007) 288294
www.elsevier.com/locate/jelechem

Electrodeposition of zinctin 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 Schirin

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 dier from the aque-
ous processes and that qualitatively dierent phases, compositions and morphologies are obtained for the metal coatings in the dierent
ionic liquid systems. We have quantied the electrochemical stripping responses using cyclic voltammetry together with compositional
analysis using SEM/EDAX and X-ray diraction. The dierences in electrochemical responses are rationalised in terms of the speciation
of both Zn and Sn chlorides in the ionic liquids that have been identied using FAB mass spectrometry. Also we demonstrate that com-
posite 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.
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 major-
ity of investigations have concentrated on imidazolium
cations with discrete anions such as BF 
4 ; PF6 and

(F3CSO2)2N . These ionic liquids have large potential win-
dows and exhibit relatively high conductivities and low vis-
cosities. 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 signicant potential for the elec-
trodeposition of electronegative metals such as aluminium
*
Corresponding author. Fax: +44 116 252 3789.
E-mail address: Andrew.abbott@le.ac.uk (A.P. Abbott).
[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 eectively
delocalise the charge. These eutectic-based ionic liquids
can be described by the general formula:
R1 R2 R3 R4 N 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 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 [710]. Considerably fewer studies

0022-0728/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jelechem.2006.04.024
 A.P. Abbott et al. / Journal of Electroanalytical Chemistry 599 (2007) 288294
have been carried out using Type 3 based liquids, which use
hydrogen bond donors as the complexing agents [11,12].
The use of simple amides, acids and alcohols as complexing
agents makes the liquids very versatile and to distinguish
them from other ionic liquids the term deep eutectic sol-
vents (DES) has been coined. DESs have been used for
electropolishing [13], polymer synthesis [14] and metal
oxide processing [15]. Most of our previous studies have
concentrated on choline chloride as the quaternary ammo-
nium salt as it is non-toxic, biodegradable and is already
used as a common component to numerous household
and industrial products. Hence it can be applied economi-
cally to large-scale processes. 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, tin, and zinctin alloys. We also show that the choice
of hydrogen bond donor aects the type of alloy and the
electrochemistry of the components in solution.
Zinctin alloys have been deposited from a variety of
aqueous baths including sulphate [16], gluconate [17] and
pyrophosphate baths [18]. The alloys are found to have
better corrosion resistance than pure zinc, particularly in
high humidity conditions and are also reported to be supe-
rior to cadmium deposits in marine environments.
2. Experimental
Choline chloride HOC2 H4 NCH3 3 Cl (ChCl)
(Aldrich 99%) was recrystallised from absolute ethanol, l-
tered and dried under vacuum. Urea (Aldrich > 99%) was
dried under vacuum prior to use. Ethylene glycol (EG)
(Aldrich 99+%), tin chloride (Aldrich) and zinc chloride
(BDH) were used as received. The eutectic mixtures were
formed by stirring the two components together, in the sta-
ted proportions, at 100 C until a homogeneous, colourless
liquid formed. Voltammetry was carried out using an
Autolab PGSTAT12 potentiostat controlled with GPES
software. A three-electrode system consisting of a platinum
microelectrode (0.5 mm diameter) (made in-house) a plati-
num counter electrode and a silver wire reference electrode
were used. The working electrode was polished with 0.3 lm
alumina paste, rinsed and dried prior to all measurements.
All voltammograms were performed at 40 C and a scan
rate of 20 mV s1. Stainless steel Hull cell panels were pre-
pared by washing with deionised water and dried, then
degreased by placing in dichloromethane (DCM) for
2 min, then removed and allowed to dry. The panel was
placed in the Hull Cell with a nickel cathode (also rinsed
with water and DCM prior to use). The cell was lled with
1ChCl:2urea ionic liquid containing 0.5 M Zn:0.05 M Sn
and 3 wt% Al2O3. The panel was plated at 10 V for
30 min, rinsed with deionised water and allowed to dry.
The current density at dierent positions across the Hull
cell was calibrated using a Ni strip 5 mm wide. Surface
analysis was carried out using scanning electron micros-
copy (Philips XL30 ESEM) and energy dispersive analysis
by X-rays (EDAX). Powder X-ray diraction was carried
289
out using a Philips model PW 1730 X-ray generator, with
a PW 1716 diractometer and PW 1050/25 detector. The
tube was a long ne focus Cu anode, Ni ltered Ka radia-
tion. The normal current operating conditions are 40 kV
30 mA. Scans are run from 15 to 110 2h with a step size
of 0.02 2h, at a speed of 1/min. Angle calibration is by a
synthetic Si sintered standard.
3. Results and discussion
As with all non-aqueous electrochemistry, the denition
of a reference potential is dicult due to the unknown
liquid junction potential. Most studies in ionic liquids have
used either ferrocene as an internal standard or a silver wire
quasi-reference electrode. With the DESs based on urea and
ethylene glycol the latter approach is used for two reasons.
Firstly: ferrocene along with many of its functionalised
derivatives is largely insoluble in the ionic liquids. Second,
the reference potential of the silver wire in both IL environ-
ments is likely to be dominated by the activity of chloride
ion. In all the experiments described here the concentration
of chloride ion is very much larger than that of any other
species in solution. The potential window of the urea: cho-
line chloride eutectic mixture is relatively small on a plati-
num electrode (1.2 V to +1.25 V vs. Ag) [15]. However,
metals can be deposited with high current eciencies (vide
infra) because the reduction kinetics of the eutectic are con-
siderably slower on other metal surfaces e.g. on Zn no sig-
nicant decomposition of the eutectic occurs above 2 V.
Fig. 1A and B show the voltammetry of ZnCl2 and SnCl2
in ChCl mixtures with urea and ethylene glycol, respectively.
The peak reduction potentials for tin are very similar in both
the urea and glycol based liquids (0.38 V and 0.35 V,
respectively) suggesting rstly that the silver wire does act
as a stable reference electrode and secondly that the hydro-
gen bond donor does not signicantly aect the mechanism
of tin ion reduction (where this is a combination of thermo-
dynamic and kinetic eects). The reduction potentials for
zinc are dierent in the urea and glycol based liquids
(1.00 V and 0.85 V, respectively) suggesting that the zinc
complexes present in solution may dier in the two liquids.
In aqueous solutions the dierence between the standard
reduction potentials for the two metals is 0.62 V. The dier-
ence in the metal reduction potentials in the urea-based
liquid is exactly the same as that in water, 0.62 V, while that
in the ethylene glycol based liquid is only 0.50 V. Fig. 1B
also illustrates the dierence in deposition kinetics for Zn
and Sn, as the charges associated with deposition and strip-
ping of the metal are approximately equal despite a 10-fold
dierence in the concentration of the two metal salts.
It is also evident from Fig. 1 that the currents for reduc-
tion and oxidation of zinc are signicantly dierent
between the two liquids despite the concentrations being
similar. For example the ratio of the cathodic peak cur-
rents, ip(EG)/ip(urea), observed during Zn deposition,
Fig. 1, shows a ratio of approximately 15. The magnitude
of this ratio can be explained, in the most part, by the
290 A.P. Abbott et al. / Journal of Electroanalytical Chemistry 599 (2007) 288294
Fig. 1. (A) Voltammograms (scan rate 20 mV s1) for a Pt microdisc
electrode (0.5 mm diameter) immersed in 1ChCl:2urea containing 0.05 M
SnCl2 (solid line) and in 1ChCl:2urea containing 0.5 M ZnCl2 (dotted
line). (B) Voltammograms (scan rate 20 mV s1) for a Pt microdisc
electrode (0.5 mm diameter) immersed in 1ChCl:2EG containing 0.05 M
SnCl2 (solid line) and in 1ChCl:2EG containing 0.5 M ZnCl2 (dotted line).
dierence in viscosity, g, of the two liquids (gurea = 1072 cP
@ 20 C; gEG = 50 cP @ 20 C) [11,13]. These viscosities
are related to the diusion coecients, D, of reacting spe-
cies by Waldens Rule (below) [19], where the subscripts 1
and 2 denote the viscosities and diusion coecients of a
reacting species in two diering media.
D1 g1  D2 g2
It can easily be shown for a diusion-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:
p in a change in reduction potential of the metal. Fig. 1 sug-
ip EG=ip urea DEG =Durea
Inserting the ratio of diusion coecients derived from the
viscosity values (Waldens Rule) into this expression gives a
value for the ratio ip(EG)/ip(urea) of 5. This indicates that
viscosity eects only account for approximately one-third
of the observed dierences, and the remaining discrepancy
could be accounted for by variations in surface area of the
electrode together with dierences in the deposition kinet-
ics (since the deposition peaks have qualitatively dierent
shapes).
SnCl2 is considerably less soluble in the ChCl:urea sys-
tems and at the concentration shown in Fig. 1 produces a
slightly turbid yellow solution suggesting that the solution
is actually beyond its saturation limit for tin chloride. This
may account, in part, for the smaller voltammetric
response of SnCl2 (in relation to ZnCl2) observed for the
urea system (see Fig. 1).
To elucidate the cause for the dierent voltammetric
responses FAB mass spectra were run of both ChCl:2urea
and ChCl:2EG each containing ZnCl2, then SnCl2 and
nally a mixture of the two metals in a 10:1 ratio. In the
positive ion analysis mode, peaks of m/z = 104 and 243
were the only signals observed and these are known to cor-
respond to the species Choline+ and [2Choline Cl]+ and
shows that no signicant cationic metal-containing species
are formed. The negative ion spectra are considerably more
complex due to the isotope splitting of the metal chloride
species. A signal at 174 is common to all spectra [Choline
2Cl]. The signals at m/z = 95 and 97 were also observed
corresponding to [Cl. urea] and [Cl. EG]. Where just
tin is present the only species identied in both liquids is
centred at m/z = 225 [SnCl3]. We have previously studied
eutectic mixtures between just SnCl2 and ChCl and found
both SnCl 
3 and Sn2 Cl5 [9], but none of the di-tin species
were detected in either the urea or EG case.
For the zinc containing liquids a signicant dierence is
observed between the urea and EG systems. In urea the
only zinc containing species is ZnCl 3 whereas in EG
ZnCl 
3 ; Zn2 Cl5 and Zn3 Cl7

were detected. The most
probable explanation for the observed dierences between
zinc chloride in these two liquids is the ligand properties
of the two complexing agents. Urea will act as a far stron-
ger ligand for ZnCl 3 than ethylene glycol. Its absence from
the FAB-MS spectrum is not unexpected as it is rarely seen
as a metal complex with this technique. No mixed metal
complexes (e.g. ZnSnCl 5 were observed in either the urea
or EG liquids, which is in contrast to what was found in the
ZnCl2/SnCl2/ChCl eutectic where it was the dominant spe-
cies [7]. Eutectic mixtures between ChCl and ZnCl2 are
reported to contain ZnCl  
3 ; Zn2 Cl5 and Zn3 Cl7 . The rela-
tive proportions of each species have been quantied using
potentiometry [8]. It was found that Zn2 Cl 5 was the pre-
dominant species. 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.
The dierence in the species present will certainly result
gests 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. There is a signicant dierence between the voltam-
metric behaviour of the two liquids containing both tin and
zinc chlorides. Fig. 2 shows the response for a solution con-
taining 0.5 M ZnCl2 and 0.05 M SnCl2. In the ethylene gly-
col based ionic liquid separate deposition and stripping
signals are observed for tin and zinc. Stopping the reduc-
tive scan at 0.5 V the deposition of only tin is observed
with QC = QA. Extending the scan potential down to
1.5 V results in a separate reduction signal for zinc. The
zinc deposition response is not as sharp as that observed
in Fig. 1 for pure zinc, but this would be expected as the
deposition of zinc is now occurring on a fresh tin surface
rather than platinum. The two stripping potentials occur-
ring on the anodic sweep occur at approximately the same
potentials as the individual metals shown in Fig. 1B sug-
gesting that this is stripping of the pure metals and that this
is a two-phase alloy i.e. discrete zinc and tin phases. It is
 A.P. Abbott et al. / Journal of Electroanalytical Chemistry 599 (2007) 288294
0.450x10 -4
0.350x10 -4
0.250x10 -4
i/A
0.150x10 -4
0.050x10 -4
-0.050x10 -4
-0.150x10 -4
-1.500 -1.000 -0.500 0 0.500 1.000 1.500
E/V
Fig. 2. Voltammograms (scan rate 20 mV s1) for a Pt microdisc electrode
(0.5 mm diameter) immersed in a 1:2 ChCl:EG DES containing 0.05 M
SnCl2 and 0.5 M ZnCl2.
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. The relative areas
under the oxidation peaks vary with the lower reduction
limit. 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. 1B. However, the dierence between the reduction
potentials of the two metals in the 2ZnCl2/ChCl eutectic
is only 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 (0.62 V). Interestingly, this
could be due to the presence of mixed metal complexes
i.e. ZnSnCl
5 which are known to exist in the Type 1 sys-
tems [7].
Guaus and Torrent-Burgues [17] studied the deposition
of tinzinc alloys from aqueous sulphategluconate baths
and found a considerably more complex voltammetric
response than that shown in Fig. 2. It was shown that
the four reduction peaks observed were due to dierent
zinc and tin containing species. The response observed on
the anodic sweep is comparable with that observed with
ChCl:2EG. 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, akin
to that observed above.
Fig. 3 shows an analogous voltammogram to that
shown in Fig. 2 but using urea as the hydrogen bond donor
in place of EG. The electrochemical response in the two
ionic liquids is clearly dierent and signicantly the
response is also dierent to the response of the two individ-
ual component voltammograms for SnCl2 and ZnCl2. The
reductive potentials for tin and zinc are shifted to more
positive potentials compared to those in Fig. 2. 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. 1
and 2. The single anodic process occurs at a voltage that
is in between those for the zinc and tin processes shown
in Fig. 1. Even taking the shift in reference potential into
291
0.075x10-4
0.050x10-4
0.025x10-4
0
i/A
-4
-0.025x10
-0.050x10 -4
-0.075x10 -4
-0.100x10 -4
-1.250 -0.750 -0.250 0.250 0.750 1.250
E/V
Fig. 3. Voltammograms (scan rate 20 mV s1) for a Pt microdisc electrode
(0.5 mm diameter) immersed in a 1:2ChCl:urea DES containing 0.05 M
SnCl2 and 0.5 M ZnCl2.
account the dierence between the main onset of reduction
(0.88 V) and the oxidation peak potential (0.55 V) is
nevertheless greater than that shown in Fig. 1. Interestingly
no stripping of a tin rich phase is observed. It is probable
therefore, 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.
Bulk deposition of zinc from both EG and urea based
liquids leads to zinc deposits with small crystallites that
have negligible residual chloride. The deposits are dull
and silver coloured in all cases. Fig. 4 shows an SEM image
of a zinc lm grown in 1ChCl:2EG containing 0.5 M
ZnCl2:0.05 M SnCl2 at a current density of 10 mA cm2
for 1 h. This was typical of the morphology in both the
EG and urea based liquids and was relatively unaected
by the current density. We have previously shown that zinc
can be deposited as a crack free lm with high current e-
ciency from a 1ChCl:2ZnCl2 liquid [7]. These lms are
white in appearance and are made up of crystallites that
are slightly larger than those shown in Fig. 4 (c.a. 10
25 lm) [20]. The morphology is also similar to that
obtained from deposition from the 2ZnCl2/ChCl eutectic
Fig. 4. Scanning electron micrograph obtained by the electrolysis of 0.5 M
ZnCl2/0.05 M SnCl2 in 1ChCl:2EG at a current density of 10 mA cm2 for
1 h.
292 A.P. Abbott et al. / Journal of Electroanalytical Chemistry 599 (2007) 288294

with 3 wt% SnCl2 [10]. 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 mix-
tures used in this work have much higher conductivities
(ChCl:2urea = 1.8 mS cm1 and ChCl:2EG = 11 mS cm1
both at 40 C) [11,13].
Alternatively the deposition of tin, reported here, pro-
duced more dendritic clusters. The dendrites are built up
of simple cubic crystals as can be seen from Fig. 5. The
deposition of whisker-like deposits, which is common for
the deposition of tin from aqueous solutions, was not
observed in either ionic liquid when the current density
applied was 10 mA cm2.
Electrolysis of the mixed SnCl2/ZnCl2 solutions pro-
duced deposits with dierent morphologies depending on
Fig. 7. Scanning electron micrograph of a deposit grown from the
the hydrogen bond donor used. With urea based liquids solution shown in Fig. 3 at a current density of 10 mA cm2 for 60 min
the deposit was made up of cubic crystallites, which look (A + 1.0 V in situ anodic etch was performed in the solution for 1 min
similar to those found in Fig. 4 (not shown). Energy Dis- before deposition commenced).
persive Analysis by X-rays (EDAX) showed that they are
predominantly zinc (ca. 89%) with the remainder being

1600
EG
Urea
Intensity / cps

1200

800

400

0
20 40 60 80 100
2 / degrees

Fig. 8. X-ray diraction (XRD) analysis of the samples shown in Figs. 6

Fig. 5. Scanning electron micrograph obtained by the electrolysis of and 7.
0.05 M SnCl2 in 1ChCl:2urea, plated onto copper substrate at a current
density of 10 mA cm2 for 30 min.

Fig. 9. Scanning electron micrograph of an alloy deposit grown from the

Fig. 6. Scanning electron micrograph of a ca. 12 mm deposit grown from solution of 0.5 M Zn:0.05 M Sn in 1ChCl:2urea containing 3 wt% Al2O3
a solution of 0.5 M ZnCl2/0.05 M SnCl2 in 1ChCl:2urea + 3 wt% alumina (shown in Fig. 3) at a current density of 10 mA cm2 for 30 min. Bright
at a current density of 10 mA cm2 for 120 min. areas show high Al2O3 content.
 A.P. Abbott et al. / Journal of Electroanalytical Chemistry 599 (2007) 288294 293

Zn Electrolysis of the ethylene glycol based liquid used in

Sn
O
Fig. 2 at 10 mA cm2 gave a deposit with similar underly-
60 Al ing morphology to that shown in Fig. 7 but with dendritic
Cl
50
growths on the top. These dendritic areas showed higher Sn
content than the bulk and we assume that the dendrites are
40 pure tin. The overall Sn composition of the underlying
metal is higher in tin than that found using urea based liq-
Wt %

30
uids (ca. 4045% Sn and 5055% Zn). Hence it can be seen
20 that changes in ionic liquid composition can aect the ther-
modynamics of metal deposition by changing metal
10 speciation.
X-ray diraction (XRD) analysis was carried out on the
0
samples shown in Figs. 6 and 7 and the results are shown in
80 100 120 140 Fig. 8. The XRD spectra are notably dierent with the dis-
-2
Current density / mA cm tinct tin signals at 2h = 30, 64 and 74 being absent from
Fig. 10. Plot of elemental composition as a function of current density for
the sample deposited from the urea based liquid. Signals at
the deposits shown in Fig. 11 (data obtained from the hull cell panel 2h = 34 and 36 are largely absent from the sample pre-
shown in Fig. 11). pared in the EG based liquid and from those deposited
from aqueous solutions [17] and could be due to a homoge-
largely tin with only traces of chloride. The two metals neous Zn based alloy.
seemed evenly distributed throughout the deposit. Thick The relatively high viscosity of these solvents allows
deposits (>1 mm) showed unusual morphologies. Fig. 6 improved stability of suspensions. Colloidal dispersions
shows a ca. 12 mm deposit grown from a solution of of 1 lm Al2O3 require over 3 h to settle and this is possibly
0.5 M ZnCl2:0.05 M SnCl2 in 1ChCl:2urea, at a current aided by the high ionic strength of the liquids. A dispersion
density of 10 mA cm2 for 120 min. Regular macroscopic of 3 wt% Al2O3 was made in the mixture whose voltamme-
pores of approximately 150 lm diameter are observed with try is shown in Fig. 2. Mild agitation was sucient to
a regular crystalline architecture surrounding them. retain the alumina as a homogeneous dispersion. Cyclic

Fig. 11. Scanning electron micrograph showing dierent regions of a hull cell panel coated with an alloy deposit grown from the solution of 0.5 M
Zn:0.05 M Sn in 1ChCl:2urea containing 3 wt% Al2O3 (shown in Fig. 3) at various current densities for 30 min. A = 85 mA cm2; B = 97; C = 110;
D = 148.
294 A.P. Abbott et al. / Journal of Electroanalytical Chemistry 599 (2007) 288294
voltammetry of the dispersion showed negligible dierence
from that shown in Fig. 2.
Fig. 9 shows an SEM image of the Zn/Sn alloy depos-
ited from the EG based liquid using a current density of
10 mA cm2 for 30 min. EDAX analysis conrms the
inclusion of Al2O3 in the lms and these can be seen as
bright areas in Fig. 9. The size of the Al2O3 inclusions
appears to suggest that the particles do not aggregate in
solution or upon deposition in the lm but rather remain
as discrete entities. The Al concentration in the lm 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.
A Hull cell test was also carried out to determine the
eect of current density on the Zn, Sn and Al2O3 composi-
tion of the lm (determined by EDAX). Fig. 10 shows the
percentage of each component as a function of current den-
sity and it can be seen that this is largely unaected over the
current density range studied. It was however found that
the morphology of the surface layer was dependent on
the current density. At I = 85 mA cm2 a homogenous
deposit is formed as shown in Fig. 11A. Increasing the cur-
rent density yields a similar underlying deposit with an
amorphous surface coating (Fig. 11B) that is tin rich
(42% Sn and 38% Zn). At higher current densities
(Fig. 11C: I = 110 mA cm2) oral shaped tin deposits
are found on the surface and these aggregate at even higher
current densities (Fig. 11D: I = 148 mA cm2) these coa-
lesce to give nodular deposits.
4. 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 electrochem-
ical solvents. It is shown that zinc and tin can be electrode-
posited from these liquids both individually and as alloys.
It is shown for the rst time that the alloy morphology
and composition can be changed by judicious choice of
the ionic liquid. It is proposed that metal speciation is a
cause of metal reduction thermodynamics. It is also dem-
onstrated that composite materials can be deposited and
Al2O3 is used as an example. This could open a new avenue
for the deposition of coatings with improved wear
resistance.
Acknowledgement
The authors acknowledge the EU under the FP6 pro-
gramme for funding this work through the IONMET
Project.
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