Materials Chemistry and Physics 142 (2013) 539e544

Contents lists available at ScienceDirect

Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Electrodeposition of high Co content nanocrystalline ZneCo alloys

from a choline chloride-based ionic liquid
Qingwei Chu a, b, Wei Wang a, Jun Liang a, *, Jingcheng Hao a, **, Zisheng Zhen c
a
State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, PR China
b
Graduate University of Chinese Academy of Sciences, Beijing 100039, PR China
c
Magontec Xian Co. Ltd., Xian 710021, PR China

h i g h l i g h t s

A non-anomalous codeposition process of ZneCo alloys was observed in ChCleurea IL.

High Co content ZneCo alloy was deposited from high Co2 concentration ChCleurea IL.

The high Co content ZneCo deposit was dense, homogenous and nanocrystallized.

a r t i c l e i n f o a b s t r a c t

Article history: Zincecobalt (ZneCo) alloys were electrodeposited from a choline chloride-based ionic liquid containing
Received 31 January 2013 ZnCl2 and different concentration of CoCl2. It was found that the Co content in deposits increased with
Received in revised form the increase of the concentration of Co2 in the plating bath and the codeposition of ZneCo alloy was a
9 July 2013
non-anomalous type, i.e. more noble metal Co depositing preferentially with respect to the less noble
Accepted 29 July 2013
one Zn. Structural and composition analysis revealed that the concentration of Co2 strongly affected the
morphology and chemical content, as well as the phase structure of ZneCo alloys. A high Co content
Keywords:
(over 60 wt.%), dense, homogenous and nanocrystallized ZneCo alloy was deposited from plating bath
Alloys
Coatings
containing higher concentration of Co2.
Electrochemical techniques 2013 Elsevier B.V. All rights reserved.
Microstructure

1. Introduction
The electrodeposition of ZneCo alloy coatings with different
Co content is of great interest owing to their better mechanical
and anti-corrosion properties than pure Zn deposits [1e3]. In
addition, ZneCo deposits with higher Co content could be
possible to have interesting magnetic properties because Co has a
relatively large magnetic energy as one of the magnetic materials
[4]. It was reported that the codeposition behavior of ZneCo in
aqueous solution is anomalous process which less noble Zn de-
posits preferentially with respect to the more noble Co. Owing to
that, Co content in the ZneCo deposits obtained from aqueous
solution is very low that only can reach to 6e7 wt.% [5,6]. So far,
few works have been published on ZneCo alloy deposits with
higher Co content. Lima-Neto et al. [7] prepared Zne18Co (18 at.%
* Corresponding author. Tel.: 86 931 4968381; fax: 86 931 4968163.
** Corresponding author. Tel.: 86 531 88366074; fax: 86 531 88564464.
E-mail addresses: jliang@licp.cas.cn (J. Liang), jhao@sdu.edu.cn (J. Hao).
Co) alloy and the coating showed better corrosion resistance,
with a lifetime about three times longer than the unalloyed Zn
layer. Lichusina et al. [8] revealed that Co-rich ZneCo alloys (ca
15e18 wt.% Co) deposits exhibited good appearance and high
corrosion resistance. The resistance was comparable to that of
chromated conventional ZneCo coatings with low cobalt con-
centrations. Vlad et al. [4] obtained ZneCo (8e16 at.% Co) gran-
ular lms by electrodeposition and the lms exhibited different
magnetic properties with the change of microstructure and
compositions, showing interest for potential applications in
spintronics. The utilization of organic solvents-based salt bath,
such as zinc chlorideedimethylsulfone (ZnCl2eDMSO2) electro-
lytes with added CoCl2, is an alternative method to prepare Zne
Co lms with a wide range of Co content (from 13 to 96 at.%) [9].
However, this method is of limited use since the organic solvents
are costly and highly volatile. Therefore, if feasible method can be
developed to produce ZneCo deposits with different Co contents,
the corrosion and magnetic properties of such alloys will be
tuned to a great extent.

0254-0584/$ e see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matchemphys.2013.07.049
540 Q. Chu et al. / Materials Chemistry and Physics 142 (2013) 539e544

Ionic liquid is a molten liquid that melt below 100  C [10]. Most
metals can be deposited from aqueous solutions that can also be
obtained from ionic liquids [11]. They have wide electrochemical
windows (up to 6 V), high ionic conductivity, and good thermal/
chemical stability [10,12]. Ionic liquids have led to a great interest in
electrochemical studies due to their remarkable properties. Abbott
et al. [13] introduced a relatively new class of ionic liquid, deep
eutectic solvent (DES), which is based on eutectic mixtures of
choline chloride (ChCl) with a hydrogen bond donor species.
Eutectic solvent is a powerful and potential media for the electro-
deposition of metals coatings. By adjusting deposition mode and
condition, a series of metals and alloys have been obtained from the
eutectic-based ionic liquid, such as Zn, ZneNi, Ni, NieCo, NieP,
etc [14e18]. Up to now, few studies have been reported on ZneCo
codeposition from this kind of ionic liquid.
In this work, ChCl/urea ionic liquid with the dissolution of ZnCl2
and CoCl2 was used to deposit the ZneCo alloy. The electrochemical
reduction of Zn2 and Co2 in ionic liquid was studied by cyclic
voltammetry. Bulk ZneCo alloys were electrodeposited by pulse
plating on magnesium alloy substrates. The effect of Co2 concen-
tration in plating bath on the morphology, composition and
structure of the deposits were examined. Fig. 1. Cyclic voltammograms for Pt disk electrode in 1ChCl/2urea ionic liquid con-
taining 0.11 M ZnCl2 0.01 M CoCl2 (curve I) and 0.11 M ZnCl2 0.05 M CoCl2 (curve II)
at scan rate 50 mV s1 under 80  C.
2. Experimental

Choline chloride (ChCl) [HOC2H4N(CH3)3Cl, AR, 99.0%], urea

paper until good metallic luster, and then washed by distilled water
[CON2H4, AR, 99.0%] and zinc chloride [ZnCl2, AR, 98.0%] were
and air-dried at room temperature. The pretreatment process was
used as received. Cobalt chloride [CoCl2$6H2O, AR, 99.0%] was
performed sequentially as follows: degreasing, acid cleaning,
dried at 120  C for 24 h under vacuum. The ChCl-based ionic liquid
alkaline cleaning, uoride activation and zinc immersion (Table 1)
was prepared by mixing the ChCl and urea with a molar ratio of 1:2
[15]. After each procedure, the substrates were washed with
in a beaker at 80  C until a homogeneous, colorless liquid formed.
distilled water and then dried. The anode was a dimensionally pure
0.11 M ZnCl2 and ve different concentration levels (0.01 M, 0.02 M,
zinc plate and all electrodepositions were carried out at an average
0.03 M, 0.04 M and 0.05 M) of dried CoCl2 were then added to the
current density of 3.5 mA cm2 for 2 h using a pulsed power supply
liquid with gentle stirring to obtain navy-blue solutions.
with frequency of 2000 Hz and duty cycle of 75%.
Cyclic voltammetry was carried out using a RST5200 electro-
Surface morphologies and chemical compositions of the
chemical workstation. A three-electrode system consisting of a
deposited coatings were analyzed by a JSM-5600LV scanning
platinum disk working electrode (1.0 mm diameter), a zinc counter
electron microscopy (SEM) equipped with electron dispersive
electrode (25 mm  20 mm) and a zinc wire reference electrode
spectroscopy (EDS, Kevex). Phase structure of the coatings was
was used. The working electrode was polished with 0.3 mm
determined by Siemens D5000 X-ray diffraction (XRD) using Cu-Ka
alumina paste, cleaned in an ultrasonic acetone bath, rinsed with
radiation in the 2q 30e90 range with a scanning rate of 15 /min
distilled water and dried before each measurement. The reference
and a step of 0.02 . JEM-1200EX transmission electron microscope
electrode was a zinc wire placed in a separate fritted glass tube
(TEM) and selected area electron diffraction (SAED) were used to
containing 1ChCl/2urea [19]. All cyclic voltammograms were per-
formed at scan rates 50 mV s1 under 80  C.
Bulk ZneCo alloys were deposited on pretreated AM60B mag-
nesium alloys (mass fraction: Al 5.6e6.4%, Mn 0.26e0.4%,
Zn < 0.2%, balance Mg). The magnesium alloys of size
36 mm  20 mm  2 mm were rstly polished with 1000# sand

Table 1
Process and operation condition of electrodeposition on magnesium alloy.

Process Chemical reagent Operation condition

Degreasing NaOH 40 g L1 60e70  C

Na2CO3 20 g L1 8e10 min
Na3PO4 30 g L1
Acid cleaning H3PO4 (85%) 200 mL L1 40e45  C
Na2MoO4$2H2O 1 g L1 10e15 s
Alkaline cleaning Na4P2O7 80 g L1 70e80  C
Na2CO3 20 g L1 8e10 min
NaNO3 30 g L1
Fluoride activation HF(40%) 375 mL L1 Room temperature
5e10 min
Zinc immersion ZnSO4$7H2O 30 g L1 70e80  C
Na4P2O7 120 g L1 8e10 min
Na2CO3 6 g L1
NaF 5 g L1
Fig. 2. The inuence of Co2 concentration on Co content in ZneCo deposits.
 Q. Chu et al. / Materials Chemistry and Physics 142 (2013) 539e544 541

Fig. 3. Surface and corresponding cross-sectional micrographs of ZneCo deposits obtained from 1ChCl/2urea ionic liquid containing 0.11 M ZnCl2 and (a, b) 0.01 M CoCl2, (c, d)
0.03 M CoCl2, (e, f) 0.04 M CoCl2, (g, h) 0.05 M CoCl2 CoCl2 at 80  C.
542 Q. Chu et al. / Materials Chemistry and Physics 142 (2013) 539e544

investigate the detailed microstructure of the coating deposited at

high CoCl2 concentration level.

3. Results and discussion

Fig. 1 displays the cyclic voltammograms of 1ChCl/2urea ionic

liquids containing 0.11 M ZnCl2 and two different concentrations of
CoCl2 (0.01 M and 0.05 M) on a Pt electrode. For the lower con-
centration of Co2 in plating bath, there are two reduction peaks on
the cathodic branch of voltammogram (curve I). The small peak at
0.26 V (noted as a) is attributed to the Co2 to Co reduction
process, while the evident reduction peak at 0.16 V can be
assigned to the Zn2 to Zn reduction process [20]. In the higher
concentration of Co2 plating bath, the reduction peak at 0.22 V
(noted as a0 ) is evidently stronger and the reduction peak of Zn2
shifts negatively from 0.16 V to 0.22 V (curve II). It can be posited
that the more noble metal Co deposits preferentially to Zn, which
suggesting that the deposition process of Zn and Co is non-
anomalous type in this plating bath. This result is similar to the
deposition behavior of ZneNi from 1ChCl/2urea ionic liquid [16].
Fig. 2 shows the relationship between Co content in deposits
and Co2 concentration in plating bath. It can be seen that the
concentration of Co2 in plating bath strongly effects the compo-
sition of the deposits. With the concentration of Co2 increase from
0.01 M to 0.02 M, the percentage of Co in the deposits propor-
tionally increases from 8.24 wt.% to 16.02 wt.%. Further increasing
the concentration of Co2 in the plating bath (from 0.02 M to
0.04 M), however, leads to sharply increases of the Co percentage
up over 60 wt.% in the deposits. The Co content in the deposits then
remains almost constant with the concentration of Co2 increase
from 0.04 M to 0.05 M. The composition reference line (CRL), rep-
resenting the percentage of Co in the deposits equals to that in the
bath [21], is also shown in Fig. 2a. It is obvious that the Co content in
deposits is always above the CRL. This means that the noble metal
Co deposits preferentially in the deposition process and the code-
position of Zn and Co is non-anomalous type in this plating bath,
conrmed the result of CV testing. This non-anomalous codeposi-
tion process is different from previous studies [5,19,22], that less
noble metal Zn deposited preferentially which leading to the Co
content in deposits difcult to more than 10 wt.%.
Fig. 3 shows the surface morphologies of bulk ZneCo deposits
on magnesium alloy obtained from 1ChCl/2urea ionic liquid con-
taining 0.11 M ZnCl2 and different concentrations of CoCl2 (0.01 M,
0.03 M, 0.04 M and 0.05 M). As shown in Fig. 3a, the ZneCo alloy
deposited from the plating bath containing 0.01 M CoCl2 is made up
of cauliower-like spherical nodules with diameter ranging from 2
to 8 mm. The nodules distribute independently each other, making
the surface of the deposit highly porous. The corresponding cross-
sectional morphology shows that the averaged thickness of the
deposit is around 14 mm (Fig. 3b). Fig. 3c shows that a dense ZneCo
deposit with a signicant decrease in the size of the spherical
particles to 2e5 mm is produced when the concentration of Co2
increases to 0.03 M. However, the thickness of the deposit de-
creases to 10 mm (Fig. 3d). Upon increasing the concentration of
CoCl2 to 0.04 M, the deposited ZneCo alloy exhibits a dense and
smooth surface with homogenous spherical nodules grouped in
clusters of diverse dimensions (Fig. 3e), which is completely
different from the ZneCo deposit with low Co content. No in-
terstices are observed between the clusters, indicating that a dense
deposit can be obtained in this condition. When the concentration

Fig. 4. X-ray diffraction patterns of the ZneCo deposits obtained from 1ChCl/2urea
ionic liquid containing 0.11 M ZnCl2 and (a) 0.01 M CoCl2, (b) 0.03 M CoCl2, (c) 0.04 M
CoCl2, (d) 0.05 M CoCl2 at 80  C.
 Q. Chu et al. / Materials Chemistry and Physics 142 (2013) 539e544
Fig. 5. TEM micrograph (a) and corresponding SAED (b) of high Co content ZneCo deposit.
of Co2 continue increase (Fig. 3g), there is no signicant change of
surface morphology. The thickness of deposits reduces to around
7 mm (Fig. 3f and h). The decrease of the thickness of the deposits
with the increase of cobalt concentration in plating bath is due to
the loss of current efciency with increasing cobalt levels [23].
Therefore, the concentration of Co2 in the ChCl/urea ionic liquid
strongly inuences the compositions of the ZneCo alloys, and
further inuences the surface morphology as well as the thickness.
This result is very similar to that observed in the deposition of Nie
Co alloys from the eutectic solvent that surface morphology and
chemical composition of the deposits are signicantly dependent
on the Ni2 and Co2 concentrations in the electrolytes [17].
Fig. 4 shows XRD patterns of ZneCo deposits on magnesium
alloy obtained from plating bath containing 0.11 M ZnCl2 and
different concentration of CoCl2. For the low Co content ZneCo
deposit, the XRD pattern presented in Fig. 4a reveals that the de-
posit is composed of the undistorted hexagonal h-phase of zinc and
the bcc structural g-phase of the zinc-cobalt alloy [24]. The
diffraction peak of Mg in the pattern is aroused from the magne-
sium alloy substrate. The highest intensity is detected for the peak
associated with plane (330), indicating a preferential orientation of
the crystals of the h-phase. An increase of the plane (101) and
decrease of the plane (330) peak are observed when the Co2
concentration in the bath is increased to 0.3 M. With the Co2
concentration further increases to 0.4 M and 0.5 M, there is a slight
shift of the peaks associated with the planes (101) and (330) to the
higher angles (Fig. 4c and d), indicating that the ZneCo alloy crystal
lattice was deformed. The intensity of the diffraction peaks in the
XRD patterns is observed to be lower with an increase of Co content
in the deposit, and this suggests that amorphous components in the
deposits increase. In addition, the peaks broaden when the Co
content increases to over 60 wt.%. The broadening of the peaks can
be explained by the grain renement of the deposits. According to
the Scherrers formula, the calculated average grain size of the Zne
Co deposit with high Co content (64 wt.%) is around 15.6 nm.
Therefore, the Co2 concentrations in plating bath inuence the
microstructure, alloy compositions and grain size of ZneCo
deposits.
TEM observation was further carried out to analyze the structure
of the ZneCo deposit with high Co content (64 wt.%) and the
micrograph and corresponding selected area electron diffraction
(SAED) pattern are shown in Fig. 5. It can be seen from Fig. 5a that
the deposit is nano-structured with the grain size ranged from 20 to
543
30 nm. It is normal that there is a slight deviation between the
results from Scherrers analysis based XRD pattern and TEM
observation [10]. The SAED images attached in Fig. 5b demon-
strated that the ZneCo displayed diffractional circles indicative of
amorphous structure. The bright spots were observed for the Zne
Co coating due to its crystallization [25,26]. This is consistent with
the results of XRD analysis.
4. Conclusions
The co-deposition process of ZneCo alloys in the ChCl/urea ionic
liquid with the dissolution of ZnCl2 and CoCl2 is non-anomalous
type, which is contrary to the anomalous co-deposition in
aqueous solution. ZneCo alloys with high Co content can be
deposited successfully in this plating bath. The concentration of
Co2 in plating bath signicantly inuenced the microstructure and
the Co content in the ZneCo alloys. A dense, homogenous and
nanocrystallized ZneCo alloy with high Co content was obtained
from the ChCl/urea ionic liquid containing higher concentration of
Co2.
Acknowledgments
This work was nancially supported by Hundred Talents Pro-
gram of Chinese Academy of Sciences (J. Liang).
References
[1] M.M. Abou-Krisha, H.M. Rageh, E.A. Matter, Surf. Coat. Technol. 202 (2008)
3739e3746.
[2] S.M. Rashwan, Mater. Chem. Phys. 89 (2005) 192e204.
[3] G. Roventi, T. Bellezze, R. Fratesi, Electrochim. Acta 51 (2006) 2691e2697.
[4] L. Vlad, P. Pascariu, S.I. Tanase, D. Pinzaru, M. Dobromir, V. Nica, V. Georgescu,
Phys. B Condensed Matter 406 (2011) 1481e1487.
[5] J.B. Bajat, S. Stankovi c, B.M. Joki
c, S.I. Stevanovi&cacute, Surf. Coat. Technol.
204 (2010) 2745e2753.
[6] J.Y. Fei, G.Z. Liang, W.L. Xin, J.H. Liu, Chin. Chem. Lett. 16 (2005) 1097e1100.
[7] P.D. Lima-Neto, A.N. Correia, R.P. Colares, W.S. Araujo, J. Braz. Chem. Soc. 18
(2007) 1164e1175.
[8] S. Lichusina, A. Chodosovskaja, A. Sudavi cius, R. Juskenas,
_ D. Bu _
cinskiene,
 nas, Chemija 19 (2008) 25e31.
A. Selskis, E. Juzeliu
[9] C.C. Yang, M.F. Shu, Z. Naturforsch. A 60 (2005) 853e860.
[10] F. Endres, M. Bukowski, R. Hempelmann, H. Natter, Angew. Chem. Int. Ed. 42
(2003) 3428e3430.
[11] F. Endres, Chem. Phys. Chem. 3 (2002) 144e154.
[12] A.P. Abbott, G. Capper, K.J. McKenzie, K.S. Ryder, J. Electroanal. Chem. 599
(2007) 288e294.
544 Q. Chu et al. / Materials Chemistry and Physics 142 (2013) 539e544
[13] A.P. Abbott, D. Boothby, G. Capper, D.L. Davies, R.K. Rasheed, J. Am. Chem. Soc.
126 (2004) 9142e9147.
[14] C. Gu, J. Tu, Langmuir 27 (2011) 10132e10140.
[15] H.Y. Yang, X.W. Guo, G.H. Wu, W.J. Ding, J. Chin. Soc. Corros. Prot. 30 (2010)
155e160.
[16] H.Y. Yang, X.W. Guo, X.B. Chen, S.H. Wang, G.H. Wu, W.J. Ding, N. Birbilis,
Electrochim. Acta 63 (2012) 131e138.
[17] Y.H. You, C.D. Gu, X.L. Wang, J.P. Tu, Surf. Coat. Technol. 206 (2012) 3632e
3638.
[18] Y. You, C. Gu, X. Wang, J. Tu, J. Electrochem. Soc. 159 (2012) D642eD648.
[19] P.Y. Chen, I.W. Sun, Electrochim. Acta 46 (2011) 1169e1177.
[20] M.Z. An, P.X. Yang, C.N. Su, A. Nishikata, T. Tsuru, Chin. J. Chem. 26 (2008)
1219e1224.
[21] R. Fratesi, G. Roventi, G. Giuliani, J. Appl. Electrochem. 27 (1997) 1088e1094.
[22] G. Trejo, R. Ortega, Y. Meas, E. Chainet, P. Ozil, J. Appl. Electrochem. 33 (2003)
373e379.
[23] J.L. Ortiz-Aparicio, Y. Meas, G. Trejo, R. Ortega, T.W. Chapman, E. Chainet,
P. Ozil, Electrochim. Acta 52 (2007) 4742e4751.
[24] E. Gmez, X. Alcobe, E. Valls, J. Electroanal. Chem. 505 (2001) 54e61.
[25] H. Li, Y. Wu, J. Zhang, W. Dai, M. Qiao, Appl. Catal. A Gen. 275 (2004) 199e206.
[26] A. Sagel, H. Sieber, H.-J. Fecht, J.H. Perepezko, Acta Mater. 46 (1998) 4233e
4241.