Applied Surface Science 410 (2017) 574–584

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Applied Surface Science

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Full Length Article

Zn–Mn alloy coatings from acidic chloride bath: Effect of deposition

conditions on the Zn–Mn electrodeposition-morphological and
structural characterization
N. Loukil ∗ , M. Feki
Laboratoire de Génie des Matériaux et Environnement (LGME), Université de Sfax, ENIS.B.P.W., 1173-3038, Tunisie

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

Article history: Zn–Mn alloy electrodeposition on steel electrode in chloride bath was investigated using cyclic voltam-
Received 9 December 2016 metric, chronopotentiometric and chronoamperometric techniques. Cyclic voltammetries (CV) reveal a
Received in revised form 3 February 2017 deep understanding of electrochemical behaviors of each metal Zn, Mn, proton discharge and Zn–Mn
Accepted 9 February 2017
co-deposition.
Available online 14 February 2017
The electrochemical results show that with increasing Mn2+ ions concentration in the electrolytic bath,
Mn2+ reduction occurs at lower over-potential leading to an enhancement of Mn content into the Zn–Mn
Keywords:
deposits. A dimensionless graph model was used to analyze the effect of Mn2+ ions concentration on
Electrodeposition
Zn–Mn alloy
Zn–Mn nucleation process. It was found that the nucleation process is not extremely affected by Mn2+
Nucleation concentration. Nevertheless, it significantly depends on the applied potential.
Morphology Several parameters such as Mn2+ ions concentration, current density and stirring were investigated
Structure with regard to the Mn content into the final Zn–Mn coatings. It was found that the Mn content increases
with increasing the applied current density jimp and Mn2+ ions concentration in the electrolytic bath.
However, stirring of the solution decreases the Mn content in the Zn–Mn coatings. The phase structure
and surface morphology of Zn–Mn deposits are characterized by means of X-ray diffraction analysis
and Scanning Electron Microscopy (SEM), respectively. The Zn–Mn deposited at low current density
is tri-phasic and consisting of ␩-Zn, ␨-MnZn13 and hexagonal close packed ␧-Zn–Mn. An increase in
current density leads to a transition from crystalline to amorphous structure, arising from the hydroxide
inclusions in the Zn–Mn coating at high current density.
© 2017 Published by Elsevier B.V.

1. Introduction as Mn is more electronegative than Zn, it dissolves first as Mn2+

High performance sacrificial electroplated coatings have always
been required in the metal finishing industry. Recently, the auto-
motive industry has shown a great interest in alloy coatings Zn–X
(X = Fe, Co, Ni, Mn. . .) as an alternative for toxic and high cost
cadmium coatings [1]. Compared to pure metal coatings, electrode-
posited Zn–X alloys have been proved to offer better properties
depending on the alloying element. Zn–Mn coatings appear to be
particularly attractive since these deposits exhibit an enhanced cor-
rosion resistance than pure Zn. In fact, Boshkov et al. [2] reported
that the alloying element, Mn, has been proposed to its dual protec-
tive role affording the highest corrosion resistance of these alloys
[2]. Boshkov and co-workers [3,4] explained this dual role of Mn;
∗ Corresponding author.
E-mail address: nloukil87@gmail.com (N. Loukil).
ions, causing a slight increase of pH due to oxygen reduction. After
its total dissolution from the coating surface, the dissolution pro-
cess continues with that of Zn. Because of the higher pH value, Zn2+
ions react immediately with the medium and form zinc hydroxide
chloride ZHC. The same authors [3,4] reported that ZHC inhibits the
activity of the cathodic oxygen reduction, increasing the anticorro-
sive properties of Zn–Mn coatings.
Several published reports investigated the effect of the Mn
content on enhancing the anticorrosive properties of the Zn–Mn
coatings. A Zn–Mn alloy containing approximately 15–40% shows
the highest corrosion resistance [5]. Other researchers reported
that the optimum behavior of Zn–Mn alloys is achieved for minimal
Mn content of 20% [6].
According to literature, the Mn content co-deposited in the
Zn–Mn alloys can be controlled under several operational param-
eters (solvent choice, bath composition, agitation, current density,
organic additives, temperature, pH. . .) such that alloy properties

http://dx.doi.org/10.1016/j.apsusc.2017.02.075
0169-4332/© 2017 Published by Elsevier B.V.
 N. Loukil, M. Feki / Applied Surface Science 410 (2017) 574–584
(structure, homogeneity and porosity. . .) change systematically
[7]. This is mainly due to the induced changes on the mechanism
and kinetics of electrodeposition [8].
Regardless of the plating bath type, electrodeposition of Zn–Mn
is complicated in view of the relatively large gap between
Zn deposition potential (E◦ (Zn2+ /Zn) = −0.76 V/HSE) and Mn (E◦
(Mn2+ /Mn) = −1.18 V/HSE). It should be noted that those two poten-
tials are more negative than that of hydrogen evolution which
remains inevitable. Because of this fact, complexing agents are
usually required to overcome the Zn–Mn electrodeposition prob-
lems. They act by bringing Zn and Mn deposition potentials closer,
enhancing Mn content in the alloy and limiting hydrogen evolution.
Zn–Mn alloys are extensively electrodeposited from sulfate
acidic electrolytes containing some complexing agents. Citrate ions
[9,10] are namely the most widely used as complexing agent. How-
ever, the deposition of Zn–Mn alloys from these electrolytes shows
often harmful drawbacks. The electrolytes with citrate ions have
two major problems [11], namely: (i) bath instability because of
Mn(III)–citrate complex precipitation [12,13] and (ii) low current
efficiency [1] in view of the high stability constants of metal com-
plexes that leads to a higher over-potential for metal reduction
[9,13].
Alternative acidic bath based on ammonium chloride has been
proposed, since ammonium species favor the co-deposition of Mn.
However, ammonium ions generally produce ammonia and nitrite
which are extensively toxic [11–14]. Furthermore, the removal of
metallic ions from the waste streams is difficult. Due to the new
environmental regulations, the use of an acidic aqueous bath devoid
of ammonium and citrate ions is compulsory. In this regard, a sim-
ple KCl electrolyte without strong complexing agent shows several
benefits, compared to other bath types, like high current efficiency
and good bath stability. Sylla et al. [15] developed an alternative
simple aqueous chloride electrolyte containing ZnCl2, MnCl2 , KCl
and H3 BO3 . Boric acid (H3 BO3 ) has been proposed in view of its
good results to inhibit both hydrogen formation and zinc deposi-
tion by acting as a buffer and/or adsorbing at the electrode surface
and blocking then the active centers [15]. Hence, the corresponding
current efficiency is near 100%.
Moreover, Bucko et al. [16] emphasized that Zn–Mn deposits
obtained from chloride electrolyte are generally smooth and com-
pact in a wider current density range. The overall greater corrosion
stability of Zn–Mn deposits has been shown from acidic chloride
bath [17]. Owning to these benefits, attention has been focused on
the chloride bath for Zn–Mn alloy electrodeposition, a few years
ago. Meanwhile, no data have been reported on the nucleation and
growth mechanisms of Zn–Mn alloys electrodeposition. In return,
several published studies have been only focused on the nucle-
ation and growth mechanisms of either Zn [18] or Zn-alloys such
as Zn–Ni alloys [19]. In this work, an attempt was made to get an
insight into the initial stages of nucleation and crystal growth pro-
cess of Zn–Mn electrodeposition from a KCl electrolyte. This study
was performed using chronoamperometric methods to understand
Zn–Mn electrodeposition under controlled potential conditions.
The goal of the present work was to investigate Zn–Mn co-
deposition from a simple additives-free chloride bath on carbon
steel. For this, a detailed investigation must be carried out to bet-
ter understand pure Zn, pure Mn and Zn–Mn alloys deposition at
different Mn2+ ion concentrations in the electrolytic bath. The elec-
trochemical process was examined by cyclic sweep voltammetry,
chronopotentiometry and chronoamperometry.
The influence of electrodeposition conditions namely, the Mn2+
ions concentration, the applied current density and the stirring
were investigated with the aim to establish a relation between
the deposition conditions and Mn amount in the Zn–Mn deposits.
The Zn–Mn alloys obtained galvanostatically were character-
ized by analyzing their chemical composition, morphology and
575
Table 1
Chemical compositions of the electrolytic baths.
Chemical composition Concentration (M)
Bath 0 Bath 1 Bath2
ZnCl2 – 0.3 0.3
MnCl2 ·2H2 O – 1 0.3
KCl 1.25 1.25 1.25
H3 BO3 0.4 0.4 0.4
structure using atomic absorption spectrometry, Scanning Electron
Microscopy (SEM) and X-ray diffraction (XRD), respectively.
2. Experimental details
The chemical compositions of the two used baths are reported in
Table 1. Before each experiment, the pH was accurately adjusted to
4.5 using dilute hydrochloric acid (HCl) and/or potassium hydrox-
ide (KOH) solution. The electrolytic baths were prepared with
analytical grade chemicals. The electrochemical measurements
were carried out in a conventional three electrode cell, using a
potentiostat autolab 302N coupled to a computer with specific data
acquisition software installed. Various electrochemical methods
like linear and cyclic sweep voltammetry, chronopotentiometry as
well as chronoamperometry were performed.
The working electrode was a carbon steel electrode with a sur-
face area of 0.8 cm2 . The specimens were cold covered in epoxy
resin. Prior to each experiment, the steel substrate surfaces were
mechanically polished, degreased in alcohol and then pickled in a
chloride medium.
The electrodeposition of pure Mn was also studied using the
supporting electrolyte (bath 0) containing 1 M of Mn salt. The work-
ing electrode considered for pure Mn electrodeposition was a glassy
carbon electrode. The reference electrode was a saturated Ag/AgCl
electrode. All potentials are referred to this electrode. The anode
was suitably chosen to avoid precipitation in the bath. All experi-
ments have been conducted at 25 ◦ C.
Zn–Mn coatings were electrodeposited galvanostatically under
different current densities for 30 min. The active surfaces of steel
electrodes were of 12 cm2 .
To determine the Zn and Mn content in each deposit, the latter
was stripped from the working electrode surface in dilute H2 SO4
solution (1 M) containing 2 g/l hexamethylenetetramine (HMTA)
as dissolution inhibitor for the steel substrate. Then, Zn and Mn
concentration in the obtained solution was determined by atomic
absorption spectrometry (Analytic Jena ZEENIT 700). For each
deposit, the quantitative analysis was realized in triplicate.
The surface morphologies of the electrodeposited Zn–Mn coat-
ings were observed using JEOL 5410 Scanning Electron Microscope
(SEM). Crystalline structures were analyzed by X-ray diffractome-
ter (XRD), using X-ray D8 Advance Bruker machine with a CuK∞
radiation. The measurements were performed in the 2 range of
10–90◦ .
3. Results and discussion
3.1. Effect of anode material on bath stability
In the preliminary experiments, the counter electrode was a
platinum Pt placed in a single compartment cell. Whatever the bath
used (bath 1 or 2), a transition from pink, due to the color of Mn salt,
to brown color is observed. A precipitation of a brown solid is then
observed into the working solution, as shown in Fig. 1. A qualitative
test confirms that this precipitate is a Mn-based precipitate.
The brown precipitate exhibits an amorphous structure as
described in the XRD pattern shown in Fig. 2. In this regard, a
576
Fig. 1. Effect of Pt used as a counter electrode on appearance of electrolyte KCl + H3 BO3 containing both Mn and Zn salts: (a) before deposition (b) after deposition.
study was conducted in a compartmentalized cell with the aim
to localize the precipitation and devote the phenomenon. The
anolyte was separated from the catholyte by fine porosity glass
frit tube. It is thereby shown that the precipitation is occurring at
the anodic compartment that has been quickly filled with anode
sludge. According to literature [20], formation of manganese diox-
ide and evolution of oxygen gas are the main reactions taking place
at the anode. Most of studies on Mn [21] and Mn alloys electrode-
position using a platinum counter electrode signposted that this
brown precipitate is originating from Mn oxides, suggesting that
the anodic polarization has been sufficient to enable the Mn2+ oxi-
dation. As a matter of fact, the Pt anode material exhibits a high
oxygen overvoltage [21].
Previous works [22] presumed that precipitation can be due
to the hydrolysis of manganese tri-chloride and manganese tetra-
chloride, which may be occurred at the anode.
In order to better understand the anodic processes on Pt, anodic
potentiodynamic polarizations were performed in different elec-
trolytic baths: the supporting electrolyte KCl + H3 BO3 (bath 0) and
the Zn–Mn electrolyte (bath 1). As shown in Fig. 3, the anodic pro-
cess depends on the salts-containing electrolyte. For the supporting
electrolyte (bath 0), the anodic peak, appearing at about 1.2 V vs.
Ag/AgCl, is related to chlorine evolution. It is striking to note that
chlorine gas is continually evolving at the Pt counter electrode as a
secondary product during electrodeposition [6,21]. However, this
anodic peak is masked in the curve recorded from the bath 1. A
small anodic peak that appears at almost 1 V corresponds to the
50
45
40
35
intensity (a.u)
30
25
20
15
10
5
0
0 10 20 30 40
2θ (degree)
Fig. 2. XRD pattern of the as-obtained brown precipitate during Zn–Mn electrode-
position using a Pt anode.
N. Loukil, M. Feki / Applied Surface Science 410 (2017) 574–584
oxidation of Mn2+ to MnO2 [23], as shown in the enlarged zone in
Fig. 3. Moreover, a more significant increase in the anodic current,
attributed to oxygen evolution from apart of 1.6 V vs. Ag/AgCl, for
bath 1 compared to that of bath 0 is observed. As already described
in a previous work [24], the presence of Mn2+ catalyzes the oxy-
gen evolution rate. That’s why in this work, the pH of the working
electrolyte (bath 1) decreases from 4.5 to 2.7 after a deposition
experiment. The fall in the pH is due to the oxidation of water at
the anode [25].
As pointed in literature [21,26], the formation of MnO2 depends
on the anode material. The selection of anode material is based on
the rate of Mn2+ oxidation to MnO2 . It is obviously that this oxide
would decrease the solution electrical conductivity and increase
the cell voltage, because of its high electrical resistance [21]. To
prevent this solution contamination, it is compulsory to use a solu-
ble anode in order to preserve the bath stability. For the subsequent
experiments, a pure Zn plate was retained as anode material.
3.2. Cyclic voltammetry studies
3.2.1. Mn electrodeposition on glassy carbon
According to literature regarding pure Mn electrodeposition
[26–30], there are a discrepancy due to the use of different
electrolyte compositions, electrode materials and plating condi-
tions. According to Sylla et al. [15], the potential at which Mn
50 60 70
Fig. 3. Anodic voltammetric curves recorded from bath 0 and bath 1 on Pt substrate
(scan rate = 5 mV/s).
 N. Loukil, M. Feki / Applied Surface Science 410 (2017) 574–584
Fig. 4. Cyclic voltammogram of Mn deposition from bath 0 containing 1 M of MnCl2
on a glassy carbon electrode (scan rate 100 mV/s).
deposition on steel substrate starts could not be detected due to the
concomitant hydrogen evolution in an acidic chloride bath. More-
over, Genasan et al. [6] demonstrated that Mn electrodeposition
study is complicated as Mn is readily oxidized during the anodic
sweep. On the basis of these observations reported in literature, a
cyclic voltammogram, shown in Fig. 4, is recorded on a glassy car-
bon electrode at 100 mV s−1 in order to detect the exact potential at
which Mn2+ ions reduction occurs. It is well known that the over-
voltage of hydrogen evolution on the glassy carbon is high. Thus,
distinction between the reactions of Mn2+ reduction and hydrogen
evolution at low cathodic potential is possible. This voltammo-
gram (Fig. 4) confirms that Mn deposition takes place at around
−1.55 V vs. Ag/AgCl. Such occurrence has been reported for pure
Mn deposition on glassy carbon electrode in previous published
results dealing with acidic chloride bath [15,30]. In the backward
scan from −2 V vs. Ag/AgCl, a slight anodic peak, corresponding
to Mn dissolution, is detected at −1.33 V vs. Ag/AgCl. The voltam-
mogram recorded from an acidic chloride bath, in another work,
exhibits a similar dissolution peak at about −1.34 (± 0.01) V [30].
It has to be noted that the magnitude of this anodic peak is small.
This could be attributed to a spontaneous and rapid chemical disso-
lution of the deposited Mn which occurs simultaneously with the
electrochemical one during the anodic scan, as it was suggested by
Ewa Rudnik [30]. It is important to note that the easy dissolution
of Mn deposit is due to its weak stability in acidic media [6,15].
3.2.2. Effect of Mn2+ concentration on Zn–Mn electrodeposition
The Zn–Mn electrodeposition process in presence of various
Mn2+ concentrations was investigated. Corresponding voltammo-
grams were recorded for several Mn2+ concentrations, namely 0,
0.3 M (bath 2) and 1 M (bath 1). The potential interval was scanned
from − 0.6 V to the cathodic direction up to −2 V and the back scan
was ended before anodic steel dissolution. The scan rate was fixed
at 20 mV/s. Fig. 5 shows typical voltammogram for Zn deposition
recorded from Mn2+ ions-free electrolyte ([Mn2+ ] = 0 M, i.e. the sup-
porting electrolyte (bath 0) containing only Zn2+ ions). As it can be
seen in Fig. 5, the cathodic current increases sharply from −1.03 V
vs. Ag/AgCl and gives rise to a cathodic peak at around −1.2 V vs.
Ag/AgCl. This peak is related to Zn2+ reduction during the cathodic
scan. Previous studies [31] demonstrated that this reduction pro-
cess involves the species ZnCl4 2− , which is reduced to Zn via the
following reaction:
ZnCl4 2− + 2e → Zn + 4 Cl−
577
0.3
0.2
0.1
E (V vs. Ag/AgCl)
0
j (A/cm²)
-2.2 -2 -1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
-0.1
[Mn2+]= 0 M -0.2
[Mn2+]=0.3 M
[Mn2+]=1M -0.3
Fig. 5. Typical Cyclic voltammograms performed on steel from electrolytic bath:
1.25 M KCl + 0.4 M H3 BO3 + 0.3 M ZnCl2 , containing different Mn2+ concentrations
0 M; 0.3 M (bath 2) and 1 M (bath 1).
The current density then stays steady between −1.3 and −1.5 V
vs. Ag/AgCl, at about 42 mA/cm2 . Therefore, the reduction of Zn2+
ions is limited by diffusion, i.e. controlled by mass transfer [32]. A
new increase in current density is due to hydrogen evolution on
the freshly formed Zn deposit [32].
When Mn2+ ions are present (at 0.3 and 1 M) in the electrolyte
already containing Zn2+ ions, the two corresponding voltammo-
grams exhibit similar features to that of pure Zn. The potential
at which the cathodic peak arises is similar to that obtained dur-
ing the reduction of pure Zn. This peak is followed by a current
hump at approximately −1.5 V vs. Ag/AgCl, when [Mn2+ ] = 0.3 M,
corresponding to both Mn2+ ions and H2 O reduction.
It can obviously be seen in Fig. 5 that increasing Mn2+ ion con-
centration from 0.3 to 1 M depolarizes the Mn deposition potential
to −1.5 V vs. Ag/AgCl, 50 mV more positive than that obtained for a
Mn2+ ion concentration of 0.3 M, −1.55 V vs. Ag/AgCl. Taking in the
mind the gap between Zn and Mn deposition potentials, increasing
Mn salt concentration seems to be beneficial to reduce this gap and
subsequently to bring Zn and Mn discharging potentials closer.
Increasing Mn2+ concentration until 1 M generates important
current fluctuations below −1.7 V vs. Ag/AgCl, as shown in Fig. 5.
This is attributed to an accelerated reactions of both hydrogen
evolution via H2 bubbles and manganese reduction [15]. These
fluctuations were also observed by Boudinar et al. [33] in elec-
trodeposition of Mn–Bi. This suggests that a higher Mn2+ ions
concentration into the electrolyte enables its faster reduction at
the cathode. This result was in accord with previous results given
by Xu et al. [26]. As a matter of fact, Xu et al. [26] investigated
Mn salt concentration effect on pure Mn electrodeposition. Xu and
his co-workers demonstrated, by investigating the partial current
density of Mn2+ reduction, that Mn electrodeposition reaction was
significantly accelerated with increasing Mn2+ concentration.
Accordingly, a higher Mn percent in Zn–Mn deposits is expected
to be incorporated. This fact is obeyed to the normal co-deposition
[34]. That is to say, Mn amount into Zn–Mn deposits will increase
with increasing Mn2+ ion concentration in the electrolyte.
Regarding the anodic scan, the anodic peaks seen for the two
Mn2+ concentration (Fig. 5) show two shoulders. This suggests that
the film deposited during the cathodic scan does not contain only
the pure Zn phase. The potential range of the anodic peak is between
−1.08 V and −0.1 V vs. Ag/AgCl, that is very close to pure Zn disso-
lution potential range (−1.08 V to −0.2 V vs. Ag/AgCl). This suggests
(1) that the Zn–Mn alloy deposited during the cathodic scan contains
578 N. Loukil, M. Feki / Applied Surface Science 410 (2017) 574–584

t(s)
0 t(s)
0
0 2 4 6 8 10 0 2 4 6 8 10
-0.05
-0.05
-0.1
j(A/cm²) -0.1 -0.15

j(A/cm²)
-0.2
-0.15
-0.25
E=-1.52 V
E= -1.52 V
-0.2 E=-1.58 V -0.3 E= -1.58 V
E=-1.61 V (b)
(a) -0.35 E= -1.61 V
-0.25 E=-1.75 V E= -1.75 V
-0.4

Fig. 6. Current transients for initial stage of Zn–Mn electrodeposition on steel at cathodic potentials ranging between −1.52 and −1.75 V; (a): bath 1 (b): bath 2.

a high percentage of Zn. Meanwhile, it is striking to note that the
magnitude of the anodic peak recorded from the bath 1 is the small-
est. This denotes that rising Mn2+ concentration in the electrolytic
bath decreases the Zn amount in the Zn-Mn alloy deposited dur-
ing the cathodic sweep and consequently favors Mn incorporation
in the Zn–Mn coatings. The decrease of anodic peak magnitude
is also probably due to additional inhibiting effect of Mn2+ ions
towards Zn reduction. These observations support the above sug-
gestion according to which Zn–Mn deposits richer in Mn may be
obtained as Mn2+ concentration in the electrolytic bath increases.
On switching the potential scan to the anodic direction from
−2 V, the absolute value of the current density is greater than that
observed during the potential scan in the cathodic direction, lead-
ing to two crossover: a nucleation overpotential (E) at the cathodic
region and a crossover potential at zero current region (Eco), which
is equal to the reversible metal/ion potential [35]. This is character-
istic of three dimensional (3D) nucleation and subsequent crystal
growth process [36].
3.3. Transients analysis
To better understand the phenomenon of Zn–Mn alloy nucle-
ation mechanism during the early stage of deposition, different
current transients recorded from bath 1 and 2, in a potential win-
dow between −1.52 and −1.75 V vs. Ag/AgCl, are shown in Fig. 6.
These transients exhibit similar behavior; the transients can be
divided into three regions. In the first region, an initial decrease
in the current is related to the charging of the double layer [37].
The second region corresponds to an increase in the cathodic cur-
rent density until a maximum current value jmax reached at a
time tmax . This step is due either to the growth of a new phase
and/or to an increase of the number of nuclei [37]. The third region
corresponds to a plateau of current density which is typical to a
diffusion-controlled process [37].
As the deposition potentials are more negative, jmax increases
in magnitude, denoting arise of the nucleation and growth rate.
Similarly, jmax increases as Mn salt concentration in the electrolytic
bath is higher.
Scharifker and Hills [38] developed a theoretical model to ana-
lyze the current-time transient results of chronoamperometric
experiments. According to this model [39], there are two limiting
nucleation mechanisms: the instantaneous and the progressive.
Instantaneous nucleation corresponds to a slow growth of nuclei
on a small number of active sites; all are activated in the same time.
So, the number of nuclei would be constant during the deposition
process and all nuclei have similar age and size [38]. In return, pro-
gressive nucleation corresponds to fast growth of nuclei on many
active sites, all activated during the course of electro-reduction
[40]. The number of nuclei increases during the process.Thus, the
age of nuclei will be different [41].
The experimental chronoamperometric data, shown in Fig. 6,
are normalized to a non-dimensional plots (j/jmax )2 vs. t/tmax and
compared with the theoretical plots derived for instantaneous
and progressive three-dimensional (3D) nucleation/growth models
[38], whose equations are given for instantaneous (2) and progres-
sive nucleation (3):
 j 2 1.9542
   t 2
= 1 − exp −1.2564 (2)
jmax t tmax
tmax
 j 2    t 2  2
1.2254
= t
1 − exp −2.3367 (3)
jmax tmax
tmax
The theoretical (instantaneous and progressive) and experimen-
tal results for Zn–Mn electrodeposition from bath 2 and bath 1 are
presented in Figs. 7 and 8, respectively. Fig. 7 shows the nucleation
mechanism of Zn–Mn alloy deposition from bath 2, containing the
lowest Mn2+ ions. The two curves recorded at potentials of −1.52
and −1.58 V do not confirm to either of the models of diffusion-
controlled 3D nucleation, however, the rising parts of the transients
are located near to the progressive nucleation. As soon as the
potential turns to more negative values, the nucleation process
confirms well the progressive nucleation process. But at longer
time (t > tmax ), the experimental (j/jmax )2 is much larger than that
calculated from the theoretical model. Two facts can explain this
behavior: hydrogen reduction, as reported by other authors, and
manganese incorporation in Zn–Mn deposits [42,43].
On the other hand, Fig. 8 related to the nucleation mechanism
of Zn–Mn alloy deposition from bath 1, shows that the initial parts
of the transients recorded at potentials ranging between −1.52
and −1.61 V vs. Ag/AgCl match the progressive nucleation (t < tmax ).
These results indicate that during the initial stage of Zn–Mn elec-
trodeposition on steel substrate, the reaction sites on the surface
are activated progressively. The number of formed nuclei is less
than the maximum saturation value and the new nuclei begin to
grow progressively [43].
As shown also in Fig. 8, an increase in potential deposition until
E = −1.75 V induces a deviation in the 3D nucleation mechanism.
The current time is well fitted by the progressive nucleation model,
at the initial stage (t/tmax )=1, and approaches to the instantaneous
model till around (t/tmax )=2.
The above data prove that as soon as the applied potential is
shifted to more negative values, the nucleation process is modified,
suggesting that Mn is probably being more incorporated into the
deposits. It must be also stressed that the nucleation mechanism
for Zn–Mn electrodeposition is not extremely affected by the Mn2+
ions concentration in the electrolytic bath.
 N. Loukil, M. Feki / Applied Surface Science 410 (2017) 574–584
Fig. 7. Non dimensional plots (j/jmax )2 vs (t/tmax ) of the chronoamperometric curves for Zn–Mn electrodeposited from bath 2.
3.4. Galavanostatic deposition and characterization of Zn–Mn
coatings
3.4.1. Effect of Mn2+ concentration in the plating bath on
deposition potential Ed , Mn content and current efficiency
Electrodeposition can be performed by controlling either the
potential or current. In industrial coatings preparation, the cur-
rent step method, also known as the galvanostatic method, is the
most practical [44]. The advantage of the galvanostatic method is
that the thickness of the as-deposited layer can be easily controlled
according to the Faraday’s law [45].
According to voltamogramm data described in Fig. 5, it is clear
that Zn2+ ions reduction is already under diffusion control before
Mn is being electrodeposited. Therefore, co-deposition of Mn and
Zn as well as formation of Zn–Mn alloys with different composi-
tions, by changing the current density, seem to be possible. On
the basis of this assumption, the applied current densities jimp
should be superior to the limiting current density of Zn deposi-
tion in attempt to obtain Zn–Mn alloys with high Mn amount.
Galvanostatic experiments were carried out in a range of current
density varying from 40 to 200 mA/cm2 . Fig. 9 presents the evolu-
tion of the deposition potential Ed during Zn–Mn electrodeposition
from the two working baths: bath 1 ([Mn2+ ] = 1 M) and bath 2
([Mn2+ ] = 0.3 M).
As seen, a further increase in current density jimp into the same
bath leads to a notable shift of Ed towards lower values. For instance,
579
Zn–Mn alloys deposited from the bath 1, comprising 1 M of Mn2+
ions concentration, at 40, 60, 80, 140 and 200 mA/cm2 exhibit an
average deposition potential Ed −1.52, −1.58, −1.61, −1.75 and
−2 V vs. Ag/AgCl, respectively.
Similarly, it is clear that rising Mn2+ ions concentration mod-
ifies the shape of the chronopotentiometric curves. At the same
deposition condition (jimp = cte), reduction potentials Ed are sig-
nificantly shifted towards more negative values when Mn2+ ions
concentration is higher.
Fig. 10 shows the Mn content into the Zn–Mn alloys electrode-
posited from the two baths 1 and 2 at different current densities
jimp . Namely, the Zn–Mn alloys deposited from bath 1 contain a
greater amount of Mn as compared to that obtained from bath
2. Comparing Ed at a constant current density jimp = 40 mA/cm2
(Fig. 9), the deposition potential Ed moves from −1.31 to −1.52 V
vs. Ag/AgCl, 210 mV is more negative, when the Mn2+ ions con-
centration increases from 0.3 to 1 M, respectively. As a result, the
Mn content into the Zn–Mn film is enhanced from 0.3 to 0.98 wt%
(Fig. 10). Thus, increasing Mn2+ concentration is obviously benefi-
cial for an easier Mn incorporation. This is in agreement with the
basic principles of normal alloy electrodeposition [46].
The composition analysis of these alloys indicates that Mn
co-deposition is only possible if the current density is equal to
40 mA/cm2 . Further experiments, conducted at current densities
lower than 40 mA/cm2 (Results are not shown), revealed that
no Mn has been incorporated in the coatings implying that the
580 N. Loukil, M. Feki / Applied Surface Science 410 (2017) 574–584

Fig. 8. Non dimensional plots (j/jmax )2 vs (t/tmax ) of the chronoamperometric curves for Zn–Mn electrodeposited from bath 1.

current density of the onset manganese deposition is estimated to
be about 40 mA/cm2 . Besides, it is stressed to note that there is a
critical value [16,47] of the deposition current density where Mn
content is rapidly improved. As it can be seen in Fig. 10, regardless
the electrolytic bath, this value is about 60 mA/cm2 . This value is
so close to that of 50 mA/cm2 stated in a previous study on Zn–Mn
deposition from additives-free electrolyte [47].
As soon as the deposition current density is higher than
40 mA/cm2 , as Ed is lower and thus becomes closer to that of Mn
(Fig. 9). This will facilitate the deposition rate of the less noble
metal, Mn. Whatever the electrolytic bath, an appreciable increase
in the Mn content is observed with increasing jimp (Fig. 10). Similar
results have been pointed out [2,16] that the increase in deposi-
tion current density is beneficial for enhancing Mn content into
Zn–Mn alloy. This significant increase in Mn amount is explained
by the fact that the deposition current density is applied where
Zn2+ ions are reduced under diffusion limiting current density.
Thus, further increasing in current density (i.e. corresponding to
more negative cathodic potentials) enhances merely the Mn depo-
sition and hydrogen evolution reaction [15]. However, there is
a small decrease in the Mn amount at higher current densities
(200 mA/cm2 ), as shown in Fig. 10. This limitation of Mn co-
deposition might be attributed to a certain inhibitor effect caused
by the concomitant hydrogen evolving reaction [47]. Indeed, in
spite of the descending shift of the deposition potential Ed (Fig. 9),
the Mn content is almost stable at very high current densities,
revealing subsequently a significant strengthening of the hydrogen
evolving kinetic at high current densities. This intensive hydrogen

Fig. 9. Potential-time transients for Zn–Mn alloy electrodeposition from the two electrolytes bath 1 and bath 2 at various current densities (jimp ).
 N. Loukil, M. Feki / Applied Surface Science 410 (2017) 574–584
Fig. 10. Dependence of Mn content in Zn–Mn alloys on the current density from
two acidic chloride baths (bath 1 and bath 2).
95
85
current efficiency (%)
75
65
55
45
0 50 100 150 200
jimp (mA/cm²)
Fig. 11. Current efficiency for Zn–Mn alloys deposition from (bath 1 and bath 2) at
different current densities.
evolution causes probably a detachment of Zn–Mn alloys in the
form of fine powders from the cathode causing a loss of final weight
of the Zn–Mn coatings electrodeposited at high current densities
[47]. This plausible reason explains the fall in the current efficiency
at high current densities, as shown in Fig. 11. Such occurrence has
been reported in recent investigations on Zn–Mn coatings [6,47].
As shown in Fig. 11, the highest current efficiency is observed at
low current density. This finding is very close to the results reported
by Bucko et al. [16]. Moreover, it should be underlined that the
cathodic current efficiency increases with the raise of Mn2+ con-
centration in the electrolytic bath [26]. In this regard, Ganesan and
his co-workers [6] demonstrated that hydrogen evolution reaction
decreases with increasing Mn2+ concentration from around 0.4 to
2 M.
3.4.2. Effect of stirring on Mn content
Taking into account all previous considerations, namely the cur-
rent efficiency and the Mn content, bath 1, containing 1 M of MnCl2 ,
was retained to study the effect of stirring and to characterize
Zn–Mn alloys. Fig. 12 illustrates the Mn content in the Zn–Mn plated
without and with stirring of the solution, at different applied cur-
rent densities jimp . As can be seen in Fig. 12, stirring of the solution
decreases abruptly the Mn amount. Previous studies showed simi-
lar results [15–34]. It may be assumed that stirring of the electrolyte
enhances electrodeposition of Zn. This could be due either to an
acceleration of the diffusion controlled Zn2+ reduction [15] or to
the removal of hydrogen bubbles from the metallic surface by the
stirring that leads to an increase of its active area and consequently
to a decrease in the real current density [34].
581
14 without stirring
with stirring
12
10
% Mn in alloy
8
0
0 50 100 150 200 250
jimp (mA/cm2)
Fig. 12. Effect of stirring the solution on Mn content in Zn–Mn alloys electrode-
posited from bath 1.
bath 1
bath 2
3.4.3. Effect of the applied current density jimp on the morphology
and crystallographic structure of Zn–Mn alloys
The effect of current density jimp on the morphology and
structure of Zn–Mn deposits obtained from bath 1 were inves-
tigated using SEM and XRD, respectively. Visual examination of
the obtained Zn–Mn deposits indicates that all deposits cover
completely the substrate surface and their appearance depends
systematically on jimp .
At same deposition conditions (jimp = cte), it should be stated
that the Zn –Mn coatings electrodeposited from the both baths
250 (bath 1 and bath 2) show a similar morphology. Nevertheless, some
differences can be observed as current density jimp increases for the
same electrolytic bath. On the basis of visual observations, Zn–Mn
coatings electrodeposited at low current density seem to be gray
colored and slightly dendritic, whereas those produced at high val-
ues, containing an enhanced Mn content, are darker, porous and
powdery. The difference in color may be due to Mn content into
the deposits. These visual observations are in good agreement with
the literature results [6,16].
According to SEM examination of the Zn–Mn deposits, the mor-
phology varies from fine grains to coarse grains as jimp increases.
These observations reveal that a further incorporation of Mn into
the Zn matrix alters significantly the surface morphology of the
Zn–Mn alloys.
Moreover, a large quantity of dendrites is clearly observed, par-
ticularly on the edges of Zn–Mn deposits, when the jimp increases.
As mentioned earlier, the co-evolution of hydrogen is a strong con-
comitant reaction when Mn2+ reduction occurs. In fact, hydrogen
bubbles formation leads subsequently to a poorly adherent, den-
dritic and rough coatings (observed by naked eye) [6,47,49]. This
finding is more pronounced for Zn–Mn deposited from the bath 1 at
200 mA/cm2 . As denoted previously in the corresponding transient
curve at this current density (Fig. 9), the descending evolution of
Ed for longer deposition time may be ascribed to an increase of the
effective cathodic area. So, this increase seems to be linked to this
particular morphology.
To illustrate the effect of current density on surface morphology
and structure properties, SEM micrographs of two selected sam-
ples deposited at 60 and 140 mA/cm2 are presented in Fig. 13 (a, c).
Fig. 13-a presents the Zn–Mn coating produced at low current den-
sity (60 mA/cm2 ). The latter exhibits a homogeneous deposit with
hexagonal crystals. A more dendritic morphology is observed in the
sample obtained at 140 mA/cm2 (Fig. 13c), but in this case the den-
drites show coarse-grained deposit with non-uniform crystal size.
This Zn–Mn deposit is clearly more porous, due to hydrogen evolu-
tion during Zn and Mn co-deposition. This agrees well with results
582 N. Loukil, M. Feki / Applied Surface Science 410 (2017) 574–584
Fig. 13. SEM micrographs and X-ray diffraction patterns of two Zn–Mn samples deposited onto steel substrate from bath 1 at different current densities (a–b): 60 mA/cm2 ;
(c–d): 140 mA/cm2 .
previously stated [16,48,50], evidencing that a dendritic shape is
characteristic of metal coatings deposited at very negative deposi-
tion potentials (i.e. high current densities) as the growth process is
under diffusion control.
Fig. 13(b, d) show typical diffractograms for the two selected
Zn–Mn coatings electrodeposited from bath 1. Only peaks whose
relative intensity is above 30% are considered. The X-ray diffraction
pattern of the considered Zn–Mn coatings reveal that jimp affects
significantly the structure of the obtained deposits.
The phases were identified after an accurate analysis of the peak
positions and comparison with structural parameters obtained in
previous works on Zn–Mn alloys electrodeposited from chloride
acidic baths [27,34,51]. It can be stated from Fig. 13b that the film
electrodeposited at 60 mA/cm2 , containing 5.5%, Mn is tri-phasic
consisting of three crystalline phases. An additional diffraction peak
corresponding to the Fe substrate is also detected. The XRD diffrac-
togram (Fig. 13b) shows a mixture of ␩ Zn (a solid solution of less
than 1% of Mn in Zn) and intermetallic Zn–Mn phases with differ-
ent crystallographs namely, monoclinic ␨-MnZn13 [15] and ␧-HCP
(Hexagonal Close Packed) with crystal orientations (101) and (112).
Very similar structure properties were reported in a previous work
[34] dealing with Zn–Mn coatings deposited from an acidic chloride
bath. The two crystalline phases ␨-MnZn13 and ␩-Zn detected in the
XRD diffractogram corresponding to the sample electrodeposited
at 60 mA/cm2 may have their origin in the high Zn content and
subsequently the low Mn amount (5%) in the coating [34]. Results
previously obtained from acidic chloride bath [15] confirm also the
result of the present work. Sylla et al. [15] demonstrated that ␧-
Zn–Mn was the main phase detected. Similarly, in this work, the
␧-HCP (101) is the major phase in the XRD pattern (Fig. 13b), while
the two others detected phases appear with weak reflection lines.
Several works [2,34] reported that the Zn–Mn coatings consisting
of only ␧-Zn–Mn phase provide the best corrosion protection.
It is striking to note that the ␩-Zn phase [51] has also Hexago-
nal Close Packed (HCP) structure. Thus, the hexagonal morphology
observed in SEM photograph is basically attributed to this phase.
Such occurrence is in agreement with the results of Ortiz et al. [51].
Contrary to the Zn–Mn deposited at low current density
(60 mA/cm2 ), the diffractogram corresponding to the Zn–Mn
deposited at higher current density (140 mA/cm2 ), containing
11.4% of Mn, seems to be metallic glass or amorphous [16,21]. It
is clear from Fig. 13d that there are no significant signal attributed
to the crystalline structure of Zn, Mn or Zn–Mn alloy. This indicates
a transition of the Zn–Mn deposit from crystalline, at low current
density, to an amorphous structure at high current density. This
finding also corroborates that reported by Gong et al. who investi-
gated electrodeposition of Mn [28,52,53] and Mn alloys [49]. These
authors noticed that after exceeding a critical deposition current
density, a transition from crystalline to amorphous structure may
occur in the Mn alloy electrodeposits such as (Sn–Mn) [49]. The
crystalline to amorphous transition in Mn and Mn alloys is due to
the extremely high nucleation rate induced by the high applied
overvoltage and by the strong hydrogen evolution and potential
incorporation [49,50].
Visual examinations denote that Zn–Mn coatings obtained
under high current densities are dark tending to be black deposits,
particularly at the edges of Zn–Mn samples. According to literature
[54], the oxy/hydroxide compounds are responsible for the black
appearance. Likewise, black Mn deposits obtained at high current
densities are well documented [21]. Additionally, recent research
 N. Loukil, M. Feki / Applied Surface Science 410 (2017) 574–584
[28] demonstrated the formation of black films at the edges of
Mn samples at current densities above 150 mA/cm2 . This finding
confirms then that the oxy/hydroxide inclusions are strongly incor-
porated into Zn–Mn deposits.
The most probable explanation for oxy/hydroxides formation is
the intense hydrogen evolution occurring in parallel to Zn–Mn co-
deposition at high current densities. Because this large amount of
hydrogen gas evolved at the cathode surface, hydroxyl ions (OH− )
are abundant in the near-cathodic layer. Local pH in the vicinity
of the cathode surface becomes then much higher than that of the
bulk solution, leading to a quick alkalization of the metal/solution
interface [17–26]. It is well known that the hydroxides forma-
tion Zn(OH)2 and/or Mn(OH)2 is excessively occurring at high pH
resulting at the cathode surface. Pourbaix [55] stated that pH at
which insoluble Zn(OH)2 and Mn(OH)2 starts to precipitate are
around 5.5 and 7.5, respectively. Bucko et al. [16,47] studied exten-
sively the Zn–Mn co-deposition and reported that the buffering
effect ascribed to boric acid and the complexation with Cl− ions
can prevent hydroxide formation only to a limited extent, but the
formation of Zn(OH)2 and Mn(OH)2 can occur at sufficiently high
pH.
Several authors [28,50,54] demonstrated that hydroxide com-
pounds greatly inhibit crystal growth and subsequently lower
appreciably the current efficiency, as demonstrated above in Fig. 11.
Hence, Zn–Mn coatings predominantly grow as hydroxides at high
current densities.
4. Conclusion
Zn–Mn coatings were successfully electrodeposited on steel
substrate from an additives-free chloride bath at current den-
sities superior to the limiting current density of Zn deposition.
An electrochemical investigation of Zn–Mn electroplating process
with different Mn2+ ions concentration (0.3 and 1 M) has been
conducted. Results revealed that the increase in Mn2+ ions con-
centration enables its faster reduction on the cathode and acts as
inhibitor towards Zn deposition.
A dimensionless graph model was used to analyze the effect of
both Mn2+ ions concentration and the applied cathodic potential on
Zn–Mn nucleation process. This study showed that the initial stage
of Zn–Mn electroplating depends mainly on the applied potential.
Several deposition parameters were explored in this study,
namely Mn2+ ions concentration, current density and stirring con-
ditions. Their effects on the Zn–Mn electroplating process, i.e. the
resulting Mn content into the coatings, the current efficiency as
well as the coating morphology were investigated. To sum up,
results showed that Mn content in Zn–Mn coatings is significantly
enhanced with the increasing of either Mn2+ concentration or the
applied current density, in particular. Indeed, chronopotentiometry
results display that increasing of each those two deposition condi-
tion, the deposition potential Ed is shifted towards more negative
values, close to that of Mn. This, in turn, favors Mn incorporation
into the deposit.
Moreover, it was concluded that the electrolytic bath containing
1 M of Mn2+ shows a simultaneous improvement of both cathodic
current efficiency and Mn content. For this reason, the electrolyte
containing 1 M of MnCl2 was selected as a better solution to conduct
further experiments.
Increasing the current density far from the limiting current den-
sity of Zn deposition generates an increase in the Mn amount
in Zn–Mn alloys electrodeposits. The Mn content is markedly
improved at a critical current density of 60 mA/cm2 . However, a fur-
ther increase in the current density until 200 mA/cm2 has a reverse
effect and causes a decrease in Mn content. This finding is due
583
mainly to hydrogen evolution that becomes excessively intense at
high current densities.
The deposition current density significantly affects the surface
morphology and crystal structure. XRD studies shows that the
Zn–Mn alloy electrodeposited at a low current density, more accu-
rately at 60 mA/cm2 , is tri-phasic and containing mainly a mixture
of ␩ Zn, ␨-(MnZn13 ) and ␧-HCP. Meanwhile, in the case of a high
current density, i.e. 140 mA/cm2 , the Zn–Mn coating is amorphous.
This transition from crystalline to amorphous structure is certainly
due to the incorporation of non-metallic hydroxide inclusions in
the Zn–Mn alloy electrodeposits at high current densities.
Acknowledgement
This work was supported by the Ministry of High Education and
Scientific Research, Tunisia.
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