Journal of Alloys and Compounds 719 (2017) 420e428

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Journal of Alloys and Compounds

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Synergistic effect of triton X100 and 3-hydroxybenzaldehyde on Zn-Mn

electrodeposition from acidic chloride bath
N. Loukil*, M. Feki
Laboratory of Material Engineering and Environment, ENIS, Sfax, Tunisia

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

Article history: The effect of two non-complexing additives, namely Triton X100 and 3-hydroxybenzaldehyde (3-HBA) on
Received 4 March 2017 Zn-Mn alloy deposition was investigated. The study was carried out using a simple KCl-based bath. To
Received in revised form this end, cyclic voltammetry associated to the switching potential method, bulk electrolyses and scan-
6 May 2017
ning electron microscopy were used. Electrochemical study, from additives-free bath, showed that the
Accepted 14 May 2017
potential of beginning Zn-Mn alloy deposition (E ¼ 1.52 V vs. Ag/AgCl) stands between those of Zn
Available online 15 May 2017
(E ¼ 1.03 V) and Mn (E ¼ 1.65 V) alloying elements. The coatings obtained from this bath are Mn-poor
alloys with dendritic structure, and the current efficiency is low (60%). It was found that the conjunction
Keywords:
Electrodeposition
of triton X100 ad 3-HBA suppresses completely the individual electrodeposition of Zn. The synergistic
Zn-Mn alloys effect of additives favors Zn and Mn co-deposition, but Mn-rich alloys are deposited only from E ¼ 1.8 V
Triton X100 vs. Ag/AgCl. The coatings obtained at lower cathodic potentials are adherent, smooth and bright. The
3-HBA current efficiency is enhanced and reaches 85%. Voltammogram data, from a comparative study using
polyethylene glycol (PEG8000) instead of triton X100, display prominently the vital role that plays the
hydrophobic head of triton X100 molecule in enhancing Mn incorporation into Zn matrix. Moreover, the
switching potential technique demonstrated that at cathodic potentials higher than 1.8 V, the hydrogen
evolution reaction is catalyzed when Mn-rich are deposited such that it gives rise to a higher pH increase
at the cathode surface. This pH increase leads to an intense precipitation of hydroxides that blocks the
alloy deposition process.
© 2017 Published by Elsevier B.V.

1. Introduction content show the highest corrosion resistance among Zn alloys

Electrodeposited Zinc has for long time been widely used to
protect mild steel from corrosion. However, the high dissolution
rate of Zn coatings, in severe aggressive environments where so-
dium chloride and/or sulfur dioxide are present, limits the service
life of Zn coatings [1]. To overcome this problem, various Zn-based
alloys were considered to meet demands for longer lasting coatings
finishes [2]. Among the various Zn-based alloys, Zn-Ni, Zn-Co and
Zn-Fe have received the widest attention in industry [1e4]. In
recent research on Zn-based binary, several authors have found Zn-
Mn alloys have markedly attractive features not only in plating
industry but also in potential magnetic applications [1,5] and in
hydrometallurgical process for recycling of spent Zn-Mn batteries
[6]. On the basis of several corrosion studies in aggressive media, it
has been reported that Zn-Mn coatings containing 10e30% of Mn
* Corresponding author.
E-mail address: nloukil87@gmail.com (N. Loukil).
[7e9].
To derive benefit from the advantages of Zn-Mn deposits, many
efforts have been made to overcome the difficulties arising from the
co-deposition of the alloying elements Zn and Mn. These difficulties
arise from the following facts i): the large gap between the stan-
dard potentials of Zn (E (Zn2þ/Zn) ¼ 0.76 V/HSE) and Mn (E
(Mn2þ/Mn) ¼ 1.18 V/HSE), ii) these two potentials are notably
more negative than that of hydrogen evolution reaction, and iii) Zn-
Mn coatings are obtained under the so-called normal co-
deposition.This means that electrodeposition of the less noble Mn
is unfavored in comparison with Zn [2,10]. For these reasons, co-
deposition of Zn and Mn, and notably the elaboration of Mn-rich
coatings, is a difficult issue. Consequently, the electrolytic bath
should be judiciously formulated. The common way to permit co-
deposition of these alloying elements is to shift the deposition
potential of Zn closer to that of Mn, by using a strong organic
complexing agent [11e14]. However, the important drawbacks of
the numerous baths thus formulated, notably those related to

http://dx.doi.org/10.1016/j.jallcom.2017.05.142
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 N. Loukil, M. Feki / Journal of Alloys and Compounds 719 (2017) 420e428
process control and current efficiency [15,16] seem to explain why
no commercial application has appeared so far [2]. Alternative
baths were suggested, for instance those based on ammonium salts
(NH4Cl, (NH4)2SO4, NH4SCN), since ammonium species favor the
incorporation of Mn in the Zn matrix [17,18].
Regardless of the mentioned drawbacks, these baths pose an
environmental problem related to the use of ammonium salts and
organic complexing agents [2e21]. Indeed, the organic ligands and
ammonia (from NH4þ species) hinder or completely inhibit metal
hydroxide precipitation during the treatment of the related
wastewater by the widespread neutralization/precipitation tech-
niques [2e19]. To avoid the adverse effects of complexing agents on
Zn-Mn deposition process, another pathway has been next tried.
This path involves the use of suitable surfactants (called potential
additives by some authors [20,21]), acting by adsorption on the
cathode surface and shifting thus the reduction potential of Zn2þ
ions towards that of Mn2þ species. Nevertheless, the list of sur-
factants tested for Zn and Mn co-deposition from simple KCl-based
baths was appreciably shorter, including PEG (polyethylene glycol)
of unknown molecular weight [20] and a commercial additive,
named FRA 700, commonly used for pure Zn plating industry [21].
It is striking to note that no more data about FRA700 are reported
by authors, as it is a proprietary additive. According to results re-
ported in Ref. [20], PEG investigated in different concentrations
does not significantly reduce the gap between the deposition po-
tentials of Zn and Mn. Independently of the extent of improvement
in current efficiency and Mn content, it is obvious that the use of
these potential additives instead of complexing agents presents a
considerable advantage from an environmental viewpoint.
The scope of the present work was to study the effect of two
selected non complexing additives on Zn-Mn alloy electrodeposi-
tion process. For this purpose, an acidic potassium chloride bath
was chosen. The chloride bath was retained since it possesses a
number of intrinsic advantages, among them the ability to plate
satisfactory on cast iron and carbonitrired steel and the easy
treatment of wastewater by the common neutralization/precipita-
tion technique [2,19,21].
The two used additives were: Triton X100, a non-ionic poly-
ethoxylated surfactant and 3-hydroxybenzaldehyde (3-HBA). These
additives were selected on the basis of a set of preliminary exper-
iments using different organic compound types, commonly known
as non complexing plating additives.It is to be noted that no data
have been earlier reported in the literature concerning the effect of
neither triton X100 alone nor a mixture of triton X100 and 3-HBA on
Zn-Mn alloy electrodeposition from acidic potassium chloride bath.
To conduct this study, the individual influence of triton X100 and
3-HBA on the electrodeposition mechanism of Zn, Mn and Zn-Mn
was first investigated. Thereafter, the effect of both additives on
Zn-Mn deposition process was examined. For comparison, an
additive-free electrolyte was used as reference.
Cyclic voltammetry associated to the switching potential vari-
ation method was used for detailed investigations of the influence
of the individual and joint influence of organic additives on the
reduction mechanism of Zn-Mn electrodeposition. To confirm the
most relevant data obtained from the voltammograms, bulk elec-
trolyses at fixed cathodic potentials, followed by chemical analysis
were carried out. To complement this electrochemical study, a
morphological characterization of electrodeposited Zn-Mn coatings
was realized.
2. Material and methods
2.1. Electrolyte preparation
Electrodeposition study of Zn-Mn coatings on carbon (or mild)
421
steel was performed using an acidic chloride electrolyte. The
composition of the base electrolytic bath S0 (additive-free bath)
was judiciously formulated in the laboratory. All reagents used
were analytic grade.
For comparison, individual electrodeposition of Zn and Mn
coatings was firstly studied on steel from the base electrolyte
devoid of ZnCl2 salt (bath S1) or MnCl22H2O salt (bath S2), respec-
tively. All acidic baths compositions are gathered in Table 1.
Thereafter, Zn-Mn co-deposition was investigated from bath S0
before and after adding the additives.
The electrolyte pH was regularly adjusted to 5.2 using dilute
hydrochloric acid (HCl) or potassium hydroxide (KOH) solution. All
experiments have been conducted at room temperature (25  C).
The used additives in the present study, namely: triton X100
(octylphenolpoly(ethylenglycolether)n, n ¼ 10) and 3-HBA have the
chemical structures shown in Fig. 1.
Triton X100 belongs to the class of nonionic surfactants [22]. It is
a water-soluble compound owning to its hydrophilic group [22,23].
However, for the used bath S0 which is highly charged in salts, in
particular KCl, turbidity was observed just after the addition of
triton X100 to the bath. It is to note that nonionic surfactants in
aqueous solutions may cloud or become turbid by way of des-
olvation [24]. To overcome this salting-out effect [25], sodium
isopropyl benzene sulphonate (Sodium Cumene sulphonate SCS), a
hydrotrope agent [24], was added in a proportion of (3/2) in volume
compared to triton X100 into the bath S0 to enhance triton X100
solubility. Indeed, hydrotropes have the ability to prevent the
clouding process. It is known that short-chain alkyl benzene
sulphonates increase the cloud points (CPs) of a nonionic surfactant
[24]. All experiments were performed with homogenous and stable
working baths.
2.2. Electrochemical studies and coatings electrodeposition
For studying Zn and/or Mn electrodeposition mechanism, cyclic
voltammetry experiments were carried out in a conventional three
electrode cell using an Autolab potentiostat, PGSTAT302N,
controlled by NOVA 1.8 software allowing data acquisition. The
potential scan was initiated in the cathodic direction from the OCP
(EOCP ¼ 0.59 V vs. Ag/AgCl) and then switched to the positive
direction. Unless otherwise stated, the switching potential is fixed
at 2 V vs. Ag/AgCl. The scan rate was fixed at 20 mV/s.
Zn-Mn coatings were electrodeposited potentiostatically under
different cathodic potentials using a rectangular cell with 250 ml
capacity. The used electrodes were connected to a digital dc power
supply (hp) providing current and voltage in the ranges of 0e2 A
and 0e8 V.
The working electrodes were a carbon steel disk of 1 cm
diameter for electrochemical tests and carbon steel panel with an
active surface of 12 cm2 for electrolysis experiments. The disk
specimens were cold covered in epoxy resin. Prior to each experi-
ment, the working electrode surface was first mechanically pol-
ished with various grades of silicon carbide papers (up to 600 grit).
Then, it was degreased in alcohol and pickled in hydrochloric acid
Table 1
Composition of the acidic electrolytic baths.
Chemical element Concentration (M)
S0 S1 S2
KCl 3.2 3.2 3.2
H3BO3 0.4 0.4 0.4
ZnCl2 0.4 e 0.4
MnCl2 2H2O 0.4 0.4 e
422 N. Loukil, M. Feki / Journal of Alloys and Compounds 719 (2017) 420e428

Fig. 1. Structural formula of (a): 3-HBA; (b): Triton X100.

medium (10%) for 30 s just before use. (a) 0.05

As stated in our previous work [26], using a Pt as a counter
electrode generates an electrochemical oxidation of Mn2þ ions to E (V vs. Ag/AgCl)
0
MnO2 that leads to a decrease of the bath conductivity. Besides to -2.2 -2 -1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
that, chlorine is anodically evolved. Hence, Pt seems to be unde-
-0.05
sirable in the commercial process. To avoid these drawbacks, a
soluble pure Zn plate was used as a counter electrode for both
electrochemical and bulk electrolysis studies. All potentials were -0.1

referred to Ag/AgCl reference electrode.

j(A/cm²)
-0.15

2.3. Morphology and chemical composition of the coatings

-0.2
The surface morphologies of the electrodeposited Zn-Mn coat-
ings were observed using JEOL 5410 Scanning Electron Microscopy -0.25
S1
(SEM). To determine the Zn and Mn content in each deposit, the
KCl + H3BO3
latter was stripped from the working electrode surface in dilute -0.3
H2SO4 solution (1 M) containing 2 g/l hexamethylenetetramine
(HMTA) as dissolution inhibitor for the steel substrate. Then, Zn and -0.35
Mn concentration in the obtained solution was determined by
atomic absorption spectrometry (Analytic Jena ZEENIT 700). For
(b)
each deposit, the quantitative analysis was realized in triplicate. 0.4

3. Results and discussion S2

S0 0.3
3.1. Cyclic voltammetry studies of the electrodeposition of Mn, Zn
and Zn-Mn without additives
0.2
3.1.1. Mn electrodeposition
Typical cyclic voltammogram obtained on steel from solution S1
without any additive, is shown in Fig. 2-a. For comparison, the same 0.1
figure shows the volatmmogram related to the supporting elec-
trolyte (KCl þ H3BO3; pH ¼ 5.2). E (V vs. Ag/AgCl)
Regarding the voltammogram recorded from the supporting 0
electrolyte (Fig. 2-a), the current density starts to increase sharply -2.2 -2 -1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
j (A/cm²)

from a potential of 1.1 V vs. Ag/AgCl. This current is ascribed to

hydrogen evolution reaction HER. Comparing the two voltammo- -0.1
grams in Fig. 2-a, it can be seen that the reduction curve related to
S1 is shifted towards more negative potentials and characteristic
features, namely: two well defined cathodic peaks and a small -0.2
anodic peak, are clearly observed. In our knowledge, the apparition
of those feature characteristics of Mn electrodeposition on steel
from an acidic chloride bath was not observed in previous works -0.3
during voltammetric studies [9,21,27]. It is to make clear that the
well-defined cathodic peak is preceded by a small one, less clearly
observed. These two cathodic peaks are attributed to Mn electro- -0.4
deposition. For the first small peak, the cathodic current density
increases below around 1.5 V vs. Ag/AgCl and achieves its Fig. 2. (a): Cyclic voltammograms recorded from the supporting electrolyte and for Mn
electrodeposition in the additive-free electrolytic bath S1; (b): Cyclic voltammograms
maximum at approximately 1.55 V vs. Ag/AgCl. The second broad
for Zn and Zn-Mn electrodeposition in the additive- free electrolytic baths S2 and S0,
cathodic peak, corresponding to the bulk deposition of Mn, starts to respectively.
appear at around 1.65 V vs. Ag/AgCl and achieves its maximum
 N. Loukil, M. Feki / Journal of Alloys and Compounds 719 (2017) 420e428
at 1.8 V vs. Ag/AgCl. The last broad peak is followed by a current
hump ascribed to hydrogen evolving which occurs faster than that
observed from the supporting electrolyte. This is to say, the slope of
the HER curve from S1 is higher than that obtained from the sup-
porting electrolyte. This means that Mn deposited during the
cathodic sweep enhances HER. This result confirms the assumption
of some authors who stated the Mn catalytic effect for HER [10]. In
this connection, it is interesting to remember that Mn is extensively
used as alloying metal for Ni in order to increase its electrochemical
activity for hydrogen evolution reaction [28]. Concerning the low
cathodic current density observed in the potential range from
approximately 1 V up to 1.5 V vs. Ag/AgCl, it is also related to
HER. Indeed, Diaz et al. [29] demonstrated, using an electro-
chemical quartz crystal microbalance EQCM for studying pure Mn
electrodeposition from a chloride bath, that Mn electrodeposition
does not occur in this potential range. However, hydrogen evolu-
tion reaction takes place slightly [29]. Under these conditions, the
weakness of current density observed for HER from S1, in the po-
tential range from 1 to 1.5 V vs. Ag/AgCl, suggests that Mn2þ ions
inhibit HER before metallic Mn is electrodeposited. Similar Mn2þ
inhibition effect has been reported in previous works dealing with
Mn electrodeposition from solutions containing less than 30 g/l
Mn2þ ions [9,30]. According to Xu et al. [30], this inhibition effect
could be attributed to Mn2þ ions adsorption at the cathode surface,
modifying the HER mechanism. In absence of Mn2þ ions, Hþ is
adsorbed at the cathodic surface and directly discharged. However,
when Mn2þ ions are present, they participate in the HER [30]. As
expressed by Xu et al., further extensive studies are required to
explain this conjecture.
Taking into account the above results, HER reaction is inhibited
by Mn2þ ions before Mn is electrodeposited, while it is then cata-
lyzed by the formed Mn coating. These opposite effects of Mn2þ
species and metallic Mn on the HER, occurring during Mn elec-
trodeposition, were not clearly specified in previous works.
Concerning the two successive reduction peaks observed for Mn
deposition, their apparition at near potentials (Fig. 2-a), associated
to the high magnitude of the second peak, as compared to that of
the first one, signify as a rule that Mn deposition involves the
reduction of two types of Mn2þ ions [31]. According to this rule, the
first little peak is high probably due to the reduction of Mn2þ ions
adsorbed at the cathode surface, while the second intense peak is
linked to the reduction of Mn2þ ions present into the solution [31].
This suggestion supports the adsorption hypothesis previously
advanced when discussing HER inhibition by the adsorbed Mn2þ
ions.
It is striking to note that the characteristic reduction peak,
observed in this work (Fig. 2-a) lets us easily determine the po-
tential of beginning Mn deposition (1.65 V vs. Ag/AgCl). A well-
defined peak has not been observed for Mn2þ reduction in previ-
ous studies dealing with Mn deposition on steel from acidic chlo-
ride bath [19,27,29]. In these works, these authors estimated the
potential values of starting Mn deposition on the basis of the cur-
rent density increase observed during the cathodic-going scan. Still
more, the results of these studies for Mn2þ reduction potential vary
due to the use of different deposition conditions and particularly
electrode materials. Genasan et al. [27], for example, conducted a
cyclic voltammetry study of Mn electrodeposition on Pt electrode
using an acidic chloride electrolyte (pH ¼ 4). No reduction peak(s)
was observed during this study. On the basis of the cathodic current
density variation, the authors estimated that Mn2þ reduction starts
at around 1.6 V/SCE on Pt substrate, and concluded that Mn
electrodeposition study is complicated not only by the interference
of the concomitant hydrogen evolution reaction, but also by the fact
that the deposited Mn is readily oxidized during the anodic sweep.
Coming back to Fig. 2-a, a slight anodic peak starts at 1.33 V vs.
423
Ag/AgCl during the backward scan from -2 V vs. Ag/AgCl. This peak
corresponds to the dissolution of the remaining Mn, already
deposited during the cathodic scan. As shown in Fig. 2-a, the
magnitude of this anodic peak is smaller as compared to that of the
cathodic peak. As stated in previous works [26,29], this finding can
be explained by the easy dissolution during the anodic sweep of the
deposited Mn in acidic bath [21,27,29]. This dissolution takes place
according to a non-faradic process [29].
Concerning the potential at which Mn dissolution peak begins, a
value (1.34 V vs. Ag/AgCl) closer to that observed in this work
(1.33 V vs. Ag/AgCl) has been reported by Rudnik [33] when
studying Mn deposition on glassy carbon electrode from an acidic
chloride bath. Nevertheless, many authors [27,32] reported that no
oxidation peak was shown in the voltammograms recorded during
Mn deposition on steel substrate.
3.1.2. Zn electrodeposition
The voltammogram recorded from the solution S2, containing
only ZnCl2 salts, describes a well-defined reduction peak starting
from 1.03 V vs. Ag/AgCl and centered at approximately 1.2 V vs.
Ag/AgCl. This peak is associated to the reduction of Zn2þ ions,
proceeding in a single step. Next, a new increase in current density
is observed due to hydrogen evolution on the Zn film already
deposited. Such occurrence has been reported in many works
[33,34]. On the positive sweep, an anodic peak begins at 1.06 V vs.
Ag/AgCl, reaching its maximum intensity at a potential of 0.5 V.
This peak is related to the anodic dissolution of Zn electrodeposited
during the cathodic sweep. The high intensity of the anodic peak, in
comparison with that of the cathodic peak, means that Zn depo-
sition carries on during HER. On the other hand, the fact that the
potential at which the dissolution begins is practically closer to that
of the beginning of deposition indicates that the reduction process
is reversible. The same finding has been reported by others authors
[34,35].
3.1.3. Zn-Mn electrodeposition
The addition of Mn2þ ions to the electrolyte S2 (solution S0)
modifies the shape of the cyclic voltammogram, especially at high
cathodic potential values (Fig. 2-b). As shown in this figure, the
cathodic peak observed for Zn deposition at 1.2 V vs. Ag/AgCl is so
similar to that obtained from solution S2 containing only Zn2þ ions,
being appeared approximately at the same potential value. This
peak is followed by current plateau between 1.3 and 1.5 V vs. Ag/
AgCl reflecting a mass-transport controlled reduction of Zn2þ ions.
In return, the corresponding reduction peak for Mn is not so clearly
defined. Nevertheless, a significant increase in the current density
starts from 1.52 V vs. Ag/AgCl. This current density increase could
be attributed to simultaneous Zn and Mn deposition accompanied
by hydrogen evolution [19,27,36]. It is advisable to point out that
hydrogen bubbles were seen by naked eye in this potential range.
At more cathodic potentials (below 1.7 V vs. Ag/AgCl), important
current density fluctuations are observed. Similar fluctuations were
also observed by Boudinar et al. [37] when studying the electro-
deposition of Mn-Bi. The authors attributed these fluctuations to an
intense hydrogen evolution. As far as we are concerned, the origin
of these fluctuations will be discussed later in a next section.
As seen also in Fig. 2-b, when Mn2þ and Zn2þ ions are both
present in the electrolyte, the potential of beginning of Zn and Mn
co-deposition (E ¼ 1.52 V vs. Ag/AgCl) is lower than that observed
for the deposition of Mn alone (E ¼ 1.65 V vs. Ag/AgCl). This
finding is in agreement with the general rule according to which
the deposition potential of an alloy (or of an intermetallic com-
pound) stands usually between those of the alloying elements
taken separately [38]. This observation has not been reported in
previous works dealing with electrochemical studies of Zn-Mn co-
424 N. Loukil, M. Feki / Journal of Alloys and Compounds 719 (2017) 420e428
deposition.
According to Fig. 2-b, the anodic peak seen during anodic scan
shows two shoulders. This suggests that the coating deposited
during the cathodic scan does not contain only pure Zn phase.
Moreover, the decrease of the maximum current density of the
anodic peak can also be due to a diminution of the dissolved pure
Zn quantity, consolidating subsequently a joint deposition of Zn-
Mn alloy during the cathodic sweep. Furthermore, the dissolution
potential (Ediss) range of the solid phases deposited from the so-
lution S0 is very close to that of pure Zn (Fig. 2-b), suggesting that
the coating, already formed, is mainly composed of pure Zn.
Taking into account the results described above, it is possible to
deposit a Zn-Mn alloy from a chloride bath free of additive (s), using
a cathodic potentials lower than 1.52 V vs. Ag/AgCl.
To validate the results of this electrochemical study, bulk elec-
trolysis at a cathodic potential at 1.55 V vs. Ag/AgCl was con-
ducted. This experiment leads to a Zn-Mn alloy coating, containing
4.9 wt % Mn with a current efficiency close to 60%. As shown, the
electrolysis results support well voltammogram data.
Thus, it can be concluded that a chloride bath even without
additives lets obtain Zn-Mn coatings. However, the Mn content in
the Zn-Mn alloy obtained at E ¼ 1.55 V is low. In order to obtain
Mn-rich deposits, it is compulsory to apply cathodic potentials
lower than 1.55 V. Or, for all potential less than 1.52 V, the alloy
deposition is highly concurrenced by HER that favors a dendritic
structure formation [39,40]. As illustration, Fig. 3-a shows that the
Zn-Mn alloy obtained at 1.55 V is dendritic and spongy. The
dendrites are mainly formed at the edges of the cathode. The
coating is composed of cauliflower, irregular or coalesced round
crystallites (nodules) distributed over the whole substrate surface.
Similar coatings appearance was reported in acidic additives-free
baths [10,41].
The use of triton X100 and 3-HBA in this work aims to avoid the
above drawbacks, namely the low current efficiency and the den-
dritic structure.
Fig. 3. SEM micrographs of Zn-Mn deposits on steel substrate deposited at E ¼ 1.55 V. These deposits were obtained from S0 (a): without additives (b): in presence of Triton X100
(c): in presence of Triton X100 and 3-HBA.
3.2. Cyclic voltammetry study of Zn-Mn co-deposition in presence
of additives
The effect of triton X100 and 3-HBA on Zn-Mn co-deposition
from chloride electrolyte was separately examined, firstly. There-
after, the two additives were simultaneously used.
3.2.1. Individual effect of triton X100
Fig. 4-a presents the individual influence of triton X100 and 3-
HBA on the electrochemical process of Zn-Mn deposition. Before
discussing the curves in this figure, it is to be noted that preliminary
electrochemical experiments on the supporting electrolyte
(KCl þ H3BO3) containing the two additives showed that the latters
are not electro-active under the experimental conditions used in
this study.
As seen in Fig. 4-a, the addition of triton X100 to the electrolyte S0
induces a deep change in the voltammogram shape, shifting the
Zn2þ discharging potential to more negative value, i.e. to
about 1.5 V vs. Ag/AgCl. Indeed, the current density of the
remaining cathodic peak, observed at 1.24 V for Zn deposition is
strongly reduced when compared with that obtained at 1.2 V from
the additives-free electrolyte S0 (Fig. 4-a). Triton X100 brings down
the deposition potential of Zn from 1.2 toward 1.5 V, revealing
an increase in the overvoltage of Zn deposition. This strong inhi-
bition of Zn2þ reduction favors the incorporation of Mn in the Zn
matrix. This makes co-deposition of Zn and Mn possible, even if Zn
still deposits preferentially. Consequently, this leads us to conclude
that the sharp increase in current density observed below 1.5 V vs.
Ag/AgCl is due to the reduction of both Mn2þ and Zn2þ ions. This co-
deposition is obviously accompanied with HER. To make sure of this
result, bulk electrolysis was carried out from triton X100-containing
electrolyte S0 at a cathodic potential of 1.58 V vs. Ag/AgCl. This
experiment actually leads to a Zn-Mn alloy with 17 wt% Mn content
and a current efficiency exceeding 70%. These results are in good
accordance with voltammogram data.
In addition to the enhancement in current efficiency and
 N. Loukil, M. Feki / Journal of Alloys and Compounds 719 (2017) 420e428 425

(a)
0.4

S0
0.3
S0 + Triton X100
S0 + 3-HBA
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

-0.2

(
-0.3

-0.4

(b) 0.25

0.2
S0 + Triton X100
S0 + Triton X100 + 3-HBA 0.15

0.1

j(A/cm²)
0.05
E (V vs. Ag/AgCl)
0
-2.2 -2 -1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
-0.05

-0.1

-0.15

-0.2

-0.25

Fig. 4. Typical voltammograms obtained from S0 (a): in absence and presence of tested additives Triton X100 and 3-HBA added separately; (b): in presence of Triton X100 and the
mixture of Triton X100 and 3-HBA.

particularly Mn content induced by triton X100, the latter shows
also a beneficial effect on Zn-Mn coating morphology. As seen in
Fig. 3-b, no dendritic structure is observed: the deposit is smooth
and slightly bright.
The inhibition effect of triton X100 on Zn deposition is associated
with the adsorption of the latter onto the steel substrate [42]. The
adsorbed molecules form an adlayer that almost covers a portion of
the active sites onto the electrode/electrolyte interface, blocking
consequently the active centers where the electrodeposition may
occur. As a result, an additional energy is required for the metallic
ion discharge exhibiting a higher cathodic over-potential [43,44].
This over-potential is necessary so that reduction process competes
favorably with adsorption phenomenon, allowing thus the forma-
tion of Zn nuclei on the electrode surface. So, at sufficiently nega-
tive potential, the additive is desorbed from the cathode surface,
leaving vacant the previously occupied active sites. At these vacated
sites where the reduction process of Zn2þ ions occurs, leading to the
sharp increase in cathodic current density at 1.5 V vs. Ag/AgCl
(Fig. 4-a) [41,45].
To display prominently the adsorption assumption of triton X100
on steel surface, infrared spectroscopy was used. For this purpose,
the steel electrode was potentiostatically polarized at E ¼ 1.53 V
426 N. Loukil, M. Feki / Journal of Alloys and Compounds 719 (2017) 420e428

from the electrolyte S0, devoid of metallic ions (Zn2þ and Mn2þ) and 0.4
containing the investigated additive, then removed and washed by
distilled water. After drying at room temperature, the electrode
surface was analyzed via IR spectroscopy (reflexion mode). 1g/L PEG 8000 0.3
The FTIR spectrum obtained (Fig. 5) shows three main adsorp- 8g/L PEG 8000
tion bands located near 1100, 3000 and 3500 cm1. The band at
1100 cm1 is assigned to the CeO vibrations of the ether chain in 0.2
triton X100 molecules. The two overlapping bands located just
below 3000 cm1 are ascribed to the CeH vibrations in aromatic
0.1
rings as well as in methyl and methylene groups. The OeH
stretching mode of hydroxyl groups in triton X100 and eventually E (V vs. Ag/AgCl)

j (A/cm²)
adsorbed water causes the emergence of the wide absorption band
0
at about 3500 cm1. These bands, particularly that located at -2.2 -2 -1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
1100 cm1, which are characteristics of triton X100 molecules prove
that adsorption of this additive effectively occurs during cathodic
-0.1
polarization of steel electrode.
To investigate the contribution of the hydrophobic head group
of triton X100 in shifting the Zn deposition potential, electro- -0.2
chemical experiments have been carried out with electrolyte S0
containing hydrophobic group-free additive namely, poly-
ethyleneglycol 8000 (PEG8000). The voltammograms recorded in -0.3
presence of PEG8000 at different concentrations are shown in Fig. 6.
When compared to those of Fig. 4-a, only a very small cathodic Fig. 6. Typical voltammograms obtained from S0 in presence of PEG8000 added in
different concentrations.
polarization for Zn2þ reduction, proving a negligible inhibition of
Zn deposition in presence of PEG8000. This finding clearly demon-
strates the vital role of the hydrophobic head group of triton X100 in
0.25
the coverage of the cathodic surface.
Ef= -1.8 V 0.2

3.2.2. Effect of both triton X100 and 3-HBA Ef=-2 V 0.15

Before discussing the effect of both additives, it is to be noted 0.1
that when 3-HBA is added alone into the basic electrolyte S0 (Fig. 4-
a), no significant change in the shape of the voltammogram is 0.05
E (V vs. Ag/AgCl)
observed. Indeed, the Zn2þ reduction peak at 1.2 V vs. Ag/AgCl is

j (A/cm²)
0
slightly displaced by about 10 mV towards negative potentials, -2.2 -2 -1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
while its intensity remains similar to that obtained without any -0.05
additive. This result suggests that 3-HBA cannot be considered, in -0.1
itself, as a potential additive as stated above for triton X100. By
incorporating 3-HBA in S0 containing already triton X100, the -0.15
reduction process is markedly modified as shown in Fig. 4-b. The -0.2
little cathodic peak recorded for Zn individual deposition at
around 1.24 V vs. Ag/AgCl in presence of triton X100 alone is -0.25
completely suppressed when adding 3-HBA (Fig. 4-b). The use of 3-
Fig. 7. Dependance of the volatmmogram shapes on the limit cathodic potential. The
HBA in conjunction with triton X100 leads then to a total inhibition voltammograms are recorded from S0 containing both triton X100 and 3-HBA.
of Zn deposition in this range of potential. The cathodic current
density is negligible until the deposition potential of Zn-Mn alloy,
i.e 1.52 V vs. Ag/AgCl. The entire suppression of the Zn2þ reduc- additives on Zn-Mn co-deposition. The Mn content, obtained in this
tion peak demonstrates the beneficial synergistic effect of the two case, is slightly higher than that obtained in presence of only triton
X100: i.e. 17.9 wt%. Moreover, the deposit morphology is signifi-
cantly improved (Fig. 3-c). As seen in Fig. 3-c, the Zn-Mn deposit is
102
smoother and brighter when 3-HBA is added in conjunction with
100 triton X100. Additionally, the current efficiency is more enhanced
and reaches 85%.
Transmittance (%)

98 To illustrate the Zn deposition inhibition extent induced by the

used additives, Table 2 displays the cathodic current densities,
96
estimated from voltammogram data (Fig. 4-a and b), at a constant
94 potential E ¼ 1.2 V vs. Ag/AgCl. This table also shows the degrees
of surface coverage for the additives, evaluated from equation (1)
92 [46], where j and jS are the current densities without and with
additives respectively, measured at the considered potential value.
90
0 500 1000 1500 2000 2500 3000 3500 4000 4500
wavenumber (cm )
q ¼ ð1  js=jÞ (1)
Fig. 5. FTIR spectrum for a steel electrode potentiostatically polarized for 15 min at
E ¼ 1.53 V in the supporting electrolyte (3.21 M KCl þ 0.4 M H3BO3) containing As expected, calculation shows that the highest coverage degree
tritonX100. is obtained for the system containing the mixture of triton X100 and
 N. Loukil, M. Feki / Journal of Alloys and Compounds 719 (2017) 420e428
Table 2
Cathodic current densities and degrees of surface coverage obtained at E ¼ 1.2 V vs.
Ag/AgCl for the studied additives.
Additive nature Cathodic peak current Degree of surface coverage q
density (A/cm2)
Triton X100 9.26 103 z 0.87
3-HBA 7.18 102 z 0
Triton X100 þ 3-HBA 8.03 104 z 0.98
Without additives 7.18 102 z0
3-HBA. This reflects the resulting additional enhancement of
simultaneous deposition of Zn and Mn when the two additives are
used in conjunction.
Referring to the literature dealing with adsorption phenomena
[39,47], it was assumed in our case that the presence of hydroxyl
group, arranged in benzene ring of 3-HBA, would strengthen the
adsorbability of triton X100 on the metal surface. Consequently, it
enhances the degree of coverage.
Coming back to Fig. 4-b, two peaks are observed during the
reverse scan from 2 V vs. Ag/AgCl. These peaks are attributed to
individual deposition of each alloying elements, i.e. Mn (1.65 V vs.
Ag/AgCl) and Zn (1.2 V vs. Ag/AgCl). The apparition of these peaks
as well as the shape of the cathodic part observed during the
reverse scan in voltammgrams of Fig. 4-b, will be discussed in the
next section.
The comparison of the anodic peaks (Fig. 4-a) shows that their
intensity is reduced when triton X100 is added in the plating bath S0
and highly reduced when the both additives are used. This decrease
of amplitude could be a consequence of a decrease of Zn amount in
the Zn-Mn alloy deposited in presence of additives. This finding is
in agreement with the results reported earlier and confirms the
strong blocking effect towards Zn deposition when the two addi-
tives are used in conjunction.
3.3. Effect of HER extent on the volatmmogram shapes
During the voltammetry study of Zn-Mn co-deposition, an un-
expected phenomenon occurs at higher cathodic potentials. Deep
modifications in the cathodic part shapes of the voltammograms
are observed when the switching potential is lightly changed. As
illustration, Fig. 7 shows two voltammograms obtained from the
same solution S0 containing both triton X100 and 3 HBA, but
recorded for two different switching cathodic potentials,
namely 2 and 1.8 V vs. Ag/AgCl.
As seen in Fig. 7, the two voltammograms exhibit, on the
negative-going scan, identical cathodic features between 1.1
and 1.8 V vs. Ag/AgCl. In contrast, on the anodic-going scan, the
shape of the cathodic parts is deeply different. When the more
negative potential is fixed at 1.8 V vs. Ag/AgCl, the cathodic part of
the negative-going scan is merged with the reverse one. On the
contrary, when the switching potential is extended until 2 V vs.
Ag/Cl, a decrease in current density is shown between 1.85
and 2 V vs. Ag/AgCl. During the reverse scan (from 2 V vs. Ag/
AgCl), two small cathodic peaks are attributed to individual depo-
sition of each alloying elements. It is advisable to note that the
potential at which the Mn2þ reduction peak reaches its maximum
is shifted from the previously value 1.8 V (Fig. 2-a) to 1.65 V in
Fig. 4-b. This shift of potential, observed also by Sylla et al. [9], re-
veals a change of the substrate from steel (Fig. 2-a) to Zn-Mn coated
steel (Fig. 7). This finding means that the Zn-Mn coating formed
during the cathodic scan favors the Mn2þ reduction during the
reverse scan (Fig. 7).
This shape difference for the two voltammograms (Fig. 7) is
related to what happens at the more negative potentials, more
427
clearly between 1.85 and 2 V vs. Ag/AgCl. In this potential range,
corresponding to high current densities ranging between 175
and 200 mA/cm2 (Fig. 7), hydrogen evolution reaction is very
intense [9,10]. This leads to a strong increase of pH at the cathode
vicinity and subsequently the precipitation of metallic hydroxides,
namely Mn(OH)2 (Ks ¼ 1012.5) and/or Zn(OH)2 (Ks ¼ 1017). In this
regard, Bucko et al. [10] reported that Zn-Mn coatings deposited
from KCl-bath at high current densities (100e300 mA/cm2) are rich
in oxyhydroxides of Zn and Mn. Taking into account this occur-
rence, hydroxide chemical precipitation occurring near the
cathodic surface inhibits the course of the electrochemical co-
deposition of Zn and Mn between 1.85 and 2 V vs. Ag/AgCl.
It is striking to note that the inhibition effect is not observed
when additives are absent (Fig. 4-a). In return, the voltammogram
of Fig. 4-a shows current density fluctuations from about 1.7
to 2 V vs. Ag/AgCl. These fluctuations seem to be also attributed to
hydroxides precipitation but at a less extent than that observed in
Fig. 7 between 1.85 and 2 V vs. Ag/AgCl. Consequently, the
transformation of current fluctuations observed in Fig. 4-a into an
inhibiting phenomenon in Fig. 4-b, is ascribed to the additives ef-
fect. In this connection, it is important to remember that the used
additives (triton X100 or the mixture of triton X100 and 3-HBA) are
expected to favor Mn incorporation in the Zn-Mn coatings. There-
fore, the Zn-Mn coatings deposited during the cathodic scan in
presence of additives (Fig. 7) are richer in Mn than those obtained
from the additive-free solution S0 (Fig. 4-a). As stated before, pure
Mn deposit enhances HER. On the other hand, Bucko et al. [10]
stated that Mn-rich coatings have also higher catalytic activity for
hydrogen evolution. Thus, compared to the case without additives
(Fig. 4-a), the increase of pH at the cathode/electrolyte interface,
occurring at high current densities, is more pronounced in presence
of additives (Fig. 7). Consequently, hydroxides precipitation is more
favored under these conditions. Within the context of this
assumption, the presence of metal hydroxide inclusions at the
cathode surface is not favorable for the adsorption of the additives
and consequently prevents them from playing their role. This loss
of adsorbent efficiency seems to be at origin of the individual
reduction of Mn2þ (1.65 V) and Zn2þ (1.2 V) during the reverse
scan of the voltammogram in Fig. 7. This individual deposition of Zn
and Mn is not inhibited during the reverse scan since the pH in-
crease. Consequently, the hydroxides precipitation becomes more
and more unfavored as the potential returns to negative values
lower than 2 V vs. Ag/AgCl.
In this case, the Zn-Mn alloy formed during the cathodic scan
catalyzes, at a certain extent (according to the Mn content), the HER
induces then a pH increase sufficient to trigger the precipitation
chemical process.
Our results concerning the catalytic effect of Mn and Zn-Mn
coatings towards HER confirm the assumption already expressed
by others authors [9,10]. This catalysis associated to the use of high
current densities generates different drawbacks namely, i) a strong
decrease of current efficiency due to an excessive HER, ii): an in-
hibition of Zn-Mn co-deposition due to an intense precipitation of
metallic hydroxides and iii) bad coating quality (dendritic and
spongy). To avoid these drawbacks, the production of Zn-Mn
coatings with acceptable quality and current efficiency dictates
either to work at current densities less than 200 mA/cm2 or to use
higher H3BO3 concentration in order to increase the buffer capacity
of the bath.
4. Conclusion
This study was conducted to improve the Zn-Mn alloys elec-
trodeposition conditions via the addition of two plating additives:
Triton X100 and 3-HBA into an acidic chloride bath. The used bath
428 N. Loukil, M. Feki / Journal of Alloys and Compounds 719 (2017) 420e428
does not require complexing agents for better environment
compatibility.
Cyclic voltammetry study, from the additives-free electrolyte,
reveals that Zn-Mn alloy electrodeposition is inevitably preceded
by deposition of pure Zn. Consequently, low Mn (4.9%)-alloy
coating is obtained. Moreover, the coatings elaborated by bulk
electrolysis show poor adherence and dendritic structure, and the
cathodic current efficiency are low (60%). On the basis of the
electrochemical results, triton X100 is turned out to be a powerful
potential additive to inhibit the individual deposition of Zn. An
entire suppression of pure Zn deposition was observed owning to
the co-adsorption of the two used additives on the surface sub-
strate. A highest coverage degree is obtained for the bath S0 con-
taining both triton X100 and 3-HBA, denoting their synergistic
effect. Hence, Mn incorporation into Zn-Mn deposits is favored as a
beneficial consequence of minimizing the potential gap between Zn
and Mn co-deposition. It has been pointed out that the presence of
3-HBA not only favors further Mn co-deposition, but also prevents
dendrites formation and improves Zn-Mn deposit morphology.
A comparative study, by investigating polyethylene glycol
(PEG8000) instead of triton X100, displayed the vital role of the hy-
drophobic head of triton X100 molecule in enhancing the Mn
incorporation into Zn matrix. Moreover, the switching potential
technique demonstrated that at cathodic potentials lower
than 1.8 V, the hydrogen evolution reaction becomes very fast as it
is more catalyzed when Mn-rich are deposited. Thus, pH increases
at the cathode surface, leading to an intense precipitation of hy-
droxides that block the alloy deposition process.
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