Surface & Coatings Technology 228 (2013) 221–228

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Surface & Coatings Technology

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The influence of anion type in electrolyte on the properties of electrodeposited

Zn\Mn alloy coatings
M. Bučko a, J. Rogan a, S.I. Stevanović b, S. Stanković a, J.B. Bajat a,⁎
a
Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11120, Belgrade, Serbia
b
ICTM – IEC, P.O. Box 473, 11001 Belgrade, Serbia

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 electrolytes containing chloride or sulfate anions, was
Received 13 December 2012 investigated by chronopotentiometry. Galvanostatically obtained electrodeposits were characterized by
Accepted in revised form 15 April 2013 X-ray diffraction (XRD), atomic force microscopy (AFM), and atomic absorption spectrophotometry (AAS).
Available online 23 April 2013
It was found that Zn2+ and Mn 2+ ion reduction occurred at higher overpotentials in sulfate bath, leading
to a higher Mn content in the deposit and smaller crystallites as compared to the chloride electrolyte. AFM
Keywords:
Electrochemical deposition
images of deposits revealed that with the increase in deposition current density, bigger agglomerates formed
Zn\Mn alloy in both electrolytes, leading to higher roughness and heterogeneity of the samples. In relation to this obser-
X-ray diffraction (XRD) vation, the Zn\Mn coatings were deposited at current densities of up to 80 mA cm−2 because at higher cur-
Atomic force microscopy (AFM) rent densities the samples from sulfate electrolyte were non adherent and dendritic. Depending on the
Corrosion deposition current density, the XRD patterns of the Zn\Mn deposits produced from chloride electrolyte in-
dicated that the coatings were formed of either η- or ε-Zn\Mn phase, while the coatings obtained from sul-
fate bath consisted of ε-Zn\Mn phase. The linear polarization method showed that Zn\Mn alloys deposited
from sulfate electrolyte exhibited higher corrosion resistance in NaCl corrosive media.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction
Zn\Mn alloys offer several industrial applications. First of all, they
have been developed with the aim of improving the corrosion resis-
tance of Zn coatings on steel [1]. Although Zn has high corrosion resis-
tance in most non-aggressive atmospheric environments, corrosion
problems of zinc coatings are found in aggressive atmospheric envi-
ronments where salt and sulfur dioxide are present. To overcome
this problem, new types of zinc coatings, such as Zn\Ni, Zn\Co and
Zn\Fe are currently being used in industry [2,3]. The Zn\Mn alloy
was reported by several authors [4,5] to have even better corrosion
resistance, particularly in aggressive media.
Zn\Mn alloys consist of paramagnetic Mn and diamagnetic Zn
and it was reported that a change in Zn to Mn ratio in the alloy in-
duced interesting changes in magnetic properties of the alloy. There-
fore, there are potential magnetic applications of these alloys [6].
Finally, a large scale production of Zn\Mn alloys via electrodeposi-
tion is a promising method for recycling of spent Zn\Mn batteries,
which represent up to 90% of the European battery market [7]. Hydro-
metallurgical process of recycling, namely, means that metals from
batteries are dissolved in some solvent, for example HCl or H2SO4
Abbreviations: c.d., current density; Rp, linear polarization resistance; XRD, X-ray
diffraction; AFM, atomic force microscopy; AAS, atomic absorption spectrophotometry.
⁎ Corresponding author. Tel.: +381 11 3303 694; fax: +381 11 3370 387.
E-mail address: jela@tmf.bg.ac.rs (J.B. Bajat).
[8]. If the next step in this process involves Zn and Mn recovery by
electrodeposition, then the final product will be Zn\Mn coating [9].
Although Zn\Mn coatings may be obtained by hot-dip galvaniz-
ing [10], the most common production method is electrodeposition.
Ionic liquids have been employed in electrodepositing of Zn\Mn al-
loys [11], but aqueous electrolytes are still much more used [5]. The
standard electrode potentials of Zn 2+/Zn and Mn 2+/Mn couples in
aqueous acidic medium are significantly different, − 0.76 V/SHE for
Zn vs. − 1.18 V/SHE for Mn [12]. For this reason, various deposition
parameters must be regulated in order to achieve co-deposition of
less noble metal, Mn, with Zn. For example, it is known that the in-
crease in Mn 2+ ion concentration, shifting the deposition cathodic
potential towards negative values, or the increase in deposition cur-
rent density (c.d.), is beneficial for the increase in Mn % in the alloy
[1,13], while stirring or heating of the electrolyte leads to the opposite
effect [14,15]. Complexing agents play important role in the Zn\Mn
deposition, because the complexation brings the Zn and Mn deposi-
tion potentials closer. Various complexing agents have been used
until now, but often with some drawbacks. For instance, electrolytes
containing citrate [6] or pyrophosphate [5,16] complexing agents
are with low stability, because Mn(III) complexes precipitate in the
solution. In addition, high stability constants of metal complex ions
induce higher overpotential for metal reduction, leading to the low
current efficiency [13,17].
However, two new types of electrolytes for Zn\Mn alloy deposi-
tion, namely, simple chloride electrolyte with H3BO3 [14] and simple

0257-8972/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.surfcoat.2013.04.032
222 M. Bučko et al. / Surface & Coatings Technology 228 (2013) 221–228

sulfate electrolyte with (NH4)2SO4 [1] have appeared in literature in the
last decade. Bearing in mind that these electrolyte types are very stable,
both during storage and electrodeposition process, they could be good
candidates for a commercial production of Zn\Mn coatings. So, the
scope of the present work was to investigate the influence of the elec-
trolyte type (chloride vs. sulfate) on the characteristics of the Zn\Mn
alloys electrodeposited under the economically favorable conditions
(room temperature, low deposition c.d., and without additives). The
Zn\Mn alloys were obtained at constant c.d.s, and potential-time
curves were recorded during the deposition. The composition, mor-
phology, and structural properties of the Zn\Mn deposits were ana-
lyzed by atomic absorption spectrophotometry (AAS), Atomic Force
Microscopy (AFM), and X-ray diffraction (XRD).
and step-scan mode (range: 30−90°2θ, step-time: 0.50 s, step-
width: 0.02 ). The program PowderCell [18] was used for an approxi-
mate phase analysis. Unit cell parameters were obtained by the least-
squares method using the program LSUCRIPC [19]. The mean crystallite
size was estimated from three most intensive diffractions peaks of the
Zn\Mn (002), (100) and (101) planes, by the Scherrer formula [20]
using the appropriate instrumental resolution function for ZnO as a
standard.
For chemical composition analysis of Zn\Mn alloys, the alloys were
stripped in a known volume of HCl, and metal ion concentration was
determined by atomic absorption in AAS-PYE Unicam SP9, Philips.
3. Results and discussion

2. Experimental 3.1. Electrodeposition of Zn\Mn alloy coatings

Steel was used as substrate for electrodeposition, as a panel of In order to study the anion effects on the electrochemical behavior and
20 mm × 20 mm × 0.25 mm surface area. The steel substrates were properties of Zn\Mn alloy coatings, the samples were electrodeposited
pre-treated by mechanical cleaning (abrading successively with galvanostatically, at c.d.s between 20 and 80 mA cm−2, from sulfate
emery papers of the following grades: 280, 360, 800 and 1000) and and chloride electrolytes. A current efficiency for Zn\Mn electrodeposi-
then degreased in a saturated solution of NaOH in ethanol, pickled tion was calculated by measuring the mass gain of the deposits, and a
with 2 mol dm −3 HCl for 30 s and finally rinsed with distilled few data are presented in Table 1. As seen, the current efficiency in both
water. A Zn plate, placed parallel to the cathode, was used as a coun- electrolytes decreases with the increase in deposition c.d. In addition,
ter electrode in electrodeposition. the current efficiency is higher in chloride electrolyte, suggesting that
Electrodeposition was performed in electrolytes with two different h.e.r. is more inhibited in this solution. This is in accordance with litera-
compositions. Chloride electrolyte (pH 5.0) consisted of 1.8 mol dm−3 ture data, since it is known that the overpotential for h.e.r. is significantly
KCl, 0.4 mol dm−3 H3BO3, 0.4 mol dm−3 ZnCl2 and 1.8 mol dm−3 higher in the supporting electrolyte consisting of a chloride salt (KCl,
MnCl2, while sulfate electrolyte (pH 5.5) contained 0.6 mol dm−3 NaCl), as compared to the corresponding sulfate salt, due to the stronger
K2SO4, 0.5 mol dm−3 (NH4)2SO4, 0.4 mol dm−3 ZnSO4 and specific adsorption of Cl− ions on the cathode surface [21].
1.8 mol dm−3 MnSO4. The metal ion concentration was the same in Potentiometric E–t curves were recorded during the electrodepo-
both electrolytes. Electrodeposition was carried out at room tempera- sition and some of the E–t curves are shown in Fig. 1. It can be seen
ture (22 °C), in a single-compartment cell. All the employed electrolytes that, depending on c.d. applied, the reduction overpotential was up
were prepared using p.a. chemicals and double distilled water. The to 70–180 mV higher in sulfate than in chloride electrolyte. To ex-
Zn\Mn alloy was electrodeposited using PAR M173 potentiostat/ plain this, it has to be considered that Zn and Mn are present in
galvanostat in galvanostatic mode, with c.d.s in the range of 20– form of various complex ions, as Table 2 depicts. When the formation
80 mA cm−2. The number of coulombs passed was tuned in order to en- constants are compared, it is clear from the table that higher forma-
sure a coating thickness of ~10 μm, owing to the known current tion constants are related to sulfate electrolyte, i.e. complex species
efficiencies. of Zn and Mn in sulfate electrolyte are more stable as compared to
Saturated calomel electrode (SCE) was a reference electrode. A the corresponding species in chloride electrolyte. Additionally, high
Luggin capillary, whose tip was set at a distance of 1–2 mm from constant values indicate strong Zn complexation with NH3 in sulfate
the surface of a substrate, was used to minimize errors due to iR solution. So, this could be one of the reasons for higher overpotential
drop in the electrolytes. and lower current efficiency in the sulfate electrolyte.
Corrosion measurements were performed in aerated 0.5 mol dm−3 The observed higher current efficiency for metal deposition from
NaCl solution. The linear polarization method was employed and the chloride electrolyte could also be due to the fact that Cl − anions cat-
linear polarization resistance (Rp) was measured. Each working alyze Zn and Mn reduction process. Namely, there are plenty of arti-
electrode was potentiodynamically polarized in the potential range cles describing the higher catalytic role of Cl − ions, in comparison
between −15 and +15 mV (from cathodic to anodic) over the respec- to SO42 −, in metal or alloy deposition associated with the h.e.r. Some
tive open circuit potential (OCP). Tafel plots were obtained at a scan rate examples are the deposition of Ni\Fe [27], Co\Fe [28], and Cu [29].
of 0.2 mV s −1, starting from the open circuit potential (OCP), after the According to these data, Cl − ions adsorbed on the cathode depress
constant OCP was established. Polarization tests were conducted using the h.e.r., and, in addition, metal-chloride complex species behave
Gamry Reference 600 Potentiostat and three measurements were as an ion bridge between the cathode surface and the metal ion
performed for each sample, with very good reproducibility.
NanoScope 3D (Veeco, USA) microscope was used to study the
Table 1
coating morphology by atomic force microscopy (AFM), which oper- Deposition parameters and properties of Zn\Mn electrodeposits obtained from chlo-
ated in tapping mode under ambient conditions. Etched silicon ride and sulfate electrolyte.
probes with spring constant 20–80 Nm −1 were used. AFM images
Electrolyte Deposition Current Crystallite Unit cell Polarization
were recorded over scan area of 1000 × 1000 nm 2. The agglomerate type c.d./mA cm−2 efficiency/ size/nm parameters/nm resistance/
size dimension of electrodeposited coatings was determined from % Ω cm2
a c
AFM image profile line analysis. The measurement was based on the
assumption that the surface irregularities indicated by the profile Chloride 30 100 – – – 653 ± 5
50 90 66 0.2662 0.4953 603 ± 4
line, represented the agglomerate size. In order to calculate the ag-
70 85 37 0.2654 0.4950 590 ± 5
glomerate size distribution, a hundred agglomerates were measured 80 80 18 0.2767 0.4476 535 ± 4
on each AFM image. Sulfate 30 95 – – – 1601 ± 11
Structural analysis of the Zn\Mn alloys was studied by X-ray dif- 50 85 19 0.2760 0.4459 1240 ± 8
fraction (XRD) on an Ital Structure APD2000 X-ray diffractometer in a 70 75 14 0.2764 0.4475 932 ± 8
80 70 13 – – 544 ± 4
Bragg–Brentano geometry using CuKα radiation (λ = 0.15418 nm)
 M. Bučko et al. / Surface & Coatings Technology 228 (2013) 221–228 223

3.2. Chemical composition of Zn\Mn alloy coatings

Fig. 2 shows the Mn content in the Zn\Mn deposits for various

Fig. 1. Potential–time transients for Zn\Mn alloy electrodeposition from chloride elec-
trolyte at: a) j = 30 mA cm−2, b) j = 50 mA cm−2; and sulfate electrolyte at c) j =
30 mA cm−2, d) j = 50 mA cm−2, and e) j = 80 mA cm−2.
being discharged. On the basis of experimental results shown in Fig. 1,
it is very likely that this mechanism could also be present in Zn\Mn
deposition from chloride solution. Furthermore, the recorded E–t
curves at c.d.s. higher than 50 mA cm −2 in sulfate solution indicated
a strong effect of H2 evolution and/or rough deposit formation. Name-
ly, a significant dissipation of recorded potential values was observed,
as denoted in the curve for 80 mA cm −2 in Fig. 1.
Finally it should be noted that besides Cl − and SO42− anions, the
addition of H3BO3 and (NH4)2SO4 in chloride and sulfate electrolyte
respectively, also influences the metal deposition. The role of these
compounds is, firstly, to buffer the solution in the near-cathodic
layer in order to prevent the formation of Zn(OH)2 and Mn(OH)2
[30,31], and secondly, to decrease the potential gap between Zn and
Mn reduction. As a matter of fact, the ammonia and borate coordina-
tion compounds of Zn are more stable than the corresponding
Mn-complexes, as seen in the Table 2, so the latter role appears pos-
sible. Q. Wei et al. for example, studied extensively the influence of
(NH4)2SO4 on the electrodeposition of Mn from sulfate solution [32]
and found that the variation in the concentration of (NH4)2SO4 had
a small impact on the cell voltage and current efficiency. On the con-
trary, Zn complexation with NH3 influences strongly Zn reduction
[1,30].
In addition to the mentioned roles, H3BO3 was reported to provide
a smoother deposit and higher current efficiency for metal reduction
[7], by adsorbing on the most prominent cathode spots and conse-
quently inhibiting both the h.e.r. and metal reduction [31,33], which
could also be the reason for higher current efficiency for deposition
from chloride electrolyte.
deposition c.d.s. and two different electrolyte types. Only the deposits
obtained at c.d.s of up to 80 mA cm −2 were analyzed, because at
higher c.d.s., the coatings obtained from sulfate solution were den-
dritic and non-adherent. As seen, the Mn content of deposit increases
with the increase in deposition c.d., proving that the codeposition of
Zn and Mn is a normal type of codeposition [5,11,13,16]. This means
that the Mn reduction starts at far more negative potential values
than equilibrium potential for Zn reduction, and at such negative po-
tential, the diffusion of Zn ions plays important role in Zn reduction. It
can be seen in Fig. 2 that there is a critical value of the deposition c.d.
where Mn content rapidly increases. For chloride electrolyte, this
value is about 50 mA cm −2, whereas it is lower for sulfate electrolyte,
30 mA cm −2. A significant increase in Mn content indicates that the
deposition potential is reached where Zn reduces at diffusion limiting
c.d., so further change of deposition potential to the negative values,
enhances only the Mn deposition and h.e.r. [31].
The Fig. 2 also shows that in the whole range of investigated c.d.s,
the Mn content is higher in the samples deposited from the sulfate
electrolyte. It was shown earlier that Zn\Mn reduction takes place
at more negative potentials in the sulfate electrolyte (Fig. 1). This is
obviously beneficial for easier Mn incorporation from sulfate electro-
lyte, which is in agreement with the basic principles of alloy electro-
deposition. Namely, it is known that when two metals of different
standard potentials are codeposited, every factor that shifts the re-
duction potential to the negative values, will facilitate the deposition
of a less noble metal and thus increase its content in an alloy [34].
Based on the results shown, it may be concluded that in reference
to the chemical composition of Zn\Mn deposits, the electrolyte with
SO42− anions is more flexible, enabling the deposition of alloys with
wider range of Mn percentage, simply by altering deposition c.d.
It should be stressed at this point that a large amount of metal
oxyhydroxides may be incorporated during the electrodeposition of
Mn alloys at high c.d.s. [35]. However, we have extensively studied
the oxygen inclusions in Zn\Mn alloys, in electroplating from pyro-
phosphate [16] and chloride [36] solutions, and concluded that the ox-
ygen percent in the coatings was negligible at c.d.s up to 100 mA cm−2.
The SEM/EDS analysis of deposited coatings analyzed in the c.d. range
investigated in this work, showed up to 5 at.% oxygen, depending on
the sample, and these small amounts of O probably originated from
metal oxidation during the sample exposure to air.
3.3. Morphology of Zn\Mn alloy coatings
The surface morphology of the samples deposited from chloride
and sulfate solution with the c.d.s. of 30 and 80 mA cm −2, was

Table 2
Possible Zn(II) and Mn(II) complex species and their cumulative formation constants.

Chloride electrolyte Sulfate electrolyte

Complex Formation Ref. Complex Formation Ref.

specie constant, logβ specie constant, logβ

[ZnCl]+ −0.42 [22] [ZnSO4]0 2.30 [25]

[ZnCl2]0 −0.62 [MnSO4]0 0.92 [26]
[ZnCl3] − −0.34 [Mn(SO4)2]2− 0.97
[ZnCl4]2− −0.19 [Mn(SO4)3]4− 1.96
[MnCl]+ 0.60 [23] [ZnNH3]2+ 2.37 [1]
[MnCl2]0 0.80 [Zn(NH3)2]2+ 4.81
[MnCl3] − 0.40 [Zn(NH3)3]2+ 7.31
[ZnB(OH)4]+ 2.30 [24] [Zn(NH3)4]2+ 9.46
[MnB(OH)4]+ 1.60 [MnNH3]2+ 0.80
Fig. 2. The influence of deposition current density on chemical composition of Zn\Mn
[Mn(NH3)2]2+ 1.30
alloys.
224 M. Bučko et al. / Surface & Coatings Technology 228 (2013) 221–228

analyzed by AFM, and the results are presented in Fig. 3, as AFM images
and one-dimensional line scans. The samples deposited from the chloride
solution, as well as the coating deposited at 30 mA cm−2 from sulfate so-
lution (Fig. 3a,b,c) were bright in appearance, while the sample obtained
at 80 mA cm−2 from the latter electrolyte (Fig. 3d) was dull. The
terrace-stepped morphology is observed for Zn\Mn deposit obtained
from chloride solution at 30 mA cm−2. Contrary, the AFM image of the
deposit obtained at the same c.d. but from sulfate solution (Fig. 3c)
shows the uniformly distributed platelets, reported for pure Zn [37], as
well as for Zn deposits containing low Mn percent deposited from sulfate
solution with citrate complexing agent [13]. Deposits produced at
80 mA cm−2 (Fig. 3b,d) are similar in morphology for both deposition
electrolytes, consisting of pyramidal-shaped nodular agglomerations,
typical of Zn\Mn deposits containing up to 20 wt.% Mn [5,16]. However,
the agglomerates on the sample deposited from the sulfate electrolyte
(Fig. 3d) are quite larger and non-uniformly distributed.
The one-dimensional line scans in Fig. 3 reflect the height and
width of crystalline agglomerations, which have the form of islands.
The influence of deposition c.d., as well as the anion type in the elec-
trolyte, on the surface roughness, can be observed, i.e. for both elec-
trolyte types, it is seen that the height and width of islands slightly
increase with c.d. increase. In chloride electrolyte, the average ag-
glomeration size increases from around 40 nm for deposition c.d. of
30 mA cm −2, to around 55 nm when the c.d. is 80 mA cm −2. As
concerning sulfate electrolyte, the crystalline agglomerations cannot
be clearly distinguished on the sample deposited at 30 mA cm −2
(Fig. 3c). This is because the deposit surface is very compact and
made of flat plates connecting to each other, with no clear boundary

Fig. 3. 2D and 3D AFM images and height profiles of the Zn\Mn films deposited from chloride electrolyte at a) 30 and b) 80 mA cm−2, and from sulfate electrolyte at c) 30 and
d) 80 mA cm−2.
 M. Bučko et al. / Surface & Coatings Technology 228 (2013) 221–228 225

between them. For this reason, the coating presented in Fig. 3c is sig-
nificantly smoother as compared to the other samples. When the de-
position c.d. increases to 80 mA cm −2 (Fig. 3d), the profile line shows
higher roughness than for the sample from chloride electrolyte
obtained at the same c.d., and the agglomerations with significantly
different sizes can be noticed.
The agglomerate size distribution, calculated from the AFM images
shown in Fig. 3, is presented in Fig. 4. The majority of the agglomerations
in the coating deposited from chloride electrolyte at lower c.d. are of the
size of 40–45 nm. In addition, the coating possesses a low percentage of
agglomerations exceeding the size of 50-70 nm. The agglomerate size
distribution is very similar for the sample obtained from the same electro-
lyte at 80 mA cm−2, with the difference that the majority of agglom-
erations have the size of 50-60 nm. It can be concluded that the
electrodeposition from chloride electrolyte, enables the formation of
Zn-Mn coatings with quite uniform agglomerate distribution. On the con-
trary, the deposit obtained from sulfate solution at 80 mA cm−2 consists
of various agglomerates ranging from 30 to 90 nm, non-homogeneously
distributed on the surface (Fig. 4c). As for the coating shown in Fig. 3c, it
was not possible to determine the agglomerate size distribution, due to its
smoothness and compactness.
The smoother surface of deposit obtained at 30 mA cm−2 from sul-
fate electrolyte might be the consequence of higher overpotential relat-
ed to this c.d., for Zn and Mn reduction in sulfate electrolyte compared
to chloride, as it was observed in Fig. 1. However, the AFM data in the
present work show that for both electrolyte types, agglomeration
height increases by increasing the deposition c.d., i.e. the deposition
overpotential. This could be explained when it is known that at a higher
c.d. the Zn reduction occurs at limiting diffusion c.d., and the significant
amount of hydrogen evolves at the cathode (lower current efficiency).
This is in agreement with literature data where the increase in the ag-
glomeration size at higher deposition c.d.s. was attributed to a decrease
in the concentration of metal ions at the deposit-electrolyte interface
[38,39]. Other authors suggested that the changes in the surface energy
and growth mechanisms in the presence of hydrogen are responsible
for the increase in the agglomerate size by increasing c.d. [40]. Never-
theless, the increased deposition c.d. does not influence the agglomer-
ate growth equally in both electrolytes. The agglomerates obtained
from chloride electrolyte at 80 mA cm−2 are bigger than those
obtained at 30 mA cm−2, but they remained uniform in shape and
size, which is not the case for sulfate electrolyte. It seems that the pres-
ence of Cl− ions and H3BO3, enables easier metal reduction and inhibits
hydrogen reduction on the most active cathode places, and consequent-
ly enables the formation of uniform agglomerates even at higher c.d.s.
Moreover, it should be underlined that for deposition c.d.s. higher
Fig. 4. Aggregate size (AFM data) distribution of the Zn\Mn coatings electrodeposited
than 80 mA cm −2, the coatings from sulfate solution appear to be
from chloride electrolyte at a) 30 and b) 80 mA cm−2, and from sulfate electrolyte at
spongy with bad adhesion to the substrate. Boshkov et al. have c) 80 mA cm−2.
reported that it is impossible to obtain Zn\Mn coatings from sulfate
solution without organic additives in the electrolyte [1]. Furthermore,
other authors [41] managed to obtain Zn\Mn deposits with maxi- The XRD pattern of the Zn-Mn alloy coating obtained in the chlo-
mum Mn content of only 2.5 wt.% from sulfate electrolyte consisted ride electrolyte at 50 mA cm −2 is shown in Fig. 5a. The diffractogram
of simple Zn and Mn salts. As it has been seen in the previous analysis, indicated the presence of η-Zn-Mn phase (ICSD 643930), having hex-
the deposits with up to ~ 17 wt.% of Mn were successfully obtained agonal close packed (HCP) structure, space group P63/mmc [42]. The
from the additive-free sulfate electrolyte in the present article. This η-phase is a solid solution of less than 1 wt.% of Mn in Zn [43]. The
is probably due the beneficial effect of Mn to Zn ion ratio in the sulfate presence of only η-phase indicates complete dissolution of Mn in
electrolyte used for electrodeposition in this work. Zn, and thus, formation of a single phase solid solution. The single
η-phase was obtained by other researchers, using electrodeposition
3.4. Structural properties of Zn\Mn alloys process, when Mn content in the Zn\Mn alloy was in the range of
1–2 wt.% [41].
The structure of the Zn\Mn alloys obtained from the chloride and The diffractogram of Zn\Mn alloy coating deposited at 80 mA cm−2
sulfate electrolytes was studied by XRD analysis. The samples deposited from chloride electrolyte (Fig. 5c) indicated the presence of single HCP
at 50 mA cm−2 were chosen for comparison, since the most empha- ε-Zn\Mn phase (ICSD 105022) [42]. So, the increase in Mn content,
sized difference in the chemical content, depending on the electrolyte, as the applied c.d. in chloride electrolyte increased from 50 to
was observed at this c.d. In addition, the XRD analysis was performed 80 mA cm−2, has resulted in a formation of a new Zn\Mn phase. The
for the samples deposited at 70 and 80 mA cm−2, and some of the unit cell parameters for the samples obtained at 50, 70 (XRD pattern
diffractograms are presented also in this section. not shown) and 80 mA cm−2 are given in Table 1. Although the unit
226 M. Bučko et al. / Surface & Coatings Technology 228 (2013) 221–228

cell parameters for all samples are very similar, it seems that they slight-
ly decrease with increasing Mn content.
Contrary to the coating deposited from the chloride electrolyte,
the XRD pattern of the sample obtained from the sulfate electrolyte
at 50 mA cm −2 (Fig. 5b) indicated the existence of ε-Zn\Mn phase.
The XRD has shown that the samples obtained at c.d.s above
50 mA cm −2, are also made of a single ε-phase. As an example, the
XRD pattern for Zn\Mn coating deposited at 70 mA cm −2 from sul-
fate electrolyte is presented in Fig. 5d. The ε-phase was observed to
be the main component of the electrodeposited Zn\Mn layers for a
wide range of Mn contents (15–45 at.%), obtained independently in
various electrolytes [13,14]. In addition, we have reported that the
Zn\Mn alloys having 4–12 at.% Mn, deposited from alkaline electro-
lyte, consisted of the mixture of η- and ε-Zn\Mn phase [16]. Thus,
the ε-phase has been expected to be formed in deposits obtained at
c.d. range of 50–80 mA cm −2 from sulfate electrolyte, since the Mn
content in these samples is between 13 and 17 wt.% (Fig. 2). It can
be seen from the Table 1 that the unit cell parameters increase with
increasing c.d. and Mn content, contrary to the coatings obtained
from the chloride electrolyte.
On the other hand, cell parameters for pure Zn are: a = 0.2665
and c = 0.4947 nm [42]. Therefore, the cell parameter modification
by the presence of Mn in Zn\Mn alloy deposited from both chloride
and sulfate electrolytes affects both a and c parameters. The parame-
ter a is lower in η-Zn\Mn phase and it is higher for ε-Zn\Mn phase,
than in the case of pure Zn. Quite opposite, the parameter c is higher
in η-Zn\Mn than for pure Zn, but it is significantly lower for
ε-Zn\Mn phase.
It is interesting to note that according to the XRD patterns, all sam-
ples showed the presence of only one Zn\Mn phase, regardless of the
electrolyte and c.d. used for electrodeposition. This can be beneficial
from the point of application, because it has been documented that
single-phase Zn\Mn coatings possess higher corrosion resistance as
compared to the two-phase deposits [31].
As concerning the intensity of the diffraction lines, it can be seen
that the reflection from (101) plane is the most intense feature in
all XRD patterns (Fig. 5). Very similar observation was made for the
alloy that was a mixture of η- and ε-Zn\Mn phase electrodeposited
without any additives from chloride electrolyte [4], but this is not
the rule, since the reflections from the other planes have also been
reported to be the most intense, for instance ε(002) or ε(110) lines
[13,14].
Only two XRD patterns, for Zn\Mn coating deposited from the sul-
fate electrolyte at 50 mA cm−2 and from the chloride electrolyte at
80 mA cm−2, have shown the preferred orientation from (002) plane.
However, for the other samples investigated, the distribution of crystal-
lite orientations is homogeneous, i.e. no texture appears. The data
concerning the surface texture can be related to the electrocrystallization
theory. According to D. Li and J. Szpunar [44], the texture formation dur-
ing metal electrodeposition is a consequence of surface energy anisotro-
py. The metal ad-atoms formed in the electrodeposition, diffuse on the
cathode surface until they reach low-energy sites. A substrate surface en-
ergy is crystallographically anisotropic, which means that various crys-
tallographic planes posses various energy values. So, an ad-atom will
tend to be accommodated at the plane which has a lower energy, and
one of the planes will therefore grow preferentially [45]. However, vari-
ous factors may induce a change in surface energy, and consequently
change a deposit texture. For instance, adsorbed hydrogen, adsorbed an-
ions, or inhibitors such as H3BO3, lower the surface energy. A random
crystallite orientation of Zn\Mn coatings was also reported by other au-
thors [14].
The average crystallite sizes determined from the line broadening of
the X-ray diffraction maxima, using the Scherrer formula, are shown in Fig. 5. X-ray diffraction patterns of the Zn\Mn coatings electrodeposited at
Table 1. It is interesting to underline that all the three most intensive 50 mA cm−2 from a) chloride and b) sulfate electrolyte, c) at 80 mA cm−2 from chlo-
diffractions peaks, i.e. Zn\Mn (002), (100) and (101), have shown al- ride and d) 70 mA cm−2 from sulfate solution.
most identical crystallite size (variation is ±1 nm) in all coatings
 M. Bučko et al. / Surface & Coatings Technology 228 (2013) 221–228 227

investigated. Such a good agreement between average crystallite sizes
calculated from the three most intensive peaks is not the case for
some other Zn\Mn coatings [45], as well as some other alloy systems,
for instance Cu\Ni, where it has been found that there is a significant
correlation between the variations of a crystal plane and a crystallite
size [46].
It is evident from the Table 1 that the crystallite size of the coatings
decreases by increasing the c.d., and in addition, the crystallites ob-
tained from sulfate electrolyte are 5–50 nm smaller in comparison to
chloride electrolyte. For instance, as deposition c.d. changes from 50
to 80 mA cm−2, the crystallite size decreases from 66 to 18 nm in chlo-
ride, and from 19 to 13 nm in sulfate electrolyte. This is in agreement
with potentiometric experiments where the higher overpotential for
metal reduction from sulfate electrolyte was shown. According to the
electrocrystallization theory, metal atoms generated by the discharge
of metal ions on the cathode, may be either incorporated into the crys-
tals and thus promote crystal growth, or form a new nucleus when the
rate of crystal growth is not sufficient to accept new atoms [47]. So, the
number of newly formed nuclei will increase, whereas their radius de-
creases with the increase in deposition overpotential [38].
Whilst the XRD analysis depicts a tendency for the crystallite size
to decrease with the c.d., the crystalline agglomerations observed by
AFM obviously grow as c.d. increases. The XRD gives the average crys-
tallite size in the perpendicular direction, using the most intensive
Zn\Mn diffraction lines. On the contrary, the AFM measurement
yields the agglomerate size in the surface plane. The agglomerates
in this case are seen as surface “islands” consisting of crystallites
that stick together [48]. So, it can be concluded that for both chloride
and sulfate electrolyte, the increase in c.d. decreases the crystallite
size, however, higher number of crystallites tends to agglomerate at
higher c.d.s., which leads to a rougher and less homogeneous surface,
as AFM has shown. This tendency is more expressed in sulfate elec-
trolyte, and as a result, the coatings obtained from this electrolyte at
c.d.s. higher than 80 mA cm −2 are non-adherent and dendritic, al-
though with single crystallites of less than 13 nm in size.
easily formed on the corroding surface, when higher Mn percent in
the coating is present. These oxides have been reported to inhibit the
cathodic reduction of dissolved oxygen [50].
Furthermore, the XRD data bring the conclusion that crystallite
size also plays important role in the corrosion behavior of Zn\Mn
coatings. Is has been seen, namely, that because of high deposition
overpotential, the crystallites are considerably smaller in the coatings
grown from sulfate electrolyte, thus increasing their corrosion resis-
tance, as compared to the deposits from chloride electrolyte. This is
in accordance with literature data which showed that there was an
increase in the corrosion resistance of Zn electrodeposits as the crys-
tallite size decreased [51].
Nevertheless, according to the literature, the corrosion resistance
of Zn alloy coating can be more strongly affected by the deposit mor-
phology than by its composition [38,48]. Regarding this, it can be ob-
served in Table 1 that the polarization resistance values for Zn\Mn
alloys, irrespective of the baths used, decrease as deposition c.d. in-
creases, although the Mn content increases, proving that high Mn
content is not a sufficient condition for improving the corrosion resis-
tance. The AFM data have disclosed the tendency for discrete larger
agglomerations to be grown as deposition c.d increases, especially
on the samples grown from sulfate electrolyte, where the Rp decrease
is more expressed. Such agglomerations may lead to enlargement of
roughness and non-uniformity of deposit, and therefore may be relat-
ed to the local dissolution of alloy and lower corrosion durability [48].
Similar correlation between the deposition c.d., surface morphology
and corrosion behavior was reported for Zn\Mn deposits obtained
from pyrophosphate electrolyte [16].
To sum up, the highest corrosion resistance is observed for the
Zn\Mn coatings deposited from sulfate electrolyte at lower c.d.s.,

3.5. Electrochemical corrosion behavior in chloride environment

Polarization curves in a small potential range near to OCP were

obtained in the linear polarization test for the Zn\Mn alloy samples
deposited at different c.d.s from chloride and sulfate electrolyte. Po-
larization resistance Rp was determined from the slope of experimen-
tal curve (dE/dj) at the OCP [49], as shown in Fig. 6a for two samples.
In addition, Tafel plots were recorded and the curves for the samples
deposited at 30 and 50 mA cm −2 are presented in Fig. 6b as an exam-
ple. The more positive OCP value for the samples obtained from chlo-
ride solution, as seen in Fig. 6, denotes that the coatings are nobler
than the samples obtained from sulfate electrolyte, which is probably
the consequence of higher percent of the less noble metal, Mn, in the
coatings obtained from the latter electrolyte.
The Rp values are presented in Table 1. The data indicate that the cor-
rosion behavior of Zn\Mn samples is strongly affected by two indepen-
dent factors, i.e. chemical/phase composition and surface morphology.
Firstly, a considerably higher corrosion resistance for the deposits
obtained from sulfate electrolyte could be observed. This can be as-
cribed to the different Mn content, because it has been shown in the
previous analysis that for the entire deposition c.d. range, the Zn\Mn
alloy deposited from sulfate bath is richer in Mn, and consists of
Mn-rich ε-Zn\Mn phase, as compared to the alloys deposited from
chloride electrolyte, which have smaller Mn content, and where the
η-Zn\Mn phase was observed at lower deposition c.d.s. It has been
shown by some authors that by increasing Mn content of Zn\Mn
alloy coatings, the corrosion resistance would increase [30]. In this re-
spect, it has been suggested that higher Mn content promotes a forma- Fig. 6. Polarization curves of the Zn\Mn coatings electrodeposited from chloride and
tion of more compact passive layer made of Zn salts, which suppresses sulfate electrolyte (a) in the range of ± 15 mV, for the samples deposited at
the anodic dissolution [30]. In addition, various Mn oxides are more 30 mA cm−2, and (b) Tafel plots.
228 M. Bučko et al. / Surface & Coatings Technology 228 (2013) 221–228
due to sufficiently high Mn content on one side, and smooth, homo-
geneous surface on the another side.
4. Conclusions
On the basis of the results presented it could be concluded that an-
ions present in the plating electrolyte, i.e. Cl − and SO42− ions, have
significant influence on the current efficiency, chemical composition,
phases formed, as well as on the morphology and corrosion behavior
of Zn\Mn electrodeposited alloys.
It was shown that higher deposition overpotentials in sulfate elec-
trolyte lead to a lower current efficiency for metal deposition, but also
to the increase in Mn content and the decrease in the crystallite size.
In the bath containing sulfate ions, the percentage of Mn in the alloy
increased from ~ 2 wt.% to ~ 17 wt.% as the deposition c.d. changed
from 20 to 80 mA cm −2, while in the chloride electrolyte, the Mn
content remained in the range of 1–10 wt.%, for the same range of c.d.
According to the AFM microphotographs, crystallites tend to ag-
glomerate at higher deposition c.d.s, leading to a rougher and less ho-
mogeneous surface, in both electrolytes. However, this tendency is
more expressed in sulfate electrolyte, so the deposits from this electro-
lyte at c.d.s higher than 80 mA cm−2 are non-adherent and dendritic.
The electrodeposition from sulfate electrolyte enables the formation of
very smooth deposits at low c.d.s, but the surface of the coatings be-
comes significantly heterogeneous as c.d. increases. Contrary, deposits
obtained from chloride electrolyte are compact and smooth in wider
c.d. range.
The X-ray analysis of the Zn\Mn deposits produced at three differ-
ent c.d.s, in both electrolytes, indicated that the alloys were homoge-
neous, composed of a single phase. Higher Mn percentage in the
alloys deposited from sulfate bath, enabled the formation of ε-Zn\Mn
phase for the total range of c.d.s. between 50 and 80 mA cm−2, while
the sample deposited from chloride electrolyte at 50 mA cm−2 was
made of η-Zn\Mn phase.
The linear polarization method showed that the Zn\Mn electro-
deposits produced from sulfate electrolyte possessed higher polariza-
tion resistance (Rp) than those deposited from the chloride bath,
probably owing to the structure consisting of ε-Zn\Mn phase, higher
Mn content and smaller crystallites in the coating.
Acknowledgment
This research was financed by the Ministry of Education, Science
and Technological Development, Republic of Serbia (Grant No. III
45019).
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