ISSN: 0975-8585

Research Journal of Pharmaceutical, Biological and Chemical

Sciences

Electrodeposition of Mn-Zn Alloy Coatings with High Manganese Content

from Sulfate-EDTA Solution in the Presence of Sodium Selenate Additive.
David Gogoli*, and Gigla Tsurtsumia.

Rafael Agladze Institute of Inorganic Chemistry and Electrochemistry of Ivane Javakhishvili Tbilisi State University, Tbilisi,
Georgia.

ABSTRACT

We obtained mirror-like coatings based on a nanocrystalline, globular-shaped Mn-Zn alloy with a high
Mn content (98%) from a sulfate-ethyleneddiaminetetraacetic acidic bath in the presence of sodium selenate
(Na2SeO4) as an additive. The nanocrystalline electrodeposited Mn-Zn alloy coating, featured broad and poorly
defineddiffractograms X-ray diffractograms, which corresponded to a cubic α-Mn crystal structure. The sodium
selenate additive, concentrations and nature of components in solution affected the production of a mirror like
coating of the Mn-Zn alloy. Using cyclic voltammetry and linear sweep voltammetry, we found that the sodium
selenate additive hindered a hydrogen evolution side reaction, which proceeds in parallel with the manganese-
zinc co-deposition process. In air, the coatings with a high content of manganese were covered with a black
hydroxo-oxide. The corrosion of the alloy coating was studied in aerated 3.5% NaCl solution. The high content
of manganese in the coating provides a high negative corrosion potential for the steel substrate therefore
providing anodic protection of the steel.
Keywords: electrodeposition, Mn-Zn alloy, complexing ligands, chemical composition, current efficiency

*Corresponding author

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INTRODUCTION

Galvanic coatings of manganese and its alloys as protective material have long attracted the attention
of researchers owing to their high negative potential and ready availability. Manganese alloys with Cu, Zn, Fe,
and Ni are characterized by high sacrificial protection characteristics and by their economic efficiency, which
make these metals common components in protective coatings based on aluminum and magnesium [1].

A applications of pure manganese coatings have been hindered by their relatively high chemical activity
and brittleness, which could be addressed by changing manganese of crystalline structure. Electrodeposition of
Mn at room temperature from ultra-clean solutions by electrolysis yields plastic γ-Mn with a BCT (body central
tetragonal) structure. In a short time, the deposited film transforms into a BCC (body centered cubic) α-Mn form,
which is stable but brittle [2]. The brittle, α-Mn can be modified in the presence of additives, such as sulfite-ion
(SO32-) or selenium compounds (SeO32- or SeO42-) from manganese-ammonium sulfates or chloride solutions.
These conditions support a stable cathodic process with a high current efficiency but also induce deterioration
of the mechanical properties of coatings [3].

Many researchers have attempted to decrease the chemical activity and brittleness of manganese [4,
5]. It has been suggested that to alloying manganese with metals that have more positive standard potentials,
e.g., Cu, Zn, and others, could stabilize the of γ-Mn form. For example, incorporation of 3% Cu into manganese
contributes to stabilization of the γ-Mn form for a long period.

Special attention has been paid to coatings, that contain zinc and manganese. Such coatings with high
and low manganese contents show good protective and mechanical properties [6, 7]. The application of Zn
corrosion protection coatings for the of iron substrates is widespread. The protective properties of zinc coatings
are based on their interactions with atmospheric O 2, H2O, and CO2, to form a dense and adherent film, which
protects the iron from corrosion. Furthermore, in the case of galvanic corrosion, Zn is anodic to steel and as a
result, it becomes the anode while the ferrous substrate becomes the cathode and does not corrode [8].
Corrosion resistance of zinc coatings depends on the composition of the atmosphere in which the steel is
functioning. Its coatings are stable in dry atmospheres but unstable in humid sea environment (owing to the
effects of Cl-ions). To increase the corrosion resistance of zinc coatings, Zn is alloyed with non-deficit metals
such as manganese, which have a more negative potential than that of Zn. Manganese is anodic to Zn, thus, it
protects Zn sacrificially. Furthermore, a synergistic effect is observed in the case of Mn-Zn alloys, resulting in
better corrosion resistance compared with those of other Zn alloys. This is attributed to the formation of water
insoluble basic salts of zinc and manganese on the surface of the coatings. These protective layers inhibit
cathodic reduction of air oxygen therefore increasing the cathodic polarization of the corroded surface and
decreasing overall corrosion [9]. Ukrainian researchers [10] have obtained Zn-Mn galvanic coatings with 55%
current efficiency from manganese-zinc sulfate solutions containing sodium citrate as complexing agents.
Testing of this coatings in aggressive environments showed that their corrosive resistance depends on the
manganese content. Specifically, under high humidity conditions, traces of corrosion were observed on Zn-Mn
coatings with 20% and 50% of Mn contents after 2402 and 2506 h., respectively. In the case of pure zinc coatings
with the same thickness as the Zn-Mn coatings, protection was realized in the same environment for only 628
h. It should be noted that citrate-containing electrolytes used in the work mentioned above were unstable owing
to the formation of precipitates in solution over the time.

Zn-Mn coatings are usually electrodeposited from chloride, sulfate or pyrophosphate baths containing
complexing agents, such as-citrate-ions or ethylenediaminetetraacetic acid (EDTA) [11-17], to bring deposition
potentials close to each other, because the standard electrode potential of Zn 2+/Zn and Mn2+/Mn couples are
considerably different, (- 0.76 V/SHE for Zn and -1.18 V/SHE for Mn). The potentials of zinc and manganese are
much more negative than the potential for hydrogen evolution; hence, the reaction of hydrogen evolution
occurs during the Zn-Mn coating deposition. This effect results in low current efficiency, inhomogeneous
coverage of surface and poor adhesion on the coating to the substrate.

The main problems of the Zn-Mn deposition process are poor bath solution stability and very low
current efficiency, especially for the case of high Mn contents. The Mn content in coatings has been increased
to more than 50% by electrodeposition under a pulse regime with a very low current efficiency.

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Bozzini et al. [20] found that the addition of thiocarbamide to a sulfate-citrate bath increased current
efficiency and achieved a Mn content of 70-80% in the alloy with the favored phase being a nanocrystalline
globular ε-phase.

The goal of the present research was to obtain high quality Mn –Zn coatings with a high content of Mn
at acceptable current efficiencies, from sulfate-citrate, sulfate-EDTA solutions, containing sodium selenate (NS)
additives. NS was selected because the addition of selenite or selenate inhibits hydrogen evolution, increases
the over potential of manganese deposition, facilitates crystallization of α-Mn, improves the leveling effect of
the electrolyte, and ultimately improves the manganese current efficiency [21].

Mn-Zn alloys obtained galvanostatically were characterized by analyzing their chemical composition,
morphology, structure and the corrosion behavior of coating. Electrochemical reactions of interest were
examined by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and chronoamperometry.

EXPERIMENTAL SECTION

Electrolytes were prepared from analytical grade reagents. Electrolyte preparation, conditions of
electrolysis and calculation of alloys cathodic current efficiency have been previously reported in detail [22]. Mn-
Zn deposits were obtained from base sulfate electrolytes which contained: 2-5g∙l-1 ZnSO4∙7H2O, 6-10g∙l-1 EDTA
(Na2H2CH12O8N2∙2H2O) or trisodium citrate (Na3C6H5O7∙5.5H2O), 29-58 g∙l-1 MnSO4, 34-68g∙l-1 (NH4)2SO4.
Furthermore, NS (Na2SeO4) in the range of 0.33-1.25 g∙l-1 was added to the basic bath.

The electrochemical characterization was performed in a conventional three-electrode cell with a water
jacket. In this study, the working electrode was a carbon steel (C 0.22%, Mn 0.52%, Si 0.18%, P<0.04%, S<0.05%,
As<0.08%) electrode, composed of the same material as the substrate for the deposition of the Mn-Zn coatings,
with a surface area of 0.2 cm2. The reference electrode was a saturated Ag/AgCl electrode contacted with the
cell through a Luggin capillary. All potentials in this paper are referensed to this electrode. The counter electrode
was a Pt plate. No stirring was applied during the measurements. Prior to each experiment, the working
electrode was polished with emery papers of 600 and 1200 grades, cleaned with a soda wet swab, pickled with
1M H2SO4 for 20 s, and finally were rinsed with distilled water. The morphology and structure of deposits were
estimated from the current efficiency of the electrodeposition and densities of the alloys, and also confirmed by
scanning electron microscope (SEM) cross-section measurements.

Electrochemical experiments were performed with an Electrochemical Analyzer (CH Instruments,

Austin, TX, USA) operated with CHI600E software.

Galvanostatic electrodeposition of Mn-Zn alloys was performed on steel plates with a geometrical area
of 4 cm2. The thickness was verified by a coating thickness measurement instrument DCFN 3000EZ. The thickness
of the deposited alloy also was examined with a (SEM), (JSM-6510 series JEOL Ltd. Japan) and by X-ray diffraction
(Russian production, copper anode Кα-emission, λ=1.54184 Å). The chemical composition of the coating was
determined by the X-ray-fluorescence analysis method (Delta-Analyzer,< Innov-X Systems >USA) and with an X-
ray energy dispersion micro-spectral analyzer (JSM 6510 LM, Japan).

RESULTS AND DISCUSSION

The presence of the additive NS in solution 5 g∙l-1 ZnSO4∙7H2O, 10 g∙l-1 EDTA, 58 g∙l-1 MnSO4, and 68 g∙l-1
(NH4)2SO4 was effective in obtaining a mirror-like surface based on Mn-Zn alloy electrodeposition with a Mn high
content. The influences of the current density on the chemical composition of the alloy coating and current
efficiency are shown in Table 1.

Table 1 shows that a small increase of the current density resulted in a marked increase of the
manganese content and a decrease of current efficiency. Further increases of the current density made the
coating dendrite-like and of poor quality. Note that after removing the coating from the bath and washing in
water, it became black after several min owing to oxidation in air.This is a characteristic of freshly deposited
pure metallic manganese coating surfaces. To avoid oxidation of the deposited alloy, after removing the
electrodes from the bath they were immersed in 10% K 2Cr2O7 solution for 10 s. The electrodes were washed

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with distilled water and dried in air. SEM images (Fig. 1) of the mirror-bright coatings show that coatings featured
a nanocrystalline and globular texture.

Table 1. The influence of current density on chemical composition and current efficiency of coating.
Solution: 5 g∙l-1 ZnSO4 ∙7H2O, 10 g l-1 EDTA, 58 g∙l-1 MnSO4, 68 g∙l-1 (NH4)2SO4 , and 0.33g∙l-1 NS; pH 3.5-5.0;
t=300C; plating time 15 min

Current density, Mn content, Current efficiency of alloy,

(A cm-2) (Wt%) (%)
0.1 97.5 51.7
0.125 98.0 49.4
0.15 98.3 47.7
0.175 98.5 45.2

Fig.1. SEM micrograph of a Mn-Zn (Mn 98%) alloy electrodeposited at 0.1A∙cm-2

Results of X-ray analysis of electrodeposited Mn-Zn alloy are shown on Fig.2. Owing to the
nanocrystalline size of the electrodeposited coating, the peaks of the diffractograms were broad and poorly
defined. The diffractograms corresponded to a cubic α-Mn crystal structure. A small amount of zinc was
dissolved in the α-Mn and the most intense diffraction peak of Zn(101) was overlapped by the α-Mn (330) peak.

Fig.2. X-Ray diffractogram of a electrodeposited Mn-Zn (Mn 97.8%)

Grains in the coating had an average size of less than 10 nm as evaluated by the Scherrer method based
on the half width of the diffraction maximum.

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Any change of concentration of the solution components, either an increase or decrease, notably
decreased the mirror like appearance of the coating; the surface changed to a cloudy grey-black color, with a
spongy, non-adherent, and powdery texture. Such layers were in- appropriate for applications as protective
coatings. Our efforts to achieve the desired results by maintaining a constant ratio of the solution components,
and substituting EDTA with other complexing agents (such as gluconate, tartaric acid, and seignette salt), were
unsuccessful. Only when citrate-ions were used (at the same concentration as EDTA) and at high current
densities (≥ 0.4 A∙cm-2), were high quality, white, dense coatings with a high content of manganese obtained.
The effects of the solution composition on the appearance of the coatings could be explained by the specific
adsorption of EDTA and NS on the surface of electrode. Their concentrations on the surface effected the content
of the electrochemically active zinc and particles manganese containing complexes. Solution pH also effected
the production of high quality Mn-Zn alloy coatings. Specifically, the Mn-Zn alloy mirror-like coatings were
obtained only in the range of pH 3.0-5.5. We selected 30o C as the temperature for electrodeposition. The
thickness measured by a DCFN 3000EZ instrument for coatings deposited for 15 min varied in the range of 15-
20 μm.

The electrochemical reactions occurring at the steel electrode in basic solutions were studied by cyclic
voltammetry (Fig. 3) without NS (curve a) end with NS (curve b).

150
100
I,mA/cm2

50
0
-50 E corr.
-100
-150
-200
-250 a
-300 b
-350
-400
-450
-1.7 -1.5 -1.3 -1.1 -0.9 -0.7

Ev, Ag/AgCl
Fig.3. Typical cyclic voltammogram obtained on carbon steel from aerated basic solution: 5 g l-1 ZnSO4 ∙7H2O,
10 g∙l-1 EDTA, 58 g∙l-1 MnSO4, and 68 g∙l-1 (NH4)2SO4; pH 3.5;t=300C; without NS additive (a) and with 0.33g∙l-1
NS additive (b); scan rate 10mV∙s-1.

Scanning of the potential (10 mV∙s-1) was performed from the stationary potential of steel -690mV
(Ag/AgCl) towards more negative potentials until a cathodic potential of -1.6 V (Ag/AgCl) was reached. The
direction of the potential scan was then reversed in the positive direction until the initial stationary potential
was reached. For cyclic voltammograms, when the potential was scanned in a negative direction a visible
increase of the current was observed from -1.42 V (Ag/AgCl) in solution without NS additive (Fig. 3, carve a). At
-1.6 V (Ag/AgCl) after reversal of the scanning in a positive direction, the cathodic current increased, which
indicated the formation of a new phase before reverse scanning. An anodic peak was observed at -0.975 V
(Ag/AgCl). In the case of the NS additive (curve b) the cathodic parts of the voltammograms measured in negative
and positive directions essentially overlapped. However, the voltammograms differed considerably in their
anodic area when obtained without the NS additive (curve a); specifically, a change in the anodic area was
observed at -1.41 V (Ag/AgCl) and anodic current were detected at -1.34 V (Ag/AgCl) and -1.20 V (Ag/AgCl) with
a peak current at -1.26 V (Ag/AgCl). For further scanning of the potential in a positive direction a current peak
appeared at -0.98 V (Ag/AgCl) similar to that of the voltammograms obtained without an NS additive; however,
smaller in size. For the steel electrode, in a solution of manganese-ammonium sulfate, without zinc ions, EDTA,
and NS additives, the potential scanning in a negative direction showed a considerable increase of the current
resulting from the reduction of hydrogen or water molecules at -0.8 V (Ag/AgCl). The formation of hydrogen gas
at the electrode was detected. Reduction of Mn 2+occuared from -1.40 V (Ag/AgCl), determined by conducting
electrolysis at a controlled potential and analysis of the solution after dissolution of the deposited coating. In a
solution of manganese-ammonium sulfate with Zn2+- ions, when the potential was scanned in a negative
direction, an increase of the cathodic current was observed at -1.0 V (Ag/AgCl), which was associated with

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reduction of Zn2+ (result not presented). Owing to dissolution of the deposited Zn, the anodic current peaks
appeared at -0.98 V (Ag/AgCl) in the curves when the potential was scanned in the positive direction. This result
is in agreement with voltammetric investigations of Zn reduction by other researchers [23]. To understand the
nature of the current peaks in cyclic voltammograms measured in basic solutions with and without NS additive,
we performed cathodic polarization of a steel electrode for 10 s at potentials of -1.2 V (Ag/AgCl), -1.4 V (Ag/AgCl),
-1.6 V (Ag/AgCl). We recorded voltammograms by scanning the potential in a positive direction up to the
stationary potential of the steel electrode (Fig. 4-A, B, C).

2 A 6
4 B
1
2

I,mA/cm2
I,mA/acm2

0 0
-2
-1 -4
a
-6 a
-2 b -8 b
-3 -10
-12
-4 -14
-1.25 -1.05 -0.85 -0.65 -1.45 -1.25 -1.05 -0.85 -0.65

E,v (Ag/AgCl) E,v(Ag/AgCl)

140
C
70
0
I,mA/cm2

-70
-140
-210 a
-280 b
-350
-420
-1.65 -1.35 -1.05 -0.75

E,v(Ag/AgCl)
Fig.4. Linear voltammograms obtained for steel electrode at scaning rate 10mVs -1 in aerated solution 5 g l-1
ZnSO4 ∙7H2O, 10 g∙l-1 EDTA, 58 g∙l-1 MnSO4, 68 g∙l-1 (NH4)2SO4; pH 3.5; t=300C. A- cathodic polarization at -1.2 V
(Ag/AgCl) for 10 s without additive NS (a) and with 0.33g∙l-1 NS additive (b);
B- cathodic polarization at -1.4 V (Ag/AgCl) for 10 s without additive NS (a) and with 0.33g∙l-1 NS additive
(b);
C- cathodic polarization at -1.6 V (Ag/AgCl) for 10 s without additive NS (a) and with 0.33g∙l-1 NS additive (b).

Fig. 4-A,B,C shows that the NS additive in solution hindered the hydrogen evolution process and
together with EDTA facilitated the manganese and zinc co-deposition processes. Oxidation peaks in the curves
scanned in a positive direction, were located between -1.34 and -1.2 V (Ag/AgCl), which represented
characteristics of the alloy phase composition. Notably, similar anodic voltammograms were obtained by Sylla
and coworkers [24] in basic pyrophosphate solutions for Zn-Mn alloy coatings, but with manganese contents of
25%.

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4
3
2

Lgi,mA/cm2
1
0
-1 1-Mn-Zn
-2 2-Zn
3-Fe
-3
3
-4
-5 2
1
-6
-1.45 -1.2 -0.95 -0.7 -0.45 -0.2 0.05

E,v (Ag/AgCl)

Fig5. shows Tafel polarization curves, obtained for Mn (98%Wt)-Zn alloy (a), for pure Zn coated on steel (b)
and carbon steel (c) in 0.5 M NaCl as a corrosive aggressive media (Cl- ions).

The potential scaning (10mV∙s-1) was performed, without stirring the solution, from a potential 200 mV
more negative than the corrosion potential in the anodic direction until an anodic current of 15 mA was
obtained. The thickness of the coating in the case of Mn-Zn and Zn was 20 μm, which as measured by a DCFN
3000EZ instrument and confirmed by SEM observations.

Fig. 5 shows that the high content of manganese in the alloy determined its more negative corrosion
potential compare with that of the zinc and steel electrode. The linear parts of the curves were extrapolated to
the corrosion potential to determine the corrosion current. The corrosion current densities were 0.56, 4.78,
and 8.078 μA∙cm-2 for the Mn-Zn alloy, pure Zn coating and carbon steel, respectively. The corrosion potential
of the mirror-bright surface of electrodeposited Mn (98%Wt)-Zn alloy in aerated 3.5 % NaCl solution (pH 6.6), at
300 C was -1.269 V (Ag/AgCl). After 25 days, the corrosion potential increased to -1.260 V (Ag/AgCl); gas
formation on the surface was not observed; however, the surface became black owing to the formation of hydro-
oxides of manganese. The observed corrosion potential of the coating was considerably more negative than that
of carbon steel corrosion (-690mV, Ag/AgCl), which indicates that the coating was a good protector of steel
against corrosion. Anodic polarization of the Mn-Zn alloy coating in 0.5 M NaCl solution showed intensive
evolution of hydrogen and loss of the coating from the active area of the surface. This effect was attributed to
the removal of the passivation layer of dichromate on the coating owing anodic dissolution and interaction of
the nanocrystalline sized active manganese with water (1):

Mn +H2O⟶MnO+ H2 (1)

On the basis of these results we can conclude that, although the Mn-Zn alloy nanocrystalline mirror-
like coating with a high manganese content featured a high negative value of the corrosion potential, for
corrosion stability it was necessary to treat the coating with a solution of 10% K2Cr2O7 -to create a stable passive
layer on the surface.

CONCLUSIONS

We obtained mirror-bright nanocrystalline, globular shaped Mn-Zn alloy coatings with a high
manganese content from the solution. The conditions included:

5 g∙l-1 ZnSO4 ∙7H2O, 10 g∙l-1 EDTA, 58 g∙l-1 MnSO4, 68 g∙l-1 (NH4)2SO4, 0.33 g∙l-1 NS, pH 3-5.5; t=300C; current density
0.1 - 0.175 mA/cm2; plating time τ=15min; coating composition: 97.5 - 98.5% Mn, 2.5-1.5 % Zn; and current
efficiency 45.2 - 51.7%.

Owing to the nanocrystalline size of the electrodeposited Mn-Zn alloy coating, peaks in diffractograms
obtained by X-ray analysis were broad and poorly defined. The diffractograms corresponded to cubic α-Mn
diffraction peaks.

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The concentration of additives, such as sodium selenate (NS), and the nature of the solution
components effected the production of mirror-bright Mn-Zn alloy coatings. We found that without additive, low
quality, cloudy, grey-blackish, non-uniform coating were obtained.

Using cyclic voltammetry and linear sweep voltammetry we determined that the additive NS hindered
a hydrogen evolution side reaction, which occured in parallel with the manganese-zinc co-deposition process.
Electrodeposited Mn (98%Wt)-Zn alloy coatings maintained a more negative corrosion potential in the
aggressive environment compared with that of bare carbon steel. This layer protected the steel against
corrosion.

Treatment of the coating in a solution of 10% K2Cr2O7 helped to preserve mirror-bright nanocrystalline
Mn-Zn coating and enhanced corrosion stability owing to the formation of a passivation layer.

ACKNOWLEDGMENTS

This work was supported by Shota Rustaveli National Science Foundation (SRNSF) of Georgia (grant
number № YS-2016-18).

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