Electrochimica Acta 54 (2008) 793800

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Pulse plating of MnCo alloys for SOFC interconnect applications

Junwei Wu a,b , Christopher D. Johnson a , Yinglu Jiang a,b , Randall S. Gemmen a , Xingbo Liu a,b,
a
b

National Energy Technology Laboratory, Department of Energy, Morgantown, WV 26507, USA

Mechanical and Aerospace Engineering Department, West Virginia University, Morgantown, WV 26506, USA

a r t i c l e

i n f o

Article history:
Received 5 March 2008
Received in revised form 23 June 2008
Accepted 24 June 2008
Available online 3 July 2008
Keywords:
Interconnect
SOFC
Pulse plating
Charge and discharge
Off-time

a b s t r a c t
(Mn,Co)3 O4 Spinel is a promising coating for SOFC interconnect applications due to its high conductivity and good chromium retention capability. Electroplating of alloys followed by oxidation offers a cost
effective method to produce the desired spinels. Pulse plating is always considered as a better method
than direct current (DC) plating in the formation of alloys. In this research, cyclic voltammetry is used to
characterize dissolution potential of each element. Mn begins to dissolve at 1.4 VSCE , and cobalt begins
to dissolve at 0.7 VSCE . By means of pulse analysis, charge and discharge times are obtained, which are
found to be much shorter than the on- and off-time applied at peak current density of 300 mA/cm2 . Two
segments of charge periods show up at this peak current density. By comparing charge times at different
peak current density, one segment can be attributed to the double layer charge and another to the uniform
hydrogen bubble layer. During pulse plating, Mn content decreases with increasing off-time, and surface
morphologies change from ake like structures to crystalline structures. This resulted from increased Mn
dissolution into the solution and hydrogen bubble release from the coating during increased off-time.
Long-term (1200 h) ASR measurements demonstrate stable ASR with slight increase. The ASR value at
40,000 h was predicted to be 0.0460  cm2 . Almost no Cr was spotted on the surface. Further, more Mn
was found on the conditioned surface than the as-deposited surface which further proves faster diffusion
of Mn than Cr.
2008 Elsevier Ltd. All rights reserved.

1. Introduction
The decrease of the operating temperature of SOFC technology
makes it possible to use chromia-forming alloys as interconnects instead of LaCrO3 ceramic, allowing improved gas tightness,
machinability and high oxidation resistance and low cost [1].
However, the excessive growth of chromia scales and chromium
evaporation into cells can lead to unacceptable degradation in cell
electrochemical performance [1,2]. Applying a surface coating is
one of the most effective methods to resolve these problems [3].
Among potential coating materials, (Mn,Co)3 O4 spinel is most
promising because of its high conductivity, and excellent chromium
retention capability. Apart from that, nominal compositions of
Mn1.5 Co1.5 O4 spinel also shows good CTE match with cathode and
ferritic stainless steels [46], which has been applied to metallic
interconnects materials by means of spray, screen printing [46],
and physical vapor deposition (PVD) [7]. Electroplating of alloys to
achieve a thin lm layer, followed by controlled oxidation to the

Corresponding author at: Mechanical and Aerospace Engineering Department,

West Virginia University, Morgantown, WV 26506, USA. Tel.: +1 304 2933111x2324;
fax: +1 304 2936689.
E-mail address: Xingbo.liu@mail.wvu.edu (X. Liu).
0013-4686/$ see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2008.06.057

desired spinel phase, offers an additional deposition option. The

advantages of electroplating are that it is low cost and applicable to
complex shapes. The feasibility of using electroplating for this purpose has been substantiated by our previous work [8,9] and other
work [10]. For co-deposition, the deposition potentials of the two
metals need to be close in order to form an alloy. However, the
standard electrode potential of the Co2+ /Co is 0.28 VSCE , and that
of Mn2+ /Mn is higher, 1.18 VSCE . This signicant difference makes
it impossible to obtain any Mn from conventional electrodeposition. Lowering the concentration of the more noble metal (Co) in
the electrolyte is one possible path, but it is not too practical for
mass production as it requires strict control over solution concentration in a dynamic system. In our previous study [9], various Mn
and Co content alloy coatings were obtained by co-deposition in
0.50 M MnSO4 + 0.10 M CoSO4 solutions with some additives. However, only thin or porous coatings were obtained, requiring further
optimization of surface morphology, coating thickness, as well as
controlling the oxidation process.
There are two different conventional methods used for electroplating: DC plating and pulse plating. Pulse plating has been
regarded as alternative plating mode to DC plating. In pulse plating
three addition parameters can be varied independently for control
over lm quality, peak current density, on- and off-times [11]. Peak
current densities that are higher than typical DC plating currents

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J. Wu et al. / Electrochimica Acta 54 (2008) 793800

can be applied to get higher overpotential and more nucleation

sites, these same current densities in DC plating would lead to
rough, powdery deposits. Off-time in pulse plating enables larger
currents/voltages to be applied during the on-time, since the mass
transfer limitation is avoided and the resulting surface morphology and current efciency is improved [11]. By varying the on- and
off-time, nanocrystalline alloys and multilayer coatings have been
deposited successfully [12,13]. It can also be used to control the
composition and microstructures of depositions, as well as allowing for some additives to be replaced, and thus simplifying the
deposition process.
In the present work, Mn/Co alloys are deposited on stainless
steel 430 by pulse plating, and the effects of off-time and duty cycle
on the surface morphology and composition of coatings are studied.

preparation and substrate preparation processes were described in

previous work [9]. Different peak current densities, and on- and
off-times were controlled by Dynatronix DPR 201030.

2. Experimental

ASR measurement of one coated sample was conducted for

1200 h at 800 C. The ASR test is a four-wire resistance measurement method. Details were described in a previous publication [14].
Before and after the long-term test, the surface morphology and
composition were characterized by SEM&EDX.

2.1. Cyclic voltammograms and pulse width analysis

Both cyclic voltammetries and pulse analysis were carried out
using three solutions, which are 1.0 M H3 BO3 + 0.70 M sodium gluconate with additions of 0.50 M MnSO4 , 0.10 M CoSO4 , 0.50 M
MnSO4 + 0.10 M CoSO4 , respectively. The detailed procedure to prepare solution was described in our previous work [9].
A classic three-electrode cell was used for the experiments.
The hardware setup is displayed in Fig. 1.Two counter electrodes,
graphite rods, are applied to put both side of working electrode.
Working electrode is SS430, which was mechanically grinded with
various grades of silicon carbide papers up to 2400 grit. Saturated
calomel electrode (SCE) was used as reference electrode, and all
potentials are given with respect to this reference. Cyclic voltammetry experiments were carried out by Solartron 1287 with the
scanning rate of 15 mV/s.
The current and voltage response to the applied current pulses
are analyzed using a Tektronix TDS 784D oscilloscope using a long
on- and off-time. Also, for short on- and off-times, charge and discharge time on the double layers were recorded.
2.2. Pulse plating
The pulse plating was conducted on stainless steel 430 substrate.
The edge is covered by Teon with exposed area of 1 cm2 in order to
reduce the edge effect. Solutions were prepared with distilled water
and had a pH of 2.5. Its composition was 0.50 M MnSO4 + 0.10 M (or
0.05 M) CoSO4 + 1.0 M H3 BO3 + 0.10 M (NH4 )2 SO4 . Detailed solution

Fig. 1. Sketch of experimental setup.

2.3. Coatings characterization and oxidation

Scanning electron microscopy (JEOL 6300) was used for surface
morphology observation and an attendant energy dispersive X-ray
analyzer (EDAX) was used for chemical analysis of the as deposited
coating. For each sample, three spots were analyzed to get the average composition. One coating was further selected to be oxidized
at 800 C for 2 h to be characterized by SEM/EDX.
2.4. Long-term ASR measurement

3. Results
3.1. Cyclic voltammograms
Cyclic voltammetry results are displayed in Fig. 2 in solutions
of 1.0 M H3 BO3 + 0.10 M (NH4 )2 SO4 + 0.70 M gluconate with the
different additions of MnSO4 and CoSO4 . Curve (1) shows the
voltammetric behavior of the electrodeposition of cobalt using a
0.10 M Co(II) bath. The onset of Co deposition can be observed
at around 0.9 V, which corresponds to our previous potentiodynamic tests. On the return cycle, dissolution of cobalt starts at
0.7 V, and reaches a maximum at around 0 V. With the addition
of 0.50 M Mn(II) into 0.10 M Co(II) bath, one deposition plateau was
found at 1.5 V, which signied the deposition of Mn(II). However,
on the return cycle, only dissolution peak of cobalt was observed
and no dissolution of Mn showed up. Further cyclic voltammetry
curves were performed in pure Mn(II) solutions. Here, the same
potential of 1.5 V occurs for Mn2+ deposition, and the dissolution
during reverse scan peaked at 1.4 V corresponding to dissolution of Mn. That the current still remains negative, not positive,
is because the cathodic reduction of H+ and H2 O are still occurring
there. The dissolution of small amount of Mn will not bring the
current back to positive.

Fig. 2. Cyclic voltammograms of different solutions, scan rate 15 mV/s.

J. Wu et al. / Electrochimica Acta 54 (2008) 793800

795

Fig. 3. Potential-time transient curves at current density 300 mA/cm2 in different periods in different solutions: (a) one pulse cycle, (b) double layer charge time, and (c)
double layer discharge time.

There is no Mn dissolution peak in mixed Mn(II) and Co(II) solutions, due to the huge difference between the deposition potentials
of two cations. Displacement reaction (1) can occur during deposition:
Co2+ + Mn Mn2+ + Co

(1)

However, only a tiny peak during reverse scan is spotted in pure

Mn(II) solutions even when the scan maximum voltage is as high as
3.0 V, because of the high chemical reactivity of Mn. Beyond the
dissolution of Mn at anodic current, Mn will also dissolve according
to reaction (2):
Mn + 2H+ Mn2+ + H2

(2)

The above two reactions will dissolve Mn quickly before anodic

potential is applied, which can explain why only tiny or no Mn dissolution peaks is observed in pure Mn(II), Mn(II) and Co(II) bath,
respectively. Both of the reactions are detrimental to obtaining
high content Mn coatings. Previously, a similar result was reported
by Sylla et al. [15] using KCl + H3 BO3 matrix, who also attributed
the lack of Mn dissolution peak to the instability of the manganese deposits, which are easily dissolved in acidic media. While,
after detailed study by quartz crystal microbalance (QCM) and
SEM&EDX, Daz-Arista et al. [16] proposed that the lack of Mn
dissolution peak is due to being oxidized to Mn(OH)2 . Note that
both of their electrolytes contain 0.60.7 M MnCl2 4H2 O + 0.32 M
H3 BO3 + 2.8 M KCl. However, in our system, no hydroxide was spotted, even when current density is as high as 300 mA/cm2 , due to
chelating effect from excess amount of sodium gluconate and high
amount of pH buffer [9]. Nevertheless, the tiny Mn dissolution peak
is still related to the high chemical reactivity of Mn.

3.2. Potential transient curves

The charging of the electrochemical double layer occurs before
electron transfer can occur. This results from the overpotential to
drive the electrochemical reactions. The phenomenological models used to show a monotonically increasing overpotential with
increasing rate of electron transfer. The analysis of potential-time
curves allows determining this double layer charge and discharge
process. At the beginning of each pulse, the cathode potential must
be raised to the deposition potential before metal deposition occurs
[11]. In work on bismuthtelluride [17] and ironcobalt [18] pulse
co-deposition, the curves are found to be helpful for nding the
correct pulse on- and off-time parameters. As explained in literature [11,19], pulse on-time should be sufciently short to stay
well below a diffusion limiting condition, but sufciently long to
fully charge the double layer, and pulse off-time should be long
enough to make sure the double layer was discharged, in order to
allow the local concentration proles to relax and hydrogen bubbles to release from the substrate surfaceif these conditions are
not achieved, the effect of pulse plating is not signicantly benecial.
Fig. 3 displays one potential-time cycle for current controlled
pulses with amplitude = 300 mA/cm2 with on-time of 400 ms, and
off-time (0.0 mA/cm2 ) of 800 ms. Fig. 3(a) shows results for the
pure Mn2+ , pure Co2+ and a mixed cation solution. Cell voltage
jumps to high voltage instantaneously at the beginning of on-time,
then increases linearly with time, and at last declines to a steady
state at the off-time. The different initial cell voltages achieved
at start of on-time is due to the conductivity differences of each
solution. Note that the voltages do not drop to open circuit potential (EOCP ), which can be obtained from previous potentiodynamic
polarization results [9], but to a certain value at the off-time. All
these values are above 1.4 V. Combining with the results from
cyclic voltammetry, it can be summarized that Mn could dissolve

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J. Wu et al. / Electrochimica Acta 54 (2008) 793800

Fig. 4. Charge process visualization: (a) at peak current density of 50 mA/cm2 in 0.10 M CoSO4 , 0.50 M MnSO4 and 0.10 M CoSO4 + 0.50 M MnSO4 solutions and (b) at different
peak current density in solution of 0.10 M CoSO4 + 0.50 M MnSO4 .

in all solutions during the off-time, even in CoSO4 free solutions.

Two possible reasons are involved. Firstly, the pulse generator is
designed for high currents, so a non-negligible current at off-time
is present, which explains the non-zero potential at the off-time.
Similar results were reported before [20]. Secondly, the charge
transfer of Mn2+ at the interface is not as easy as that of Co2+ .
The overpotential is higher for Mn, so a little higher potential
appears in Mn2+ solution than that of Co2+ and Mn2+ + Co2+ solutions. Similar results have been reported in pulse plating of Cu with
additives of thiourea and chloride. Different additives can form different species, which will induce different potentials at the off-time
[21].
As shown in Fig. 3(b), two segments occur during the charge
process which has a total charge time around 100 s. These results
are different than the potential-time curves in literature [17,18]. The
reasons probably include: rstly, the time scale is micro seconds,
where as in the literature results are more often shown in millisecond time scales; and secondly, the two segment curves explain
different mechanisms and probably two layers during charge are
incorporated in the equivalent circuits. Discharge time curves are
exhibited in Fig. 3(c). Only one segment is displayed, and the double layers are discharged in 5 s. Note that the voltage at the end
of the on-time (end of Fig. 3(c)) is higher than at the start of the
on-time (start of Fig. 3(b)), which means the discharge could not
complete in 5 s. Nevertheless, the voltage difference is so tiny that
voltage has still been signicantly reduced, which indicates that a
large amount of hydrogen (bubbles) will release from the sample
surface. At the same time, Mn2+ and Co2+ will diffuse from the bulk
solution to the reaction zone, which will be involved into our later
study.
In order to clarify the two segments, additional charge periods were monitored at a low current density of 50 mA/cm2 in
0.10 M CoSO4 , 0.50 M MnSO4 and 0.10 M CoSO4 + 0.50 M MnSO4
solutions, as shown in Fig. 4(a). It is clear that only one segment
shows up, which means the second segment probably depends
on the applied current density. Accordingly, in solution of 0.10 M
CoSO4 + 0.50 M MnSO4 , the charge process is also visualized with
different peak current density from 50 to 300 mA/cm2 , as displayed in Fig. 4(b). There is only one segment in charge process
of peak current density at 50 and 100 mA/cm2 , while the second segment begins to show up at 150 mA/cm2 and further. It
is noteworthy that all of the second segments start at the critical voltage of 2.5 VSCE and the charge slope becomes steeper
with an increase in current density, which means the charge time
becomes shorter. Also, it is apparent that the charge time becomes
shorter at higher current density, similar result has been reported
[22].

3.3. Pulse plating results

Since both reactions 1 and 2 occur at the off-time of pulse plating, high duty cycle will be helpful to get high Mn coatings. A
duty cycle of 10/11 means off-time is set as 1/10th of each ontime. In this experiment on-time was set at 1 ms, 10 ms, 100 ms,
1 s and 10 s, so the corresponding off time was 0.1 ms, 1 ms, 10 ms,
100 ms and 1 s, giving a duty cycle of 10/11 for each deposition.
A solution of 0.50 M MnSO4 + 0.05 M CoSO4 + 1.0 M H3 BO3 + 0.70 M
sodium gluconate + 0.10 M (NH4 )2 SO4 was studied for Mn coating
concentration. The Mn content from EDX results are demonstrated
in Fig. 5 for a 20-min deposition with a duty cycle of 10/11. It is
obvious that with the increase of on (or off) time, Mn content in the
coating decreases. When the on time is as low as 1 ms and 10 ms,
the Mn contents are very similar and much higher than coatings
from different on- and off-times. However, it is still not clear what
the effect of on or off time is. At the same, the coatings become
denser and more compact with the increase of on and off-time (not
shown here).
Further pulse plating was carried out at the on-time of 1 ms and
10 ms, with the off-time of 1/10, 1/5 and 1/2 of the corresponding on-time. Coating surface morphologies are displayed at Fig. 6,
which demonstrates the ake like and porous structure of the coatings at 1 ms on, 0.1 ms off and 0.2 ms off, and 10 ms on 0.1 ms off.
With the increase of off-time, the morphology turns into compact
coatings, which are characterized by regularly shaped crystalline

Fig. 5. Mn content in the coatings as a function of on- (or off-)time at the same duty
cycle.

J. Wu et al. / Electrochimica Acta 54 (2008) 793800

797

Fig. 6. As deposited surface morphology of pulse plating at peak current density of 300 mA/cm2 : (a) 1 ms on, 0.1 ms off; (b) 1 ms on, 0.2 ms off; (c) 1 ms on, 0.5 ms off; (d)
10 ms on, 1 ms off; (e) 10 ms on, 2 ms off; and (f) 10 ms on, 5 ms off.

grains, with apparent grain size ranging from 1 to 3 m. EDX results

shows stronger substrate peaks than the coatings of crystalline
structure, which illustrated thinner coatings of ake like structure
(not shown here). The composition of coatings was exhibited in
Fig. 7, the ake like structure shows higher Mn content than that of
crystalline coatings.
3.4. ASR measurement
It has been suggested that ASR results only reect the conductivity of coating and subscale [23]. Therefore, ASR measurements
were carried out to characterize the conductivity of coatings. During oxidation, volume of coating will expand due to introduction of

Fig. 7. Coatings composition changes with different duty cycles at 1 ms and 10 ms

on time. (Corresponding to Fig. 5 coatings.)

oxygen. Accordingly some small defects, like pores and cracks, are
expected to be eliminated, which has been conrmed in previous
results [9].
SEM surface morphology of as-deposited coatings is demonstrated in Fig. 8. Some obvious cracks across the ne particles are
demonstrated on the surface. EDX semi-quantitative result exhibits
that Mn is 16 at.%. Also, weak Cr and Fe peaks are detected, which
mean the coating is not thick enough to prevent penetration of the
electron beam to the substrate. After 2 h oxidation at 800 C, all the
cracks have been eliminated, and only tiny spinels are spotted, as
shown in Fig. 8(b).
The oxidized coating was exposed to 800 C for 1200 h and ASR
measured. The ASR prole is shown in Fig. 9. During the initial
165 h, ASR value is not stable, probably due to the contact problem between platinum paste and sample. Then it remains stable in
the following 1000 h with only a slight increase. According to the
value obtained initially and at 1200 h, ASR value at 40,000 h was
predicted to be 0.0460  cm2 , assuming it is following parabolic
law, which is much lower than the target value of 0.1  cm2 after
40,000 h operation [1,3].
Fig. 8(c) shows the surface morphology of the coating after
1200 h of ASR measurement. Spinel size is becoming much bigger compared to the initially oxidized coating (Fig. 8(b)), so the
cubic structure much more apparent. Cross-section of the coating
shows dense, compact and good adhesion with the substrate, as
exhibited at Fig. 10(a). Also there are some internal oxidation spots
along the interface, which are probably from the silicon content
from the substrate. The total thickness is around 3 m. EDX linescan prole demonstrates clearly that the coatings are composed
of 1.5 m Cr2 O3 interlayer and 1.5 m (Mn,Co)3 O4 coating, as
shown in Fig. 10(b). The Mn and Co level are quite close, suggesting
that a signicant amount of Mn has migrated from substrate (the asdeposited surface had 16% Mn). Note that Cr peaks remain quite
low near the surface, which means little or no Cr diffuses into the
coating surface, also no Fe diffuses into the interlayer and coating.

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J. Wu et al. / Electrochimica Acta 54 (2008) 793800

Fig. 8. SEM surface morphology of Mn/Co coating: (a) as-deposited coating (Mn wt.% 16.5%); (b) after oxidation at 800 C for 2 h; and (c) after 1200 h ASR test at 800 C.

The result is the same with (Mn,Co)3 O4 coatings by thermal growth

[5,6].
4. Discussion
4.1. Charge and discharge time
During pulse plating, the charge time is the time required for
the cathode potential to reach the value corresponding to the pulse
current [11]. In pulse plating of bismuth telluride and cobaltiron
alloys, potentialtime curves have been applied to characterize the
charge and electrochemical process [17,18]. Both of their curves
include a single segment double layer charge process, stable potential period for electrodeposition, and hydrogen evolution process,
and then the discharge process.
However, it is different in this case. First, two slopes appear in the
charge process; second, there is only linear increase of cell voltage
during on-time, no sudden increase of voltage corresponding to
hydrogen evolution. The reason for the second difference is due to
the voltage in this case is much higher than that in some literature
[17,18]. Accordingly, hydrogen formation has already reached its
reduction potential during the charge process [9].
There are two possible reasons for the two charge segments.
First, the two segments correspond to different reactions. However, in solutions containing MnSO4 , CoSO4 , and MnSO4 + CoSO4 ,
all of the charge processes show two-segment charge process. The
individual cathodic deposition reactions have been characterized
previously by potentiodynamic polarization showing that different reactions occur in various solutions containing different cation

Fig. 9. Contact ASR of AISI430 substrate with Mn/Co spinel coating.

species [9]. However, little difference appears in charge processes of

different solutions; therefore, two charge segments induced by different deposition reactions are not possible. The second possibility
is that there is an intermediate layer locating between bulk solution
and the double layer. To charge the double layer, electrons have to
penetrate this layer. Considering the high peak current density, the
voltage during charge process has already exceeded the deposition
potentials of H+ (0.85 V) and water splitting (1.1 V) reactions.

Fig. 10. Cross-section SEM morphology and EDX linescan of Mn/Co coating after 1200-h ASR test.

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799

Fig. 11. Equivalent circuit of charge process at different peak current density densities: (a) ip = 50, 100 mA/cm2 , (b) ip = 150300 mA/cm2 , (c) simplied circuit from (b) Rs ,
solution resistance (quite low here); RH , Rdl , resistance due to hydrogen bubble layer and electrical double layer respectively; CH , Cdl , capacitance due to hydrogen bubble
layer and electrical double layer, respectively.

Therefore, the possible layer could be the H2 bubbles covering on

the substrate surface.
According to Fig. 4(a), only one segment charge process is displayed in all three solutions, which further proves that the charge
process has little relationship with cation species in the solutions.
From Fig. 4(b) of charge process changes with different peak current densities. Hence, the second segment will not show up until
the voltage reaches what could be regarded as the critical value for
the second segment. When voltage is positive than 2.5 VSCE (at
current densities 100 mA/cm2 ), only some isolated H2 bubbles are
formed, which will not manifest itself as a capacitance. While negative than 2.5 VSCE (at current densities 150 mA/cm2 ), uniform
H2 bubble layer will cover the substrate surface, creating an effective barrier for charge transfer during electrochemical reaction. It
is no doubt that the adherence of hydrogen bubbles can block the
metal ions from access to the surface of the electrode for deposition
[24,25], therefore, it will increase the deposition resistance. Hydrogen bubble growth mechanism has been proposed in electrode
surface wetting [26], which includes four process: some bubble
growth; coalescence to form a single bubble; further growth; and
eventually detachment from the surface. Although the applied current, 5 mA/cm2 , is much smaller than that in our case, 300 mA/cm2 ,
which will not induce instantaneous hydrogen bubble formation,
it is still possible that the hydrogen bubble cover the surface and
impede deposition.
The electrical equivalent circuit has generally been used to
model charge and discharge time of pulse plating [11,18,27,28].
The general accepted one is charge/discharge process occurs in
parallel to the faradaic process, such as Fig. 11(a), which may be
applied to our charge process at low current density of 50 and
100 mA/cm2 . However, at current densities above 150 mA/cm2 , it is
not applicable, and the other layer of hydrogen bubble in series with
double layer are proposed, as shown in Fig. 11(b). A similar circuit
has been proposed by Chen and Lasia [29] previously. Therefore,
during charge process at high peak current densities, the lower segment corresponds to double layer charge, and at that time, little or
isolated H2 bubble is formed on the sample surface. The higher segment is because of uniform H2 bubble layer when voltage reaches
more negative than 2.5 VSCE .
Furthermore, when cathodic voltage reaches more negative
than 2.5 VSCE , the double layer has nearly been fully charged,
so the equivalent circuit of Fig. 11(b) could be further simplied as Fig. 11(c), Hence, only RH and CH is responsible for the
charge when voltage is more negative than 2.5 VSCE RH could
be calculated from the RH = (Vfc 2.5)/ip , Vfc stands for the volt-

age of fully charge. To get 98.2% charge, the time required may
be calculated as  = 4RC [11]. Therefore, both the RH and CH are
obtained, as shown in Table 1. It is clear that neither RH nor CH
is a xed value. With the increase of current density, RH increases
and CH keeps going down. It is probably that at high current
density, more hydrogen bubbles are adsorbed on double layer making it more difcult for electrochemical reactions to occur, but
high current density makes it easier to get the double layer fully
charged.
Comparing the two charge segments, charge times are around
100 s and discharge times are as short as 5 s. Both of them are
much shorter than the pulse on-time that was applied, 1 ms or
10 ms. Therefore, at high current densities, on- and off-time durations will not affect the coating signicantly, even when the on-time
is 1 ms and off-time 0.1 ms. The pulse shape will only be distorted
slightly, therefore, the advantage of pulse plating over DC plating is
still obvious [11].
4.2. Effect of off-time
Electrode potential is so far from the potentials of the other metals that the latter must be deposited above their limiting current
densities before manganese will co-deposit [30]. In our previous
studies, manganese begins to deposit when cobalt has already
reaches its deposition limit during DC plating, which is helpful to
get higher Mn content. With longer on-time during pulse plating,
the cobalt gradient near the surface should be sharper than that of
short on-time until reaches its diffusion limit, hence, the Mn content should increase with the increase of on-time, however, at the
same duty cycle, the Mn content decrease with the increasing of
on-time (Fig. 5). Therefore, it could be summarized that Mn content, during pulse plating, is mainly related with off-time change,
not on-time. While in pulse plating of NiPFe [31], it has been
proposed that the hydrogen reduction reaction occurs relatively
vigorously at a low duty cycle due to faster diffusion of hydrogen
ion relative to nickel and iron ions. It may also be applied in our case,
but the difference is that water-splitting reaction probably plays a
Table 1
Resistance and capacitance corresponding to hydrogen bubble layer
Current densities (mA/cm2 )

RH ()
CH (C)

150

200

250

300

6.2
2.66

9.1
1.54

11.08
0.93

12.03
0.75

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J. Wu et al. / Electrochimica Acta 54 (2008) 793800

more important role in hydrogen production than hydrogen ion

reduction [9].
On the other hand, double layer discharge, concentration prole
relaxation and hydrogen bubble released will occur during the offtime. So with the increase of off-time, the coating becomes denser
and more compact due to hydrogen bubble release. However, this
does not help to deposit Mn because of the concentration gradient relaxation. Additionally, reactions (1) and (2) could occur at the
off-time, which also explains why the coating compositions vary
signicantly. Similar results have been obtained in pulse plating
of MnZn [32], Mn% content decrease signicantly with increasing
off-time. In MnCu pulse plating [33], the results show similar Mn
content in pulse plating and DC plating, because the Cu2+ concentration is only 5 mM, which makes it easy to reach the diffusion
limit. Additionally displacement reaction between Mn and Cu has
been proposed to occur during off-time however, it is harder to relax
the Cu concentration gradient, meaning the displacement reaction
has less effect than in our system.
Reaction between nickel and copper have been studied by quartz
crystal microbalance (QCM) [34], but it is hard to be apply in this
system, due to the high chemical activity of Mn, so a lot of hydrogen
bubbles will be produced during the reaction, which will vibrate the
weight change and crystal response frequency.
5. Conclusions
Mn/Co coatings were pulse plated on SS430 substrates from
baths developed from DC plating in previous studies. By means of
cyclic voltammetry it is found that Mn begins to dissolve in the
bath at 1.4 VSCE . Two reactions could occur during off-time and
both of them are detrimental to obtain high Mn coatings, while
cobalt begins to dissolve at 0.7 VSCE .
At the peak current density of 300 mA/cm2 , pulse analysis found
that both charge and discharge times are relatively short compared
with the on- and off-time applied, and two segment curves with
different slopes during charge occur which are hard to explain. Further pulse analysis makes it clear that the lower segment can be
attributed to double layer charge and the higher one to the uniform hydrogen bubble layer. Also the second segment shows up
only if the cathodic voltage reaches more negative than 2.5 VSCE ,
possibly corresponding to uniform H2 bubble layer.
At the same duty cycle, Mn content decreases with an increase
of on- (or off-)time. At the same on-time with different off-time,
Mn content decreases with the on-time increasing, and surface
morphologies changes from ake like structure to crystalline structures. All result from the difference of off-time. Because Mn will
re-dissolve instantly into the solution, and longer off-time will
release more hydrogen bubble from the coatings, coatings will be
more compact and crystalline.
Finally, ASR measurement is used to characterize the conductivity of the coating. In tests of 1200 h, ASR is quite stable with a slight
increase. The ASR value at 40,000 was predicted to be 0.0460  cm2 ,

assuming the increase follows parabolic law (diffusion control). No

chromium was spotted on the surface, and the coating contained
more Mn on the tested surface than as-deposited coating, indicating that the faster diffusion of Mn leads diffusion of Mn from the
substrate to the coating.
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