J. Chem. & Cheml. Sci. Vol.

3 (4), 251-258 (2013)

Electrochemical Preparation and Characterization of

Fe-Cu Alloy on Anodized Alumina Templates
R. K. PATHAK1 and PRIYANKA WAGELA2
1

Department of Chemistry,
Govt. MLB College, Indore, M.P., INDIA.
2
Department of Eng. Chemistry,
Vikrant Inst. of Tech. & Mang. Indore, M.P., INDIA.
(Received on: July 31, 2013)

ABSTRACT
We have successfully deposited nano structured Fe-Cu alloy
inside anodic aluminum oxide (AAO) templates from aqueous
electrolyte containing Iron sulfate, Copper sulphate and Boric acid
by using electrochemical methods. polarization curves,
electrochemical impedance spectroscopy(EIS), the corrosion
behavior of the Iron-copper nanocomposite coatings were
examined. The corrosion parameters determined from the
polarization curves recorded in 0.5M NaCl solution at room
temperature. The surface morphology of deposited films was
investigated by scanning electron microscopy (SEM). The
compositional analysis of electrodeposited films was investigated
by Energy dispersive X-ray spectroscopy (EDAX).
Keywords: Electrodeposition, Electrochemical Inpedance
spectroscopy (EIS), Corrosion rate (CR), Scanning Electron
Microscope (SEM), Energy dispersive X-ray Analysis (EDAX).

INTRODUCTION
Alloy electrodeposition is widely
used in the production of new materials that
require specific mechanical, chemical, and
physical properties. This technique has been
demonstrated to be very convenient because
of its simplicity and low cost in comparison
with other methods, such as mechanical
alloying, sputtering, and vapour deposition.

The electrodeposition method is suitable for

producing reproducible electrodeposited
films at the same conditions. The objective
of this study is to electrodeposits Fe-Cu
alloy coatings onto anodized aluminum film
and the corrosion behavior of Fe-Cu alloy
deposits on anodized aluminum evaluated in
comparison to the corresponding pure Fe
and Cu coating. The composition and
structure of these alloys were investigated.

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R. K. Pathak, et al., J. Chem. & Cheml. Sci. Vol.3 (4), 251-258 (2013)

The aim of this study is to

investigate the corrosion behavior of
electrodeposited Fe-Cu alloy undergoing a
long-term immersion test in aerated NaCl
aqueous solutions in order to improve the
understanding of the corrosion mechanism
of these layers in an aqueous medium. The
experimental correlation between the
operational electrodeposition parameters of
Fe-Cu alloys, such as deposition current
density and plating solution composition,
coating morphology, coating composition
and the corrosion resistance properties were

evaluated. Copper and Iron coatings were

also studied under the same conditions for
comparative purposes. The corrosion
behavior of the two different types of Al2O3copper nanocomposite coatings was
examined using electrochemical methods
such as polarization measurements and
electrochemical impedance spectroscopy.
The micro structural and composition
analysis of the electrodeposited thin films
were performed by Scanning Electron
Microscopy and Energy Dispersive x-ray
Analysis.

TABLE I: The Solution composition and operating parameters for Fe-Cu Alloy
Composition of solution
FeSO4.7H2O
CuSO4.7H2O
H3BO3
Solution pH
Temperature (0C)
Time (sec)
Frequency (Hz)
Voltage (V)

I
0.1 M
2.7802 g
4.5 g
4.5
50
30
200
19

EXPERIMENTAL METHODS
The Aluminum samples were electro
polished by electropolishing solution and
rinsed with deionised water then samples
were treated in 20% H2SO4 for 1 min to
remove any adherent oxide layer present on
the surface. Finally, the samples were again
washed in deionised water. This procedure
was repeated until a clean and smooth
surface was obtained. The electro-polished
specimen was oxidized anodically in 10%
oxalic acid at 30 volts DC for one hour using

II
0.1 M
2.4978 g
4.5 g
4.5
50
30
200
19

III
0.1M
2.7802 g
0.1 M
2.4978 g
4.5 g
4.5
50
30
200
19

IV
0.1M
2.7802 g
0.01 M
0.2496 g
4.5 g
4.5
50
30
200
19

lead as counter electrode. The temperature

of the anodizing bath was maintained at 24
0.5C by circulating chilled water through
titanium cooling coil immersed in the
solution. The pores formed during
anodization were widened by dipping for 30
minutes at 37 0.5C in 0.1M phosphoric
acid. Iron & Copper was deposited inside
these pores from an aqueous electrolyte
containing Iron sulphate (0.1 M) and Copper
sulphate (0.1 & 0.01 M) by applying high
frequency (200 Hz) alternating current. After
electrodeposition, the oxide layer was

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R. K. Pathak, et al., J. Chem. & Cheml. Sci. Vol.3 (4), 251-258 (2013)

removed partially in 0.5 M phosphoric acid

at 87C for 15 seconds to expose the shape
of Iron-copper deposited on the porous AAO
templates. All the electrolytes were prepared
from Merck pre-analysis grade chemicals
and distilled water. All electrochemical
experiments and the deposition processes
were carried out in a standard
three
electrode electrochemical cell equipped with
platinum net as a counter electrode and
saturated calomel electrode (SCE) as a
reference electrode. Fe-Cu alloy were
obtained by electrodeposition from the
solutions shown in Table I.
Energy dispersive analysis using Xrays (EDAX) was used to analyze the
distribution of the elements in the final
deposit. The surface morphology and the
microstructure of the coating were analyzed
using scanning electron microscopy (SEM)

with the help of Hitachi S-2500 Delta

scanning electron microscope. Surface
analysis used a LEICA S 440 scanning
electron microscope with an attached energy
dispersive X-ray analyzer.
A variety of electrochemical
techniques including linear and Tafel
polarization were used to evaluate the barrier
resistance properties of the coating. The
electrochemical characterization was done
using an EG&G PAR model 273A
potentiostate/galvanostate interfaced with a
computer and a three-electrode setup. All
depositions were carried out potentiostatically at -0.73 V vs. SCE.
Impedance behaviors of Fe-Cu alloy
deposits were studied by electrochemical
impedance spectra (EIS) in the frequency
range from 100 KHz to 100 MHz.

TABLE II: Corrosion parameter of Fe-Cu alloy deposit in different concentration

Constitute Concentration
of deposite
(M)
Cu
Fe
Cu-Fe
Cu-Fe

0.1
0.1
0.1 : 0.1
0.01 : 0.1

Ecorr
(V v/s
SCE)
Obs
-.711
-.693
-.745
-1.059

(V v/s
SCE)

Icorr

Rp

Corrosion
Rate

Cal
-.704
-.715
-.74
-1.056

(V/dec)
.193
.12
.095
.144

(V/dec)
.109
.149
.026
.138

(A/cm2)
6.096e-6
1.703e-6
1.73e-6
4.517e-8

(Ohm)
1.909e+3
5.829e+3
7.921e+2
2.44e+5

(mm/yr)
7.068e-2
1.98e-2
2.011e-2
5.25e-4

RESULTS AND DISCUSSION

The
corrosion
behaviour
of
electrodeposited Fe-Cu alloy under different
concentration and compared it with pure
Iron and Copper at optimum frequency and
average current density was evaluated using
Tafel polarization method. Electroplated
specimens were subjected to corrosion study

in aerated 0.5 M NaCl solution and

experimental data are given in Table 2.
Corrosion rates of the deposits were
determined by Tafels extrapolation method.
A representative Tafel plot for 0.1 M Fe
and 0.1 M Cu is shown in fig 1.The
polarization studies have been made at scan
rate of 1 mV/s in a potential ramp of 0.73 V
from OCP. Observed Ecorr and Tafels slopes

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R. K. Pathak, et al., J. Chem. & Cheml. Sci. Vol.3 (4), 251-258 (2013)

at different current densities are shown in

Table 2. The corrosion rates obtained from
the polarization plots for Fe-Cu alloy coating
are compared in Table 2 with those of Iron
and Copper in the corroding solution. The
values of Tafel slope indicate that the
corrosion rate is controlled more by cathodic

reaction. Observed results showed that, the

corrosion rate of Cu is high in compare to
Fe. Fe-Cu alloy at 1.73e-6 having about 0.1
M Cu and 0.1 M Fe was found to show least
corrosion rate. The corrosion results indicate
that pure iron coating is more corrosion
resistance.

-0.700
-0.800

E /V

-0.900
-1.000
-1.100
-1.200
-1.300
-1.400
1.000x10 -9

1.000x10 -8

1.000x10 -7

1.000x10 -6

i /A

Fig. 1. Tafel Plot of 0.1M Fe & 0.01 M Cu.

4.5

90
80

4.0

70
3.5
log(Z)(o)

50

2.5

40
30

-phase / deg(+)

60
3.0

2.0
20
1.5
1.0

10
0

log(f)

Fig. 2. Bode plot of 0.1 M Fe

Rp
Rs
Fig. 3: Electrical equivalent of electrified interface of Fe-Cu alloy deposited
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R. K. Pathak, et al., J. Chem. & Cheml. Sci. Vol.3 (4), 251-258 (2013)

(a)

255

(b)

(c)

(d)

(e)
Fig. 4: SEM image of Fe-Cu alloy deposit at different concentration
(a) 0.1M Fe
(b) 0.1M Cu
(e) Etched 0.1 M Fe & 0.01 M Cu

(c) 0.1 M Fe & 0.1 M Cu

The electrochemical behaviours of

electrodeposited Fe-Cu alloys were studied
using impedance spectroscopy. EIS was
used to evaluate the barrier properties of the
coatings and determine the polarization
resistance and the corrosion rates without

(d) Unetched 0.1M Fe & 0.01 M Cu

modifying the surface. A Bode plot of Fe-Cu

alloy deposits is given in fig 2. The solution
resistance remains the same for all deposits.
The electrical equivalent of the electrified
double layer for optimized equivalent of the
electrified double layer for optimized

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R. K. Pathak, et al., J. Chem. & Cheml. Sci. Vol.3 (4), 251-258 (2013)

deposit is given in the fig.3. The EIS data

obtained using Rs (Qdl Rp) and Rs (Qdl RpW)
Circuit where, (Rs ) is the solution resistance,
(Qdl ) is the constant phase element for
electrical double layer; (Rp) is the
polarization resistance and (W) diffusion
resistance element known as Warburg
impedance, is due to the influence of
diffusion of the oxidents and reductants on
the overall reaction rate. Rp values can be
approximately determined by fitting the
bode plot to a simple equivalent circuit
consisting of ohmic resistance, double layer
capacitance, and polarization resistance. The
equivalent circuit is shown in fig 3.The
parameters for the C.P.E. element are a
flexible capacitor, Q and an exponent n.
Since the C.P.E. is only a true capacitor
where the exponent n is unity. Bode plots
are not found to be perfect as expected from
the theory of EIS for the assumed equivalent
circuit, and this difference can be explained
as the plots obtained in the real system
represent a general behaviour where the
double layer on the interface of the
metal/solution does not behave as a real
capacitor.
Scanning Electron Microscopy was
used for the microstructural characterization
and the composition analysis. These
investigation are limited by resolution of the
SEM, satisfactory quality of SEM image
was possible when the thickness of single
Fe-Cu alloy layer exceeds-300. Based on
SEM investigation high efficiency of the
deposited thickness measured by SEM was
similar to that predicted from deposition
charge. The variation in the surface
morphology of the deposit with concentration
difference is shown in fig 4.

Energy dispersive x-ray (EDX)

analysis was carried out on both the
locations for identifying the constituents
present in the deposit. It was found that both
iron and copper were present through out the
deposit. Variation of iron and copper
concentrations in both these deposits were
calculated by EDX analysis and the data is
given in Table 3. EDX spectrum shows the
presence of aluminum and oxygen which are
from the base substrate and its conversion to
aluminum oxide. Compositional changes
along the surface are due to in
homogeneities on the porous aluminum
oxide surface resulting in non uniform
current distribution.
EDAX was used to analysis the FeCu ratio of the electrodeposits. To ensure
accuracy of the element distributions EDAX
analysis was done at several points on the
surface of the substrate. The concentration
of the constituent elements was determined
by comparing the intensities of the X-ray
spectrum to the standard intensities of the
pure element. The EDAX images are shown
in fig 5.
cps/eV
70

60

50

40

O
Fe

Al

Fe

30

20

10

0
2

10
keV

12

14

16

18

Fig. 5(a): EDAX image of 0.1 M Fe film

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20

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R. K. Pathak, et al., J. Chem. & Cheml. Sci. Vol.3 (4), 251-258 (2013)
cps/eV

cps/eV

70

60

25

50
20

40

O
Cu Al

Cu
15

O
Fe
Cu

Al

Fe

Cu

30

10

20

10

0
2

10
keV

12

14

16

18

20

Fig. 5(b): EDAX image of 0.1 M Cu film

0
2

10
keV

12

14

16

18

20

Fig.5(c): EDAX image of 0.1 Cu & 0.1 M Fe film

cps/eV

25

20

15

O
Fe
Cu

Al

Fe

Cu

10

0
2

10
keV

12

14

16

18

20

Fig.5(d):EDAX image of Unetched 0.01 Cu & 0.1

M Fe film

Fig. 5(e): EDAX image of Etched 0.01 Cu & 0.1

M Fe film

Table III. Dependence of composition on Fe-Cu alloy concentration

Sample
1
2
3
4
5

Fe-Cu alloy (M)

Fe- 0.1
Cu- 0.1:0.1
Fe-Cu:: 0.1 :0.1
Fe-Cu:: 0.1: 0.01 (Unetched)
Fe-Cu:: 0.1: 0.01 (Etched)

CONCLUSION
Effective control of the iron-copper
ratio in composite alloy coating was
achieved in the presence of small amount of

Fe (Atomic
Weight %)
2.73
0.16
1.58
0.28

Cu (Atomic
Weight %)
3.29
2.17
1.40
1.15

Al (Atomic
Weight %)
37.85
39.10
38.22
35.83
37.73

H3BO3. The homogeneous and smooth FeCu alloys were electrodeposited on steel at
different
concentration.
Chemical
composition of Fe-Cu alloys was determined
by EDX analysis. The corrosion properties

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R. K. Pathak, et al., J. Chem. & Cheml. Sci. Vol.3 (4), 251-258 (2013)

of Fe-Cu alloys were investigated. The

influence of the plating current density in
Fe-Cu alloys electrodeposition on the
corrosion resistance of these alloys was
shown. It was obtained that Fe-Cu alloy
deposited at Cu 0.1M and Fe 0.1 M
exhibited the lowest corrosion rate.
Polarization studies on these deposits show a
large reduction in the corrosion current of
these alloy compared to pure Copper.
ACKNOWLEDGEMENT
The authors are grateful to RRCAT
Indore for instrumental analysis. The
Authors would also like to thanks to Mr. P
Ramshankar.
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Journal of Chemistry and Chemical Sciences, Vol.3, Issue 4, 1 October, 2013 (229-279)