Transactions of the IMF

The International Journal of Surface Engineering and Coatings

ISSN: 0020-2967 (Print) 1745-9192 (Online) Journal homepage: http://www.tandfonline.com/loi/ytim20

Electrodeposition of Iron Films on Copper Surfaces

from Iron(III) Gluconate Solutions

S. S. Abd El Rehim, E. A. Abd El Meguid & E. M. Moustafa

To cite this article: S. S. Abd El Rehim, E. A. Abd El Meguid & E. M. Moustafa (2003)
Electrodeposition of Iron Films on Copper Surfaces from Iron(III) Gluconate Solutions, Transactions
of the IMF, 81:3, 79-82, DOI: 10.1080/00202967.2003.11871503

To link to this article: http://dx.doi.org/10.1080/00202967.2003.11871503

Published online: 08 May 2017.

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Download by: [University of Calgary] Date: 06 August 2017, At: 04:57


S. S. Abd El Rehim 1
E. A. Abd El Meguid2 *,
and E. M Moustafa 2
'Department ofChemistry, Faculty of
Science, Ain Shams University. Cairo, Egypt
2
Department of Electrochemistry and
Corrosion, National Research Centre,
Dokki, Cairo, Egypt
Downloaded by [University of Calgary] at 04:57 06 August 2017
Electrodeposition of Iron
Films on Copper Surfaces
from Iron(III) Gluconate
Solutions
SUMMARY- Iron films have been electrodeposited galvanostatical/y onto copper substrates from
slightly acidic (pH 5. 7) solutions containing ferric sulphate and sodium gluconate under different
electrolytic conditions i.e. solution composition, pH. temperature and current density. The influence
of each parameter on potentiodynamic polarisation curves, cathodic current efficiency and throwing
power of the solutions has been studied. It was found that the optimum conditions for producing
sound Fe films are: 0.038 mol dm 3 Fe,(S04) 3. 7 H20 + 0.14 mol dm 3 sodium gluconate. current
density (c. d.) of }=0.33 A dm 1, pH 5. 7 and a temperature of 25°C. The optimum solution is
characterised by its excellent throwing power. The surface morphology of the "as-deposited" Fe
films was investigated by using scanning electron microscope (SEM) while the crystal structure was
examined by using X-ray diffraction.

Keywords: electrodeposition; Fe films; acidic

•corresponding author: eameguid@hotmail com
S. S. Abd El Rehin, E. A. Abd El Meguid and
E. M. Moustafa, Trans Jnst Met Fin, 2003,
81(3), 79
gluconate solutions
INTRODUCTION
Electrodeposition of Fe films has been
extensively studied. These plated films have
many technical applications based on their
desirable physical and magnetic properties
such as in printing plates, in under-
dimensioned steel parts, in the welding of
stainless and carbon steel as well as in the
electronic industries u. Most of the previous
work was on the electrodeposition of Fe from
Fe (II) solutions3-5. However electro-
deposition of Fe from Fe (JII) electrolytes has
received less attention6- 7 as these solutions
have low throwing power. In the present work
attempts have been made to electrodeposit
bright and highly adherent Fe films onto
copper substrates from solutions that have a
good throwing power. Solutions containing
gluconate have been recently employed
successfully in the electrodeposition of Ni 8 ,
Cu 9 , Sn 10 Zn 11 and some alloys 12- 14 • The
advantages of sodium gluconate derive from
its low cost and its non-polluting effect on
the environment. This paper describes the
effects of some electrolytic conditions on
cathodic polarisation, cathodic current
efficiency, crystal structure and surface
morphology with respect to the
electrodeposition of Fe films from Fe (Ill)
gluconate solutions. The throwing power of
this solution has also been evaluated.
EXPE~ENTALDETARS
All the electrolytic solutions used were freshly
prepared from Analar chemicals and double
distilled water. Copper sheet cathode and
platinum sheet anode both of dimensions 1.5
x 2 em were used. The electrodeposition cell
used was a rectangular Perspex trough provided
with vertical grooves on each side of the walls
to fix the electrodes before each run. The
copper sheet cathode was polished mechani-
cally and then immersed in pickling solution
of300 cm 3 H2 S04 , 100 cm3 HN03 , 5 cm3 HCI
and 595 cm3 distilled water for I min., washed
with distilled water, rinsed with acetone, dried
and finally weighed. The plating solution used
contained 0.038 mol dm-3 ferric sulphate and
0.14 mol dm-3 sodium gluconate. The pH of
each solution was measured with an Electronic
Instrument Limited pH Meter 7020; where
necessary the pH of the solution was adjusted
by addition of a solution of NaOH. The
plating duration was I 0 min. after which the
cathode was withdrawn, washed with distilled
water, dried in a desiccator and weighed.
The cathodic polarisation during Fe deposition
was measured by Potentioscan Wenking Pos
73. The potentials were measured relative to
a saturated calomel electrode (SCE). Each
polarisation curve was swept from the rest
(zero current) potential into more negative
values with scan rate of I mV s-•. To avoid
contamination, the reference electrode was
connected to the copper cathode via a bridge
provided with a Luggin-Haber capillary tip,
filled with the same solution as that under test.
The surface morphology of the as-deposited
Fe films on copper substrates was examined
using a scanning electron microscope (JEOL,
JSM-T20). The crystal structure of the
deposited Fe was characterised by X-ray
diffraction analysis using a Philips Dif-
fractometer P.W. 1390 (40 kV, 25 rnA) with a
Ni filter and Coka radiation.
The throwing power (TP) of the solution
was measured using a Haring--Bium rectangular
Perspex cell fitted with one platinum sheet
anode between two parallel copper sheet
cathodes where the ratio of the far to the near
spacing was 3: I. The percentage throwing
power was calculated from Field's formula u
TP% = L-M I L+ M-2 xiOO (I)

Trans lnst Met Fin, 2003, 81 (3) 79

 Where L is the current distribution ratio (linear
ratio, 3: I) and M is the metal distribution ratio
w, w,
w. I where w. and are the weights of
the deposit on the near and far cathode
respectively. In some experiments the values of
M were measured as a function of L over a wide
range of linear ratios vwying between I: I to 4: I.
The throwing index (Tl) of each solution was
considered as a reciprocal of the slope of the
plot M vs Ll 6· Cathodic current efficiency
(~%) of the deposits was calculated as
~ = QF, IQ,,. X 100
where QF, is the real charge estimated from the
quantity of deposited Fe and Q,., is the
theoretical charge calculated from Faraday's
Law.
RESULTS AND DISCUSSION
Cathodic polarisation curves
The potentiodynamic cathodic polarisation
curves of Fe electrodeposition onto copper
substrates from gluconate solutions were
investigated under different experimental
Downloaded by [University of Calgary] at 04:57 06 August 2017
is present mainly as FeC 6 H 80 7 and
[FeC 6 H 70 7]- soluble complexes with pK
values of 4 and 13.3 respectively 11.1R. The
formation of these complex species may
inhibit the deposition of Fe because they
cannot be reduced as easily as the free Fe (Ill)
ions. In addition, the gluconate ions may be
adsorbed on the electrode surface and block
the preferential sites for Fe deposition.
However, Fe (Ill) can be electrolytically
reduced from the free and complexed species
simultaneously with H 2 evolution as a side
(2) reaction at the cathode surface. Figure I shows
the effect of pH (3.3 to I 0) on cathodic
polarisation curves at 25°C. At pH 3.3, the
cathodic polarisation curve exhibits a current
plateau followed by a rapid rise in current at
high negative potentials . Hydrogen discharge
takes place within the current plateau region
indicating that the hydrogen evolution is under
diffusion control. At higher negative potentials,
the rapid rise in current is ascribed to
simultaneous deposition of iron and evolution
of hydrogen. The limiting current decreases
significantly with increasing the pH value of
the bath and so one can expect an increase in
the cathodic current efficiency of Fe
However, in solutions above pH 13, ferrous
hydroxide precipitates 11•
The effect of the Fe (III) concentration on
the cathodic polarisation curve from slightly
acidic gluconate solutions (pH 5.7) at 25°C is
shown in Figure 2. The cathodic polarisation
shifts to more negative potentials on increasing
the concentration of Fe (III) in the bath. This
behaviour could be ascribed to the possibility
that increasing Fe (Ill) in the solution enhances
the stability of the complexes formed because
of the presence of excess gluconate ions in the
solution. Consequently, the relative abundance
of the Fe (111)-gluconate complex species
increases and this is reflected in an increase in
concentration polarisation associated with Fe
deposition. Figure 3 shows the influence of
increasing the gluconate concentration at pH
5.7 and at 25°C. The cathodic polarisation
does not change with increasing gluconate
concentration.
The influence of temperature on the
cathodic polarisation curves is shown in Figure 4.
A rise in solution temperature causes a
remarkable increase in the limiting current to
values in the region of 0.1 A dm- 2• This
behaviour could be due to a decrease in

conditions. In acidic gluconate solutions, Fe (III) deposition (~) at increasing pH values. activation overpotential of the H 2 evolution

0.4 rr===::::=::::::::==;---------r-----:tll
-+-pH= 3.3
..... pH= 5.7 0.4
-+-pH= 7.6
--0.14 molcin"'
..... pH= 10.1
0.3 --0.183 moldm-3
0.3
--0.23 molcin·'
'1'E
'1'E
"0 0.2
c( "0 0.2
c(

0.1 0.1

oJ...........,..~~~~-_j
-80 -280 -480 -680 -880 -1080 -1280
-280 -480 -680 -880 -1080 -1280 -1480
E vs. SCE/mV
Evs. SCE/mV
Figure I. Effect of pH on cathodic polarisation of Fe electrodeposition Figure 3. Effect of sodium gluconate concentration on cathodic
from a solution containing 0.038 mol dm 1 Fe/SD) 1 .7H,O + 0.14 polarisation of Fe electrodeposition from solution containing 0.038
mol dm 1 sodium gluconate at a temperature of 25°C mol dm 1 Fe,(S0) 1.7H,O at pH 5.7 and at a temperature of 25•c

0.4
-+- 0.038 mol <in·' 0.5
--- 0.048 mol <in·' - - 25"C
...... 0.057 mol <in"' - - 45"C
0.3 0.4
- - 6o·c
'I '1'E 0.3
E "0
"tl
c(
0.2 c(
0.2

0.1 0.1

0~~~~~~~--~~
0
-80 -280 -480 -680 -880 -1080 -1280
-80 -280 -480 -680 -880 -1080 -1280 -1480
E vs.SCE /mY
Evs. SCE/mV
Figure 2. Effect of Fe_,(SO ).JH,O concentration on cathodic Figure 4. Effect of temperature on cathodic polarisation of Fe
polarisation of Fe electrodeposition in the presence of 0. I 4 mol dm ·' electrodeposition from solution containing 0.038 mol dm 1
sodium gluconate at pH 5. 7 and at a temperature of 25°C' Fe_,(SO) r7H,O + 0.14 mol dm 1 sodium gluconate at pH 5.7.

80 Trans lnst Met Fin, 2003, 81 (3)

 reaction. Moreover, increasing temperature
will increase the rates of diffusion of the
reduced species. It is probable that the
temperature has a greater influence on the
diffusion rate of reducible hydrogen species
than that of Fe as evidenced from the cathodic
current efficiency data (Figure 6).
Cathodic Current Efficiency
The effect of pH on current efficiency cl» of
Fe film deposition from solutions containing
0.038 mol dm-3 Fe 2 (SO~ )3 7Hp and 0.14
mol dm-3 sodium gluconate at current density
of 0.33 A dm- 2 and a temperature of 25°C is
illustrated in Figure 5. In an electrol)'1e of pH
3.3 only H2 evolution takes place, but above
this pH, both H2 evolution and Fe deposition
occur simultaneously. The cathodic current
efficiency cl» of Fe deposition increases with
an increase in the pH up to pH 5.7 and then
tends to attain a steady value of about 43 %.
The increase in the efficiency of Fe
deposition with increasing the pH from 3.3
to 5. 7 is due to the increase in the H2
overpotential. Moreover, vigorous H2
evolution in acidic solutions may inhibit the
Downloaded by [University of Calgary] at 04:57 06 August 2017
diffusion of Fe (III) species to the cathodic
diffusion layer and concurrent H2 adsorption
and bubble formation may occur 12 · 19 .Aiso, a
passivation effect associated with the
formation of metal monohydroxide in the
catholyte and the accumulation of metal
hydroxide at the cathode surface. will inhibit
the H2 evolution reaction and enhance the
deposition of Fe~
The influence of temperature on the
efficiency of Fe electrodeposition from an
acid solution, pH 5.7, is illustrated in Figure
6. It is clear that above 30°C, the efficiency
eo
40
•
20
( pH
10 12
Figure 5. Effect of pH on cathodic current
efficiency (ttl) of Fe film electrodeposited from
solution containing 0.038 mol dm' Fe,(SO,
),.7Hp + 0.14 mol dm 3 sodium gluconate at
J = 0.33 A dm·' and at 25•c
60r-------------------,
• •
20
20 40 60
Tomp./'C
Figure 6. Effect of temperature on current
efficiency (ttl) of Fe film electrodeposited from
solution containing 0.038 mol dm'
Fe,(S0) 3.7Hp + 0.14 mol dm 3 sodium
gluconate at j = 0.33 A dm: and at pH 5. 7.
Trans lnst Met Fin, 2003, 81 (3)
decreases steeply and finally reaches a
steady state value as bath temperature is
raised. The decrease in efficiency should be
attributed to a strong acceleration of the rate
of the H 2 evolution reaction by raising
temperature as expected from the
polarisation curve (Figure 4). Moreover, the
metal deposition reaction may be
suppressed by a diffusion inhibiting effect
caused by the amount of H2 evolution and
gas bubble formation••.
The effect of applied current density on
cathodic current efficiency of iron deposition
at 25°C is shown in Figure 7. On increasing
the applied current densities the current
efficiency decreases rapidly to approach a
value of about 18% at I A dm-2 • The most
likely explanation for this trend is that the
metal deposition reaction is suppressed by a
diffusion inhibiting influence from H2 evolution
and gas bubble formation.
Figures 8 and 9 show the effect of both
Fe (Ill) concentrations and gluconate content
respectively on cathodic current efficiency of
electrodeposition of iron film at pH 5.7 and
at 25°C. These data infer that metal
deposition efficiency decreases with
increasing Fe (III) concentration in the
solution. These results are in a good
agreement with cathodic polarisation data
(Figure 2). However, changing the
concentration of gluconate ion has no
significant influence on the efficiency of Fe
film electrodeposition. From these results, it
is found that the optimum experimental
conditions for electrodepositing high quality Fe
films on copper substrates are: 0.038 mol dm-3
Fe 2 (SOJ 3 7Hp + 0.14 mol dm-3 sodium
gluconate, current density of 0.33 A dm- 2 •
pH 5. 7, and a temperature of 25°C.
60
50
40
14
.30
20
10
0
0 0.2 0.4 0.6
j/Adm""'
0.8
Figure 7. Effect of current density on cathodic
current efficiency (ttl) of Fe film electro-
deposited from solution containing 0.038
mol dm 3 Fe,(S0 4 ) 3.7Hp + 0.14 mol dm'
sodium gluconate at pH 5. 7 and at 25°C
60r---------------,
20
60 0.02 0.04 0.08
[Fo,(SO.),. 7H,O]/ mot dm_,
Figure 8. Effect of Fe,(SO, ),.7Hp concentration
on cathodic current efficiency (ttl) of Fe film
electrodeposition from a solution containing
0.23 mol dm·' sodium gluconate at pH 5. 7. j
= 0.33 A dm 2 and T = 25•c
Surface morphology and crystal
structure of deposits
The Fe films deposited on copper substrates
using the optimised gluconate solutions were
adherent, smooth and bright grey in appearance.
The brightness decreased with increasing
deposition temperature and at values above
40°C, the deposits tend to be dull. X-ray
diffraction analysis (XRD) of the Fe film
electrodeposited from the optimum electrolyte
shows that the crystal structure of the as-plated
Fe film consists of a single-phase with fcc
crystalline structure (Figure 10). The pattern
shows that the reflection of fcc phase structure
corresponds to a (II 0) preferential orientation
for the crystal grains of the deposits 20 •
The surface morphology of the as-plated
Fe films deposited under different plating
parameters on copper substrates was examined
in a scanning electron microscope. Some
micrographs of the surface of the as-plated
films are given in Figure II. Inspection of the
images obtained shows that the surface
morphology of the deposits varies from a large
grain structure to a tine grain structure with
increasing the temperature of the solution
(Figures II a and b). It is thought that
increasing the temperature results in a decrease
in the cathodic polarisation and an increase in
the rate of H2 evolution. The decrease in the
polarisation leads to an increase in the
nucleation overgrowth and consequently to the
deposition of a finer crystal structure"'.
Micro-cracks are observed on the surface of
the deposits obtained at high temperatures
(Figures II b). The presence of these micro-
cracks indicates that these deposits are highly
stressed which may be due to the precipitation
of Fe (OH) 2 on the cathode during the
electrodeposition reaction 21 •
60
1.2
• 20
0.05 0.1 0.15
]Sod. gluconMe]/ mot dm 4
0.2 0 25
Figure 9. Effect of sodium gluconate
oncentration on cathodic cu"ent efficiency (ttl)
qf Fe film electrodeposition from a solution
containing 0.038 mol dm 3 Fe,(S0),.7Hp at
pH 5.7, j = 0.33 A dm 2 and T = 25•c
(110)
0.08 0.1
Figure 10. X-ray diffraction pattern of
as-plated Fe film from a solution
containing 0. 038 mol dm 3 Fe ,(SO),. 7H ,0
+ 0.14 mol dm .J sodium gluconate at -
pH 5. 7 and at 25•c
81
 Table I. Effect of some plating variables on the throwing power TP % and throwing index Tl
for Fe film electrodeposition from gluconate solutions at pH 5.7, and plating duration 10 min.
Solutions /mol dm- 3 c.d., j lA dm-2 Temp t•c TPI% Tl
[Fe 2 (SOJJ+ [Na C6H 11 0 7]
0.038 + 0.14 0.667 25 77.8 6.25
O.o38 + 0.14 1.0 25 110.5 -18.7
0.038 + 0.14 1.0 40 98 97.5
0. 019 + 0.14 1.0 25 104 -62.5
0.038 + 0.183 1.0 25 115 -15

weight of Fe deposited on the far cathode is 3. A. M. Abd El-Halim and M. H. Fawzy,

higher than the weight on the near cathode and
then M < I. Increasing the applied current
density increases TP, which is due to the
decrease in the cathodic current efficiency for
Fe deposition at increased current densities.
Increasing both Fe (III) and gluconate
concentrations caused an increase in TP as a
result of increasing cathodic polarisation
(Figures 2 and 3). On the other hand, raising
the solution temperature lowers the throwing
power of the solution although the increased
temperature enhances the conductivity of the
Figure 11. Scanning electron micrographs of
Downloaded by [University of Calgary] at 04:57 06 August 2017
Trans. /nst. Met. Fin., 1993, 71, 125
4. Xintan Hu and Xiaolei Xu , Plat. Surf
Finish., 1998, 85, 71
5. S.Yoshimura, S.Yoshihara, T. Shirakashi
and E. Sato, Electrochim. Acta, 1994, 39,
589
6. V. Sree and T. L. Ramachar, Bull. India
Sect. Electrochem. Soc., 1960, 9, 59
7. M. Deutsch, J. R. Downing, L. G. Elliott,
J. W. Irvine, Jr. and A. Roberts, Phys.
Rev., 1942, 62, 3
8. E. A. Abd El Meguid, s:s. Abd El Rehim

solution. and E. M. Moustafa, Trans. lnst. Met.

as-plated Fe film .deposited from a solution
containing 0.038 mol dm·' Fe,(SO, ) 3.7Hp
+0.14 mol dm·' sodium gluconate, j = 0.33
A dm ' (a) T = 25 •c (b) T = 50 •c
1.2
:E 0.8
04
0~--~----~--------------~
0
L
Figure I 2. Effect of current density on the
throwing index of Fe film electrodeposition
from a solution containing 0.038 mol dm·'
Fe,(SO, )1.7Hp +0.14 mol dm·' sodium
gluconate, at pH 5. 7 and at T = 25 •c
Throwing power of the gluconate
solution
The throwing power (TP) of the slightly acidic
gluconate solution was measured using a
Haring-Blum cell under different experimental
conditions. Table I shows the percentage
values of TP calculated using the empirical
Field's formula at a distance ratio (I :3) under
the influence of different variables. The data
show that the acidic gluconate solution has
high TP values, some of which are higher than
+I 00 %. Such TP values indicate that the
The metal distribution M was plotted for
linear ratio L (within the range from L = I to
4 ) on arithmetic coordinates as suggested by
Jelinek et a/. 16 The reciprocal of the slope of
the plot is the throwing index (TJ) and
represents a direct measure of the solution
throwing power. Some representative linear
plots of M and L are given as examples in
Figure 12 and the values of Tl are listed in
Table I. It is clear from these data that the
throwing power of these gluconate solutions
is excellent and the values of both TP and Tl
are changed in a manner parallel to each other.
CONCLUSION
From the present results, it was found that
the optimum experimental conditions for
electrodepositing adherent, smooth and bright
grey Fe films on copper substrates are: 0.038
mol dm-3 Fe 2 (SO 4 ) 3 7Hp + 0.14 mol dm- 3
sodium gluconate, current density of0.33 A dm-2,
pH 5. 7 and at a temperature of 25°C. This
bath was shown to have an excellent throwing
power. The crystal structure of the as-plated
Fe film obtained from this electrolyte
consisted of single-phase with a fcc crystalline
structure
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82 Trans lnst Met Fin, 2003, 81 (3)