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ISSN 1978-5933

The Second International Conference


On Green Technology and Engineering (ICGTE) 2009
Faculty of Engineering Malahayati University

Magnetic Field Influence on Limiting Current of Tin Electrodeposition


Sudibyo1, A. B. Ismail2, M. H. Uzir1, M. N. Idris2 and N. Aziz1*
1
School of Chemical Engineering, Universiti Sains Malaysia
2
School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia
Engineering campus, 14300 Nibong Tebal, Seberang Perai Selatan, Pulau Pinang, Malaysia

Abstract

Since microelectronics has developed to one of the most important branches of industry, the manufacture of thin
metal layers is a very important process. Electrodeposition can be an alternative process to produce these layers,
which is often more productive and cheaper. However, the problem of obtaining a uniform, dense and compact
deposition had plague researchers, thus various methods have been devised to address this problem. One of the
methods of tackling this problem is magneto electrodeposition (MED). As this technology is not widely being
investigated, this work is to focus on the limiting current under magnetic field effects (MFE) on tin
electrodeposition. Measuring the limiting current using linear sweep voltametry is important in order to know
the influence of MFE on the mass transport phenomena of electrodeposition process. The effects of magnetic
fields on tin electrodeposition are investigated in terms of variations in the magnetic field strength, the electrode
area, the concentration of the electro active species, the diffusion coefficient of the electroactive species and the
kinematic viscosity of the electrolyte. The effect of a uniform magnetic field with flux density up to 0.3 T on the
electrodeposition of tin from sulphate electrolyte has been investigated. Results achieved show that, when the
magnetic field is applied parallel to the electrode surface, the limiting current density is increased due to the
magnetohydrodynamic effect. As the magnetic field strength is increased, the limiting current increases
significantly. The increment in the working electrode area, the bulk concentration and diffusion coefficient of
electro active species also leads to the increase the limiting current. Different limiting currents are observed
when there are variations in the kinematic viscosity of the electrolytes. Significant influence on the limiting
current was observed when the kinematic viscosity of the electrolytes was varied.

Keywords: Limiting current; Tin electrodeposition; magnetic field; magnetoelectrodeposition; coefficient


diffusion; kinematic viscosity

Introduction It is now well established that the currents


The control of surface microstructure of observed in electrochemical processes are modified
transition metal thin film has both scientific and in MED process [4]. This effect, called
technological importance. Electrodeposition is one of “magnetohydrodynamic effect” (MHD), is generally
convenient techniques that can control the surface explained by the appearance of a Lorentz force. It
morphology and the crystal orientation of thin metal leads to a convective movement of the species to the
films. Electrodeposition is used to improve contact electrode surface, and for the electrochemical
resistance, reflection properties of material and to systems limited by the mass transfer; it induces an
impart friction properties [1]. It is also used to impart increase of the electrolytic currents [4]. Limiting
corrosion resistance or particular desired physical or current density is the maximum current density that
mechanical properties on the surface metal. can be achieved for an electrode reaction at a given
Obtaining a uniform, dense and compact deposition concentration of the reactant in the presence of a
is one of the major problems in electrodeposition. large excess of supporting electrolyte. The mass
There are numerous studies that had been carried out transport occurs exclusively through diffusion in the
to reduce it. One of methods available to overcome diffusion layer, driven by the concentration
this problem is magnetoelectrodeposition (MED) [2]. difference of the reactant between the edge of the
MED plays a vital role in electrodeposition diffusion layer and the electrode surface [5].
process to synthesize metal alloy, thin film, For this MED technology, many researchers have
multilayer, nanowires, multilayer nanowires, dot used the fundamental hydrodynamic equations as a
array and nanocontacts which are the technology of guide to the system parameters that should control
the future to build the next generation of computing the mass transport limited current. According to
devices. MED is an electrodeposition phenomena fundamental hydrodynamic equation these
occurring under the influence of a magnetic field or parameters should include the magnetic field
the formation of a substance layer on an appropriate strength, B, the number of electrons of the redox
substrate in externally imposed magnetic fields [3]. process, n, the electrode area, A, the diffusion

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coefficient of the electroactive species, D, the mV/s and were plotted in a Tafel plot. The effect of a
concentration of the electroactive species, C, and the magnetic field on the diffusion was investigated
kinematic viscosity of the electrolyte, v [6]. Thus,
those parameters can be studied meticulously.
In this work, the study on the effect of magnetic
strength, the electrode area, the concentration of the
electro active species, the diffusion coefficient of the
electro active species, and the kinematic viscosity of
the electrolyte towards the limiting current of tin
electrodeposition will be carried out.

Experimental
1. Apparatus
The magnetic field was generated by an
electromagnet (Lake Shore EM 4, USA). The pole
pieces were of 50 mm diameter and 50 mm apart.
The induction was uniform and equal to 0.3 T in the
magnet gap. The coils temperature was controlled by
a water flow. Chronoamperometric, and linear sweep
voltammetric studies were performed using a PGP
201 potentiostat monitored by the Voltamaster 4.0
software (Radiometer analytical S.A., France). The
absolute viscosity of each electrolyte was measured
using a viscosimeter (Model DV-III, Brookfield Fig. 1. Schematic illustration of electrochemical cell
programable rheometer).
Result and Discussion
2. Cell and electrodes 1. Effect of Bulk Concentration of Electro active
The narrow gap between the pole pieces required Species
the design of a special three electrodes cell with 45
mm inner diameter as shown in Fig. 1. Fourth
platinum plates with areas of 0.32285, 0.5, 0.57485,
and 0.95285 cm2 were used as working electrodes
(WE). The counter electrode (CE) was a platinum
wire (0.95285 cm2 area) and the reference electrode
(RE) was an Ag/AgCl electrode.

3. Reagents
Tin (II) Sulphate (≥99%), Sodium sulphate
(≥99%) and Sulphuric acid (≥99%) were purchased
from R & M (Malaysia). All solutions were diluted
with distilled water. For each experiment, 40 ml
electrolyte solutions were used.
Fig. 2 Variation of the limiting current iB under
4. Procedure
magnetic field as a function of the SnSO4
The cell containing 40 cm3 of the solution was
concentration C. 0.5 cm2 working electrode area. T =
placed in the field cavity for the experiments
25-27◦C. B = 0.3 T. [H2SO4] = 0.5 M
performed under the influence of the magnetic field.
The cell was placed in the field cavity so that the
using chronoamperometry. The limiting current was
working electrode surface faced downward and was
recorded at slow sweep rates (10 mV/s) for every
parallel to the lines of the magnetic flux that run
compound at concentrations in the range from 0.025
horizontally. The magnetic field was then applied
to 0.1 M in H2SO4 0.5 (M). The magnetic field was
perpendicular to the electric field (Fig. 1). The
kept constant at 0.3 T.
measurements were carried out at 25-27 ◦C.
From Fig. 2, it is found that the limiting current
Linear sweep voltammetry (LSV) technique was
increases as the concentration of SnSO4 increases.
used to investigate the effect of magnetic field,
The increment of limiting current indicated the
working electrode area, additive material and
increasing mass transport on electrodeposition
electrolyte concentration on the limiting current
process. This increment of limiting current can be
density. Linear sweep voltammetry (LSV) were
linked to the increasing concentration of the SnSO4
performed from +2 to -2 V at a sweep rate of 10
in the electrolyte. As the concentration increases, the
free cations (Sn4+) available in the electrolyte will
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ISSN 1978-5933
The Second International Conference
On Green Technology and Engineering (ICGTE) 2009
Faculty of Engineering Malahayati University

also increase. These higher concentrations cause solutions. Limiting currents were measured using the
more efficient stirring. It will also induce a turbulent 0.5 cm2 platinum plate as working electrode.
flow within the electrolyte, which this will increase The effect of a magnetic field on the diffusion of
the flux of the species [6]. As a result, the thickness Sn4+ were investigated using chronoamperometry. A
of the Nernst diffusion layer will gradually be potential step is a cathodic potential in the diffusion
reduced and this will decrease the screening effect.
As the Nernst diffusion layer decrease, the limiting
current density will also increase [7, 8].
The MHD effect caused by the magnetic field
will also decrease the screening effect at the
deposition site [9]. This MHD effect also will create
mixing in the diffusion area and reduce the thickness
of its Nernst diffusion layer in front of the electrode
effectively. As the Nernst diffusion layer decrease,
the limiting current density will increase [7]. This
will increase the deposition rate.

2. Effect of working electrode area (A)


Fig. 4. The current response at a Pt working electrode
in SnSO4 0.01 M, Na2SO4 0.075 M, B = 0.3 T, a
cathodic potential step of 700 mV.

Fig. 3. Variation of the limiting current iB under


magnetic field as a function of the working electrode
area, A. T = 25-27◦C. B = 0.3 T. [H2SO4] = 0.5 M
and [SnSO4] = 0.1 M.
Fig. 5. The Cottrell plot at a Pt working electrode in
SnSO4 0.01 M, Na2SO4 0.075 M, B = 0.3 T, a
The effect of the electrode area (A) on limiting
cathodic potential step of 700 mV.
current under magnetic field (iB), was determined
with three different electrodes in in H2SO4 0.5 (M)
-limited current plateau.It was applied to take the
under a constant magnetic field of 0.3 T. From
working electrode from the rest potential, where no
Figure 3, it is found that the limiting current
faradaic reaction occurs, to a final value where all
increases as the working electrode area increases.
electroactive species that reach the electrode are
The increment of limiting current is due to increment
instantaneously reduced. This corresponds to a
of the current which subsequently increase the
cathodic potential in the diffusion- limited current
electrode reaction [5]. A larger area also will cause
plateau of tafel plot, where the electrode kinetics are
more effective magnetic stirring in diffusion area.
significantly faster than the rate of mass transport. In
This reduces the thickness of its Nernst diffusion
quiescent solution, the rate of reaction, and hence the
layer. This will cause the limiting current and
measured current response, is solely determined by
deposition rate increase [6].
the rate of diffusion. For a reduction reaction on the
electrodeposition system, such as the
3. Effect of diffusion coefficients of Electro active
electrodeposition of tin, the current I, is given by the
Species (D) and kinematic viscosity of electrolyte
Cottrell equation:
(v)

The influence of the diffusion coefficient (D), nFAD1/ 2 c


I (t ) 
was determined in SnSO4 0.01 M solutions using ( t )1/ 2 (1)
Na2SO4 as supporting electrolytes. The electrolyte
concentration was varied from 10 mM to saturated
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Where A is the electrode area. Equation 1 shows It seems that the decrease of the mass-transport-
that the diffusion-limited current decreases with t-1/2. limited current is due to the friction forces becoming
This is due to the decrease in concentration gradient more effective as the electrolyte viscosity increases,
with time as the diffusion layer thickness grows. preventing magnetohydrodynamic convection of the
However, natural convection arising from density solution [6].
differences in the solution, eventually perturbs the
concentration gradient and prevents further growth of
the diffusion layer. This results in a steady-state
current at long times. A plot of I against t-1/2 is
known as a Cottrell plot. Under conditions of semi-
infinite linear diffusion, such a plot will be linear,
enabling the determination of the combination nAD1/2
from equation 1[8]. This part of the graph can be
extrapolated to the origin, thereby demonstrating the
expected behavior, and the slope yields a diffusion
coefficient. One example of the choroamperometry
graph and the Cottrell plot for this experiment is
shown in Fig. 4 and Fig. 5, respectively.
Fig. 7. Variation of the limiting current iB under
Table 1. Variation of the limiting current iB on the
magnetic field as a function of the diffusion
effect of diffusion coefficient (D) and Kinematic
coefficient (D). SnSO4 0.01 M, 0.5 cm2 working
viscosity (v) of the electroactive species.
electrode area, T = 25-27◦C. B = 0.3 T.
SnSO4 Na2SO4 v Ib D
(M) (M) (Stoke) (mA) (cm2/s)
4. Effect of Magnetic strength (B)
0.01 0.075 0.0178 1.3544 0.000001
0.01 0.1 0.0179 1.3224 0.00000098
0.01 0.15 0.0184 1.2585 0.00000095
0.01 0.2 0.0188 1.2273 0.00000094
0.01 0.3 0.0192 1.1715 0.00000091

Fig. 8. Variation of the limiting current iB under


magnetic field as a function of the Magnetic strength
(B). SnSO4 0.01 M, 0.5 cm2 working electrode area,
T = 25-27◦C. B = 0.3 T.

The influence of the magnetic strength was


determined in 0.01 M SnSO4 solutions. Limiting
Fig. 6. Variation of the limiting current iB under currents were measured using the 0.5 cm2 platinum
magnetic field as a function of the kinematic plates as working electrode and Na2SO4 1 M as
viscosity (v). SnSO4 0.01 M, 0.5 cm2 working supporting electrolyte. The change in the magnetic
electrode area, T = 25-27◦C. B = 0.3 T. strength leads to the variation of the limiting current,
iB, but the value of D (diffusion coefficient) is
From Table 1, it is found that the limiting current unchanged by the magnetic field [6, 8]. Fig. 8
decreases as the concentration of Na2SO4 increases. showed that the limiting current increases as the
This decrease of limiting current can be linked to the magnetic strength (B) increases. The increment of
increment kinematic viscosity of the Na2SO4 in the limiting current indicated the increasing of mass
electrolyte as shown in Fig. 6. The variation of the transport on electrodeposition process. This
electrolyte kinematic viscosity leads to a variation of increment of limiting current can be linked to the
the electroactive species diffusion coefficient [4]. presence of magnetohydrodynamic effect.
The increasing of the electroactive species diffusion When the MHD effect is present, the convective
coefficient leads to the increment of limiting current flow will create mixing in the diffusion area and
as shown in Fig. 7. reduce the thickness of its Nernst diffusion layer in

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ISSN 1978-5933
The Second International Conference
On Green Technology and Engineering (ICGTE) 2009
Faculty of Engineering Malahayati University

front of the electrode effectively. As the Nernst This phenomenon could happen because the
diffusion layer decrease, the limiting current density magnetic field could increase the rate of transport of
will increase [7]. electroactive species to or from the electrode. The
possible force which could be responsible for the Acknowledgment
enhancement of mass transfer is known as the Lorenz Financial supports from Ministry of Higher
force [2, 10]. The Lorenz force acts on migration of Education Malaysia through FRGS grant No. 607113
charged ions inside the electrolyte and induce a is greatly acknowledged.
convective flow of electrolyte close to the electrode
surface. This convective effect on electrodeposition References:
process is known as MHD effect [11]. [1] Sudibyo, M.B. How, N. I. Basir and N. Aziz,
Study of magnetic field effects on copper
Conclusions electrodeposition. RSCE – SOMCHE 2008,
The effect of the magnetic field on limiting Kuala Lumpur, Malaysia, pp. 961 - 964 2nd -3rd
current of tin electrodeposition has been studied December 2008.
using a three electrode electrochemical cell. It is [2] Matsushima, J.T., Trivinho-Strixino, F., Pereira,
found that the limiting current of tin E.C., Electrochimica Acta. 51 (2006) 1960–
electrodeposition strongly influenced by applied 1966.
magnetic field. Under the influence of magnetic [3] Ackland, G.J. And Tweedie, E.S., Microscopic
field, the limiting currents were observed to be model of diffusion limited aggregation and
higher due to the presence of MHD effect. The value electrodeposition in the presence of levelling
of the magnetic strength, working electrode area, the molecules. School of Physics, the University of
bulk concentration, diffusion coefficient of Edinburgh, Scotland, United Kingdom, 2007.
electroactive species and the kinematic viscosity of [4] Legeai, S., Chatelut, M., Vittori, O., Chopart,
the electrolyte also found to be significantly effect on J.P., Aaboubi, O., Electrochimica Acta. 50
the mass transport of electrodeposition. The higher (2004) 51-57.
mass transport of electrodeposition can be achieved [5] James, A.M, Electrochemistry Dictionary. John
when the lowest of kinematic viscosity of Wiley & Sons, Ltd, 1984.
electroactive species and the highest magnetic field [6] Leventis, N., M. Chen, X. Gao, M. Canalas, and
strength, working electrode area and concentration of P. Zhang, Journal of Physical Chemistry B, 102
electroactive species were applied with the magnet (1998) 3512-3522.
field placed horizontally. The increment kinematic [7] Fahidy, T.Z., Progress in Surface Science 68
viscosity leads to decrease of limiting current. This (2001)155 -158.
decrease of limiting current can be linked to the [8] Hinds, G., Spada, F. E., Coey, J. M. D., Ni
decrease of the diffusion coefficient of electroactive Mhiocha´in, T. R., Lyons, M. E. G., Journal of
species. As the kinematic viscosity is increased, the Physical Chemistry B. 105(2001) 9847-9502.
the diffusion coefficient of electroactive species [9] Mogi, I., Kamiko, M., Journal of Crystal
decreases significantly. Growth. 166 (1996) 276-280
[10] Bund, A., Koehler, S., Kuehnlein, H.H., Plieth,
W., Electrochimica Acta. 49 (2003) 147-152.
[11] Coey, J. M. D., Hinds, G., Journal of Alloys
and Compounds. 326(2001) 238 – 245

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ISSN 1978-5933
The Second International Conference
On Green Technology and Engineering (ICGTE) 2009
Faculty of Engineering Malahayati University

Study of Magnetic Field Effect in Cobalt Electrodeposition

Sudibyo1, A. B. Ismail2, M. H. Uzir1, M. N. Idris2 and N. Aziz1*


1
School of Chemical Engineering, Universiti Sains Malaysia
2
School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia
Engineering campus, 14300 Nibong Tebal, Seberang Perai Selatan, Pulau Pinang, Malaysia

Abstract

Electrodeposition is used to reflect material properties and to improve contact resistance and friction properties.
It is also used to improve corrosion resistance or particular desired physical or mechanical properties on the
metal surface. Roughening is the problem in electrochemical deposition. There are numerous studies that had
been carried out to reduce it. One of the methods of tackling this problem is magneto electrodeposition (MED).
Cobalt electrodeposition is an important technology to produce magnetic alloys, cutting-wear resistant alloys and
super alloys. As the cobalt electrodeposition is very useful for technical applications, this has been choosen as a
case of study. The effects of the magnetic field strength, the electrode area, the concentration of the electro active
species, the diffusion coefficient of the electroactive species, the kinematic viscosity of the electrolyte and the
additive concentration on cobalt electrodeposition have been carried out. The electrodeposition of Cobalt in
CoSO4 solutions were studied on platinum electrodes in a three electrode electrochemical cell. The magnetic
fields were varied from 0 to 0.3 Tesla which has been introduced externally. Based on the experimental results,
the presence of magnetic field would increase limiting current. As the magnetic field strength is increased, the
limiting current increases significantly. The increment in the working electrode area, the bulk concentration and
diffusion coefficient of electro active species also leads to the increase of the limiting current. It also observed
that the presence of boric acid as an additive was lead to the smaller amount of limiting current the decrease of
limiting current. However, it is acting as a buffer to avoid the local pH rise caused by parallel hydrogen
evolution reaction (HER).

Keywords: Limiting Current; Cobalt electrodeposition; magnetoelectrodeposition; coefficient diffusion;


kinematic viscosity; Boric Acid additive

Introduction increase in the limiting current and a dramatic change


in morphology of the fractal electrodeposits [3, 5].
Cobalt is an element with excellent Both phenomena could happen because the magnetic
ferromagnetic properties. Besides, it is relatively field could increase the rate of transport of
stable against corrosion and easily to handle, which electroactive species to or from the electrode [3, 6].
makes it even more useful for technical applications This effect, called magnetohydrodynamic (MHD)
[1]. Since microelectronics has developed to one of effect, is generally explained by the appearance of a
the most important branches of industry, the Lorentz force. It leads to a convective movement of
manufacture of thin metal layers, nanowires, dot the species to the electrode surface, and for the
array and nanocontacts are a very important process electrochemical systems limited by the mass transfer;
[2]. These products are mostly in a nanoscale it induces an increase of the electrolytic currents [7].
thickness range. Electrodeposition can be an Limiting current density is the maximum current
alternative process, which is often more productive density that can be achieved for an electrode reaction
and cheaper [1, 2]. at a given concentration of the reactant in the
Roughening is the problem in electrochemical presence of a large excess of supporting electrolyte.
deposition. There are numerous studies that had been The mass transport occurs exclusively through
carried out to reduce it. One of the methods of diffusion in the diffusion layer, driven by the
tackling this problem is magneto electrodeposition concentration difference of the reactant between the
(MED) [3]. MED is an electrodeposition phenomena edge of the diffusion layer and the electrode surface
occurring under the influence of a magnetic field or [8].
the formation of a substance layer on an appropriate For this MED technology, the parameters that can
substrate in externally imposed magnetic fields [4]. be studied are somehow similar to conventional
The MFE have significant influence on electrodeposition. This is due to the fact that
electrodeposition. The most striking effects on magnetoelectrolytic deposition itself is actually based
magneto electrodeposition are the impressive on electroplating technology. Thus, similar

1
parameters such as the working electrode area, with the Voltamaster 4.0 software. The absolute
concentration of the electroactive species and the viscosity of each electrolyte was measured using a
concentration of supporting electrolyte can be studied viscosity meter (Model DV-III, Brookfield).
meticulously [9, 10]. In addition to that, the effects of Linear sweep voltammetry (LSV) technique was
variations in field strength in magneto-electrolytic used to investigate the effect of magnetic field,
deposition technology also can be observed. It had working electrode area, additive material and
being found that different strength of magnetic field electrolyte concentration on the limiting current
will effect the electrodeposited metal to a certain density. LSV were performed from +2 to -2 V at a
extend [5, 9].
Moreover, in the electrodeposition technology,
the additive concentration is also a crucial factor in
determining the electrodeposits with a smooth
surface. Boric acid was considered as cobalt systems
additive. It had being found that the presence of boric
acid in electrolyte will avoid the local pH rise caused
by parallel hydrogen evolution reaction (HER). The
results showed that the buffer contribution of boric
acid is effective in the cobalt electrodeposition at 25

C [11].
In this work, the effects of supporting and
additive electrolyte concentration are studied as a B
function of the kinematic viscosity and difussion
coefficient. The effect of magnetic strength, the Fig. 1. Schematic illustration of electrochemical cell
electrode area, the concentration of the electro active
species, the diffusion coefficient of the electro active sweep rate of 10 mV/s. Diffusion coefficients of
species, the kinematic viscosity of the electrolyte, and electroactive species were determined using
the additive concentration towards the limiting chronoamperometry. A potential step of
current of cobalt electrodeposition was also been choroamperometry is a cathodic potential at limiting
studied. current. Limiting current is then given by the Cottrell
equation:
1. Experimental
nFAD1/ 2 c
Cobalt (II) sulfate heptahydrate (≥99%) was I (t ) 
( t )1/ 2 (1)
purchased from Merck. Sodium sulphate (≥99%), and
Boric Acid (≥99.8%), were purchased from R & M Where A is the electrode area. Equation 1 shows
(Malaysia). All solutions were prepared using that the diffusion-limited current decreases with t-1/2.
distilled water. The magnet employed in this study A plot of I against t-1/2 is known as a Cottrell plot.
was a superconducting water-cooled electromagnet Under conditions of semi-infinite linear diffusion,
(Lake Shore EM 4, USA) with the pole pieces were such a plot will be linear, enabling the determination
of 5cm diameter and 5 cm apart. The intensity of the of the combination nAD1/2 from equation 1 [12, 13].
magnetic field could be adjusted with the rheostat of This part of the graph can be extrapolated to the
the control panel of the power supply from 0 to 0.3 T. origin, thereby demonstrating the expected behavior,
All electrochemical experiments were carried out in a and the slope yields a diffusion coefficient.
three electrodes cell (4.5 cm inner diameter) as
shown in Fig. 1, which containing 40 mL of the 3. Result And Discussion
appropriate electrolytic solution. The cell was placed
in the field cavity so that the working electrode 3.1 Presence of magnetic field and the influences
surface faced downward and was parallel to the lines of its Strength
of the magnetic flux that run horizontally. The
measurements were carried out at 25-27 ◦C in the
field cavity. Four platinum wires (0.1 cm diameter)
with areas of 0.32285, 0.48035, 0.63785 and 0.95285
cm2 were used as working electrodes (WE). The
counter electrode (CE) was a platinum wire (0.95285
cm2 area) and the reference electrode (RE) was an
Ag/AgCl electrode. Electrochemical experimentation
(chronoamperometry and linear sweep voltameter)
were carried out with a PGP 201 potentiostat
(Radiometer analytical S.A., France) and were
recorded and monitored by Compaq 6510 b Laptop

2
ISSN 1978-5933
The Second International Conference
On Green Technology and Engineering (ICGTE) 2009
Faculty of Engineering Malahayati University

Fig. 2. Variation of the limiting current iB under varied between 0.001 and 0.05 M using Na2SO4 0.5M
magnetic field as a function of the Magnetic strength as supporting electrolyte at a constant magnetic field
(B). CoSO4 0.01 M, 0.9529 cm2 working electrode, T (0.3T). Limiting currents were measured using a
= 25 - 27◦C. B = 0.3 T. platinum wire (0.9529 cm2) as working electrode.
Linear sweep voltammetry (LSV) were performed
Based on the results obtained from the from +2 to -2 V at slow sweep rates (10 mV/s) for
experiment, the the limiting current increases every compound.
proportionately to the magnitude of the magnetic The limiting current values of Fig. 3 show that at
strength (B) as shown in Fig. 2. The increment of higher concentrations of the electroactive species
limiting current indicated the increasing of mass magnetic stirring is more effective. This increment of
transport on electrodeposition process. This limiting current can be linked to the increasing
increment of limiting current can be linked to the concentration of the CoSO4 in the electrolyte. As the
presence of MHD effect. concentration increases, the free cations (Co2+)
When the MHD effect is present, the convective available in the electrolyte will also increase. These
flow will create mixing in the diffusion area and higher concentrations cause more efficient stirring. It
reduce the thickness of its Nernst diffusion layer in will also induce a turbulent flow within the
front of the electrode effectively. As the Nernst electrolyte, which this will increase the flux of the
diffusion layer decrease, the limiting current density species [10]. As a result, the thickness of the Nernst
will increase [13]. diffusion layer will gradually be reduced and this will
This phenomenon could happen because the decrease the screening effect. As the Nernst diffusion
magnetic field could increase the rate of transport of layer decrease, the limiting current density will also
electroactive species to or from the electrode. The increase [12, 13].
possible force which could be responsible for the In other words, typical data are shown in Fig. 3
enhancement of mass transfer is known as the Lorenz for confirming that higher concentrations cause more
force [3, 6]. The Lorenz force acts on migration of efficient mixing in the diffusion area. This is
charged ions inside the electrolyte and induce a certainly due to the fact that higher bulk
convective flow of electrolyte close to the electrode concentrations cause steeper concentration gradients
surface. This convective effect on electrodeposition and therefore higher currents, which in turn increase
process is known as MHD effect [14]. The change in the circulation producing even higher currents and so
the magnetic strength leads to the variation of the on until the magnetic force is counterbalanced by
limiting current, iB, but the value of D (diffusion friction [10].
coefficient) is unchanged by the magnetic field [7, The MHD effect caused by the magnetic field
10]. will also decrease the screening effect at the
deposition site. When the screening effect at the
3.2 The influence of bulk concentration of Nernst diffusion layer decreases, the limiting current
electroactive density also will increase [9].

3.3 The influence of working electrode area


(A)

Fig. 3. Variation of the limiting current iB under


magnetic field as a function of the CoSO4
concentration C. 0.9529 cm2 working electrode. T =
25-27◦C. B = 0.3 T. [Na2SO4] = 0.5 M. Fig. 4. Variation of the limiting current iB under
magnetic field as a function of the working electrode
To study the effect of concentrations of the area, A. T = 25-27◦C. B = 0.3 T. [Na2SO4] = 0.5 M
electroactive species on limiting current under and [CoSO4] = 0.01 M.
magnetic field, the concentration of CoSO4 was

3
To study the effect of the electrode area on
limiting current under magnetic field, the
concentration of CoSO4 was kept constant at 0.01 M
using Na2SO4 0.5 (M) under a constant magnetic
field of 0.3 T. Limiting currents were measured using
the four platinum wires (0.32285, 0.48035, 0.63785
and 0.95285 cm2 area) as working electrode.
The effect of the electrode area (A) on limiting
current under magnetic field (iB), was determined
with three different electrodes in in Na2SO4 0.5 (M) Fig. 6. Variation of the limiting current iB under
under a constant magnetic field of 0.3 T. From Fig. 4, magnetic field as a function of the diffusion
it is found that the limiting current increases as the coefficient (D). CoSO4 0.01 M, [Na2SO4] = 0.05 –
working electrode area increases. 0.4 M, Boric acid 0 – 0.12 M, 0.9529 cm2 working
The increment of this limiting current due to the electrode, T = 25-27◦C. B = 0.3 T.
increment of current which subsequently increase the
electrode reaction [8]. A larger area also will cause The influence of supporting electrolytes, was
more effective magnetic stirring in diffusion area. determined by keeping the electroactive species
This reduces the thickness of its Nernst diffusion constant (CoSO4) and by changing the s supporting
layer. This will cause the limiting current and electrolytes (Na2SO4). The concentration of CoSO4
deposition rate increase [10]. was 0.01 M in 0.05 – 0.4 M Na2SO4. The change of
supporting electrolyte concentration leads to the
3.4 The influence of supporting electrolyte variation of difussion coefficient and electrolyte
concentration kinematic viscosity. Rheometer is used to measure
the viscosity of electrolyte and it was divided by its
Table 1. Variation of diffusion coefficient (D) and density to yield the kinematic viscosity; the results
Kinematic viscosity (v) of the electroactive species are tabulated in Table 1. Limiting currents were
on the effect of supporting electrolyte (Na2SO4) measured using the 0.9529 cm2 platinum wire as
concentration working electrode. The diffusion coefficient value for
Co2+ were investigated using chronoamperometry.
CoSO4 Na2SO4 D x 106 v From Fig. 4, it is found that the limiting current
(M) (M) (cm2/s) (Stoke) decreases as the concentration of Na2SO4 increases.
0.01 0.05 6 0.01313
The decrease of limiting current can be linked to the
increment kinematic viscosity of the Na2SO4 in the
0.01 0.1 5.6 0.01402 electrolyte as shown in table 1. The variation of the
0.01 0.2 4.9 0.01500 electrolyte kinematic viscosity leads to a variation of
the electroactive species diffusion coefficient [7]. The
0.01 0.3 4.4 0.01598
increasing of the electroactive species diffusion
0.01 0.4 4.25 0.01679 coefficient leads to the increment of limiting current
as shown in Fig. 5. It seems that the decrease of the
mass-transport-limited current is due to the friction
forces becoming more effective as the electrolyte
viscosity increases, preventing MHD convection of
the solution [10].

3.5 The influence of additive electrolyte


concentration

The effect of additive electrolyte concentration on


magnetic electrodeposition was determined in CoSO4
0.01 M solutions by adding different amounts of
boric acid, from 0 to 0.12 M. Limiting currents were
Fig. 5. Variation of the limiting current iB under measured using the 0.9529 cm2 platinum wire as
magnetic field as a function of the kinematic working electrode. The effect of a magnetic field on
viscosity (v). CoSO4 0.01 M, [Na2SO4] = 0.05 – 0.4 the diffusion of Co2+ were investigated using
M, 0.9529 cm2 working electrode, T = 25-27◦C. B = chronoamperometry. The change in the electrolyte
0.3 T. composition leads to the variation of difussion
coefficient and electrolyte kinematic viscosity.
Fig. 7 shows the variation of the limiting current
iB under magnetic field as a function of the kinematic
viscosity (v) by adding different amounts of boric

4
ISSN 1978-5933
The Second International Conference
On Green Technology and Engineering (ICGTE) 2009
Faculty of Engineering Malahayati University

acid. The influence of additive on limiting current is


give linear graph; it curves downward confirming
that higher concentrations of boric acid cause
decrease stirring effect of MHD.
This is certainly due to the fact that higher
additive concentrations cause steeper kinematic
viscosity of electrolyte gradients. The increment of
the electrolyte kinematic viscosity leads to the
decreasing of the diffusion coefficient of
electroactive species. This causes the decreasing of
limiting current as shown in Fig. 8. [7]. It seems that
the decrease of the mass-transport-limited current is
due to the friction forces becoming more effective as
Fig. 8. Variation of the limiting current iB under
the electrolyte viscosity increases, preventing MHD
magnetic field as a function of the diffusion
Table 2. Variation of diffusion coefficient (D) and
coefficient (D). CoSO4 0.01 M, [Na2SO4] = 0.5 M,
Kinematic viscosity (v) of the electroactive species
Boric acid 0 – 0.12 M, 0.9529 cm2 working electrode,
on the effect of Additive concentration
T = 25-27◦C. B = 0.3 T.
CoSO4 Na2SO4 H3BO3 v D x 106
convection of the solution [10]. Although the
(M) (M) (M) (Stoke) (cm2/s)
presence of boric acid leads to decrease the limiting
0.01 0.5 0 0.0171 4.0 current, it is useful as a buffer to avoid the local pH
0.01 0.5 0.01 0.0173 3.6 rise caused by parallel hydrogen evolution reaction
0.01 0.5 0.04 0.0175 3.3 (HER) [11]. The Increment of HER caused a
roughness on the surface metal of electrodeposits.
0.01 0.5 0.05 0.0179 3.2
0.01 0.5 0.08 0.0182 2.9 4. Conclusions
0.01 0.5 0.12 0.0192 2.5
A homogeneous magnetic field has been applied
in a three electrode electrochemical cell and oriented
perpendicular to the electrode surface causes the
increment of the limiting current. The effects of the
magnetic field strength, the electrode area, the
concentration of the electro active species, the
diffusion coefficient of the electroactive species, the
kinematic viscosity of the electrolyte and the additive
concentration on cobalt electrodeposition have been
studied. The experimental results showed that those
parameters also found to be significantly effect on the
mass transport of cobalt electrodeposition. Higher
limiting current of electrodeposition was achieved
when higher magnetic field strength, working
Fig. 7. Variation of the limiting current iB under electrode area and concentration of electroactive
magnetic field as a function of the kinematic species and also when lower concentrations of
viscosity (v). CoSO4 0.01 M, [Na2SO4] = 0.5 M, supporting and additive electrolyte were applied. The
Boric acid 0 – 0.12 M, 0.9529 cm2 working electrode, increment concentrations of supporting or additive
T = 25-27◦C. B = 0.3 T. electrolyte lead to the increase of the kinematic
viscosity of electrolyte and also lead to the decrease
of the diffusion coefficient of electroactive species. It
also observed that the presence of boric acid as an
additive was lead to the smaller amount of limiting
current the decrease of limiting current. However it is
acting as a buffer to avoid the local pH rise caused by
parallel hydrogen evolution reaction (HER) which
results to the smoother surface of electrodeposits.

5. Acknowledgment

5
Financial supports from Ministry of Higher electrodeposition. RSCE – SOMCHE 2008,
Education Malaysia through FRGS grant No. 607113 Kuala Lumpur, Malaysia, pp. 961 - 964 2nd -
is greatly acknowledged. 3rd December 2008.
[3] Matsushima, J.T., Trivinho-Strixino, F., Pereira,
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