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

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

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The Second International Conference
On Green Technology and Engineering (ICGTE) 2009
Faculty of Engineering Malahayati University
front of the electrode effectively. As the Nernst
diffusion layer decrease, the limiting current density
will increase [7].
possible force which could be responsible for the
enhancement of mass transfer is known as the Lorenz
force [2, 10]. The Lorenz force acts on migration of
charged ions inside the electrolyte and induce a
convective flow of electrolyte close to the electrode
surface. This convective effect on electrodeposition
process is known as MHD effect [11].
Conclusions
The effect of the magnetic field on limiting
current of tin electrodeposition has been studied
using a three electrode electrochemical cell. It is
found that the limiting current of tin
electrodeposition strongly influenced by applied
magnetic field. Under the influence of magnetic
field, the limiting currents were observed to be
higher due to the presence of MHD effect. The value
of the magnetic strength, working electrode area, the
bulk concentration, diffusion coefficient of
electroactive species and the kinematic viscosity of
the electrolyte also found to be significantly effect on
the mass transport of electrodeposition. The higher
mass transport of electrodeposition can be achieved
when the lowest of kinematic viscosity of
electroactive species and the highest magnetic field
strength, working electrode area and concentration of
electroactive species were applied with the magnet
field placed horizontally. The increment kinematic
viscosity leads to decrease of limiting current. This
decrease of limiting current can be linked to the
decrease of the diffusion coefficient of electroactive
species. As the kinematic viscosity is increased, the
the diffusion coefficient of electroactive species
decreases significantly.
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ISSN 1978-5933
This phenomenon could happen because the
magnetic field could increase the rate of transport of
electroactive species to or from the electrode. The
Acknowledgment
Financial supports from Ministry of Higher
Education Malaysia through FRGS grant No. 607113
is greatly acknowledged.
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