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Magnetic-field effects on fractal electrodeposits

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15 July 1999

Europhys. Lett., 47 (2), pp. 267-272 (1999)

Magnetic-eld eects on fractal electrodeposits

J. M. D. Coey1 , G. Hinds1 and M. E. G. Lyons2
1 2

Physics Department, Trinity College - Dublin 2, Ireland Chemistry Department, Trinity College - Dublin 2, Ireland

(received 26 January 1999; accepted in nal form 19 May 1999)

PACS. 81.15Pq Electrodeposition, electroplating.

Abstract. A uniform magnetic eld unexpectedly alters the form of copper deposits grown in a at electrochemical cell; the patterns change from radial to unidirectional when the cell is horizontal and vice versa when the cell is vertical. The electrodeposits are characterised by their chirality and fractal dimension. Complex impedance spectra show that the eective diusion coecient of the copper ions is doubled in a eld of 1 T. The results demonstrate that the eld produces a body force comparable to that of gravity. From dimensional analysis, it is inferred that the eld modies convective ow on a scale of a few microns close to the cathode.

Well-documented eects of magnetic elds on chemical reactions are uncommon [1]. In electrochemistry it is known that elds in the 1 tesla range can inuence the rate of deposition of metal in simple redox reactions [2-4], although no mechanism has yet been established. It has been suggested that the magnetic eld somehow alters the ion concentration near the electrode surface [5], or that convection currents are enhanced by the Lorentz force acting on charged species in solution [6, 7]. The surface morphology of the deposit is also inuenced by the eld [7]. Electrodeposits formed around a central cathode in a at cell have a characteristic fractal form [8] which is sensitive to the electrolyte concentration and applied voltage [9], and may be inuenced by magnetic eld [10]. Here we investigate a familiar electrochemical reaction, the electrodeposition of copper, in the presence of a magnetic eld. We have discovered that the form and fractal dimension of the electrodeposits depend on the magnitude and direction of the applied eld, and the orientation of the cell. Furthermore, the processes of diusion and electron transfer change by about a factor of two in elds of 1 T. Chirality, and asymmetry of stringy deposits obtained when the eld is applied in the plane of the cell establish that the magnetic body forces are comparable to those involved in convection. As no measurable direct inuence of the Lorentz force on the diusion coecient is anticipated, it is suggested that the eld acts to increase convection in the diusion layer. The fractal electrodeposits were grown from solutions of 0.2 M CuSO4 in a at cell with a central cathode and ring anode, at an applied voltage of 6 V. A permanent magnet ux source [11] was used to apply variable elds, B , of up to 1 T either parallel or perpendicular
c EDP Sciences



Fig. 1. Copper electrodeposits grown around a central cathode in a horizontal at circular cell (diameter 22 mm, thickness 2 mm) a) in zero applied eld, b) 0.4 T upwards, c) 0.8 T downwards, d) 1 T horizontally, and in the same cell oriented vertically, e) in zero eld and f) in 1 T perpendicular to the plane of the cell.

to the plane of the cell, which could be mounted either horizontally or vertically. Images of the resulting fractal patterns were analysed using the box-counting method [12]. Some typical fractal electrodeposits are shown in g. 1. With the cell horizontal dense radial growth is observed in zero eld (g. 1a), but when the eld is applied perpendicular to the plane of the cell a branching spiral pattern forms instead (g. 1b). If the direction of the eld is inverted, the chirality of the spiral is reversed (g. 1c). Furthermore, when the magnetic eld is applied parallel to the plane of the cell, a stringy deposit appears (g. 1d). It was surprising to notice that growth of the stringy deposit predominated in one specic direction perpendicular to the eld. Repeated measurements showed that this direction is the one in which the gravitational force and the Lorentz force are acting in unison. With the cell vertical, a dense deposit grows upwards from the electrode (g. 1e); it becomes stringy in a vertical eld, but turns into a branching spiral when the eld is perpendicular to the plane (g. 1f). Chirality with respect to the eld direction is opposite to that in g. 1b). These results are summarized in table I; the inuence of magnetic eld on chirality and fractal dimension, Df ,

j. m. d. coey et al.: magnetic-field effects on fractal electrodeposits


Fig. 2. a) Fractal dimension and b) chirality of electrodeposits grown with the cell horizontal as a function of applied eld. The fractal dimensionality is shown for the eld vertical () and horizontal (). Chirality is dened as the inverse radius of curvature of the main branches of electrodeposits like those in g. 1b) and c).

is presented in g. 2. There is a broad increase in fractal dimension in a perpendicular eld, but a clear decrease, from 1.8 to 1.6, when the eld is applied in-plane, corresponding to the increasingly stringy nature of the deposit. Complex impedance measurements were carried out with a view to elucidating the eect of the eld on the electrodeposition process. The electrochemical behaviour of the redox couple Cu2+ /Cu may be divided into two distinct regimes, an activation regime where the rate of reaction is governed by the kinetics of the electron transfer at the electrode, and a mass transport regime where diusion of ions towards the electrode is rate-limiting. In potentiodynamic polarisation plots (cyclic voltammetry) the electron transfer process is ratelimiting in the Tafel region close to the rest potential, whereas mass transport is dominant

Table I. Form of copper electrodeposits in zero eld or 1 T. Cell Horizontal B=0 dense radial Vertical dense unidirectional B = 1 T (vertical) branched chiral stringy unidirectional B = 1 T (horizontal) stringy unidirectional branched chiral



Fig. 3. a) Cole-Cole plots of the complex impedance spectrum of a 0.2 M CuSO4 solution with () and without () a 1 T magnetic eld. b) Plot of Z vs. 1/2 showing the eect of the eld on the diusion coecient (eq. (1)).

in the region of the limiting current plateau. Complex impedance measurements provide quantitative information about both processes. A small ac voltage is applied at the electrode and the magnitudes of the real (Z ) and imaginary (Z ) parts of the impedance are measured as a function of frequency. At high frequencies the kinetics of the electron transfer are ratedetermining and a characteristic semicircle is observed in the Cole-Cole plot of Z against Z . At low frequencies the rate of diusion becomes dominant and a straight line is observed. Here the Warburg impedance ZW is given by [13] ZW = kB T e 1/2 , z 2 e2 NA A 2D1/2 (1)

where D is the diusion coecient, = zeV /kBT , A is the area of the electrode, z = 2 for Cu2+ and V is the dc potential. Hence, the diusion coecient of the ionic species in solution may be calculated from the slope of the plot of ZW against 1/2 . Reproducible complex impedance data for the Cu2+ /Cu system obtained with a platinum working electrode in 0.2 M CuSO4 appear in g. 3. The Cole-Cole plot shows the semicircle characteristic of activation control and the straight line associated with the diusional Warburg impedance. The eect of the magnetic eld is to shift the upper intercept of the semicircle with the real axis. This corresponds to a decrease in the electrochemical rate constant kET in the 1 T eld. An opposite eect appears on the diusion coecient obtained from the slope of the plot of ZW against 1/2 in the Warburg region. From eq. (1) we calculate that D increases from 8 1010 m2 s1 to 1.6 109 m2 s1 in a eld of 1 T. This is similar to the increase that is achieved by gentle stirring with a rotating electrode. The zero-eld value

j. m. d. coey et al.: magnetic-field effects on fractal electrodeposits


is in good agreement with the literature [14]. Evidence for the two eects was also seen in potentiodynamic polarisation plots under similar conditions [4]. The Warburg region in similar experiments with a fractal electrode was ill-dened. Mass transport is the rate-limiting factor for the electrodeposits of g. 1. The increase of diusion coecient in the eld is consistent with the change in form of the electrodeposit. As the rate of mass transport increases, it has been found that the fractal dimensionality of zinc deposits increases and their form changes from diusion-limited aggregation (DLA) to dendritic [15]. The branched spiral deposits we observe are characterized as intermediate between DLA and dendritic in form. The problem is to understand how a magnetic eld can have such an impressive eect on diusion and therefore on the mobility of the copper ions in solution. The direct eect of the Lorentz force should be utterly negligible given the low ion velocities ( 400 m/s) and short mean free paths ( 1 nm). The results with the cell vertical establish that convection of the solvent near the cathode is important for mass transport. The Lorentz force associated with a current density j A/m2 produces a magnetohydrodynamic body force of magnitude jB per unit volume. Direct evidence that the body force is signicant is the unidirectional nature of the stringy deposits whenever B is applied in-plane, and particularly the fact that these strings tend to grow in the sense where the gravitational force and the Lorentz force add (g. 1d). Further evidence is the change from unidirectional to branched when the cell is vertical and the eld is applied perpendicular to the cell (g. 1e and f). The relevant quantity here is the dimensionless ratio Rg = jB . g (2)

This number will be 1 when the Lorentz and gravitational forces are equal in magnitude. In our case, j 2 104 A/m2 at the beginning of the experiment and 1000 kg/m3 so Rg 1 when B = 0.5 T. The sense of the chirality induced in the branched electrodeposits when the cell is horizontal and eld vertical is that expected from the Lorentz force (g. 1b and c), showing that it plays a role here too, when the gravitational and Lorentz forces are perpendicular. The dimensionless ratio RB = qB 6r (3)

of the transverse to the longitudinal forces acting on the moving ions turns out to be of order 108 if r is taken as the radius of the Cu2+ hydration sphere ( 1 nm), q = 2e and is the viscosity of the solution ( 103 Ns/m2 ). To yield observable chirality, RB should be of order 0.1 which means that when B = 1 T and q = (4/3)r3 , where is the positive charge density in solution, r should be a few m. This we interpret as the size of an eddy or of a convection cell. Recent observations by Devos et al. of bubble tracks on nickel electrodes support the idea that the eld inuences convective ow [7]. In conclusion, by growing fractal electrodeposits in dierent orientations with and without an applied magnetic eld, we have demonstrated unequivocally that the magnetic eld has an inuence comparable to that of gravity. From impedance spectroscopy we show that the eld increases the eective diusion coecient D, thereby promoting mass transport during electrodeposition. The phenomenon is related to convection on a scale of a few microns in the diusion layer near the cathode. The eld may modify streamline convection on a very small scale, but it is unlikely to create turbulence [16], since Reynolds number is of order 1.

272 ***


We are grateful to Siddharta Sen and R. Skomski for helpful discussions. The work was partly supported by Enterprise Ireland.
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