THE INFLUENCE OF MASS TRANSFER ON THE

MECHANISM OF ELECTROPOLISHING OF NICKEL IN

AQUEOUS SULPHURIC ACID*

I. L. ALANIS’

and

D. J. SCHIFFRIN*

t Canning 258, 1414 Buenos Aires, Argentina

* Wolfson Centre for Electrochemical Science, Chemistry Department, The University, Southampton, So9
5NH, U.K.

(Receiued 26 October 1981)

Abstract-The effect of mass transfer on the elcctropolishingof nickel in sulphuricacid solutions has been
studied using a rotating disc electrode technique. Two well d&ted regions for different rotation rate-s have
been observed having (a) pure diffusioncontrol, and (b) mixed kineticand diffusioncontrol. The presenceof
a solid layer of a hydrated nickelsalt covering a contaminated oxide layer is proposed. The rate of chemical
attack of the underlyinglayer apes to depend on the SO4‘- ion concentration for H2S04 concentrations
greater than 8 M. When the rate of mass transfer is increased,changes in the morphology of the surface are
observed, polishing gives way to levelling, and finally either to metallographic etching or corrosion. The
disappearance of electropolishing is observed in general when the rate of mass transfer is sufficient to
eliminate from the surface the solid layer of hydrated nickel sulphate, and the results indicate a coupling
between diffusional rates in the solution and ionic transport through the oxide or contaminated oxide phases.

INTRODUCTION caused by the formation of a compact thin film on the

Although the electrolytic polishing of metals has been
known for many years[l, 21, its mechanism still re-
mains obscure. The original ideas of Jacquet[l, 21,
Elmore[3J, Edwards[4,5] and Wagner[6] were based
mainly on the establishment of a diffusional field at the
metal-solution interface, composed of either a salt of
the metal or a metal ion aozeptor diffusing to the metal
surface. Wagner’s model was found to apply in the case
of the electropolishing of tantalum from H2S04 + HF
mixtures[7] and of aluminium in HJP04[8].
Krichmar[9] derived a quantitative theory of
smoothing by a diffusion mechanism, and the levelling
of the microrelief on a metal surface caused only by the
establishment of a diffusional field in the solution was
found to be in good agreement with theoretical
predictions[ lo].
The importance of diffusion control in the setting of
electropolishing conditions has been repeatedly
established[ll-131 and in some instances, the coup-
ling of thermal effects and convective flow have been
observed[14].
However, there appear to be two simultaneous
mechanisms in operation during the electropolishing
of metals:
(a) the above mentioned diffusionally controlled sur-
face levelling, and
(b) a smoothing of the surface on a microscale which is
responsible for the surface brighteuing[15].
Hoar et al.[15,16] proposed that the second effect is
* Most of the work reported here was carried out at Sector
Electroquimica Aplicada, I.N.T.I., Buenos Aires, Argentina.
__
metal surface which results in the random removal of
metal atoms from it, due to the random arrival of
cation vacancies present in the film. The existence of a
solid film on the surface during anodic brightening has
been confirmed by a variety of techniques[ld-191.
From the point of view of its nature and composition,
it is important to noteCU] that electropolishing con-
ditions can occur in the same potential range at which
the metal is in the passive or transpassive state, ie,
covered by a slowly dissolving layer of metal oxides.
Whether passivity or brightening occurs, depends on
the concentration of the electropolishing solution; in
dilute solutions the metal passivates or transpassivates,
whereas polishing occurs in concentrated solutions.
Passivity in dilute solutions is not always a necessary
condition for polishing; there are cases where polishing
appears to occur in the active dissolution region[20],
for example, in the electropolishing of Fe and Co from
methanolic solutions of sulphuric acid.
A better understanding of the influence of mass
transfer on electropolishing, requires the control of the
hydrodynamic profile, since experiments performed
under natural convection conditions can result in
complex thermal effects[14]. In order to solve this
problem, Hoar et aL[21,22] used a linear channel flow
past a horizontal anode in their studies of elec-
tropolishing of copper in o-phosphoric acid[21], mag-
nesium in ethanolic o-phosphoric acid and nickel in
aqueous sulphuric acid[22]. These authors found the
expected dependence of current with flow rate pre-
dicted by Levich[23]. The use of a channel geometry
presents the disadvantage that the mass transfer
coefficient on the sample is not uniform, which may
838 I. L. ALANISAND
result in an inhomogeneous current distribution. From
this point of view, the rotating disc electrode geometry
is preferable, sinceit ensuresa uniform thickness of the
diffusion layer across the whole electrode surfacer231.
This system was used by Daguenet et aI.[24,25] &
study the electrowlishina of aluminiumr241 in maa-
nesium perchlorate, an> of nickel i> <ulphu&
acid[25]. In both cases, as in the work of Hoar et al.,
the expected diffusion controlled behaviour was ob-
served, although at high rates of rotations a limiting
current was noted. Also, the surface morphology
obtained was dependent on rotation rate. In the case of
nickel in 12 M H$O,, the surface polishing was
impaired at 2000 rev min-’ and gave way to uneven
corrosion behaviour at 10,000rev min- I. Similar
qualitative information had already been reported by
Walton[26]. Therefore, the study of mass transfer
effects is essential for the understanding of the mech-
anism of electropolishing.
The system Ni-H,SOo was chosen for this study as
an example of a metal that shows a transition between
transpassivity and electropolishing as the acid concen-
tration is varied between dilute up to 12 M sulphuric
acid solutions[25].
EXPERIMENTAL
In order to study the influence of the rate of mass
transfer on the anodic dissolution of Ni under polish-
ing conditions, a rotating disc electrode technique was
employed.
The working electrode was made of 99.995 Ni bar
(Gallard Schleiger C2541) machined in the form of a
cylinder of 5 mm diameter and pressed into an ap-
propriate Teflon rotating disc electrode holder. The
metal was not annealed before use and the grain size
was of the order of 0.2 mm. Before each run, the
electrode was polished under water with 600 abrasive
paper and then rinsed with distilled water and alcohol.
This ensured that no recesses were formed at the edge
of the nickel electrode after prolonged use, which
would have resulted in a disruption of the hydro-
dynamics of the system. The electrode was elec-
tropolished in 10 M sulphuric acid to a mirror finish
before use. The surface was examined before and after
each experiment with a metallographic microscope.
Twelve sulphuric acid concentrations were studied
at different rotation rates and potentials in the anodic
end before oxygen evolution. A conventional three
electrode cell was employed. The counter electrode was
isolated from the solution and electrical contact was
made by means of a fritted disc. A Hg./Hg,S04/K2S04
{sat) reference electrode was used and a Luggin
capillary was placed near the edge of the rotating
electrode. All potentials were referred to the normal
hydrogen electrode. A LYP Electronica (La Plats,
Argentina) potentiostat and rotating disc assembly
were used, and measurements were performed in the
15&4C@Orev min - ’ rotation rate range. Higher veloc-
ities could not be used due to the breakdown of
convective conditions.
The solutions were prepared from Baker P.A.
HISOo and water doubly distilled from alkaline
permanganate. Mallinckrodt P.A. NiSOa.6HZ0 was
employed without further purification.
D.J. SCHIFFRIN
Before measurements were taken, the solutions were
saturated with 4 N tank nitrogen. All measurements
were performed at a temperature of 20 f 0.3 “C. The
solubility determinations were performed by keeping
solid NiS0.+.6HZ0 in contact with appropriate H1S04
solutions for periods up to 4 months, and the resulting
sulphuric acid and nickel ion concentrations were
determined volumetrically, in the latter case, using an
EDTA titration technique.
RESULTS AND DISCUSSION
The effect of a varying concentration of H2S04 on
the transpassive dissolution of nickel is shown in
Fig. 1.As has been observed previously for more dilute
solutions[27], there is an increase in the transpassive
current as the acid concentration rises, caused by an
increase in the rate of attack of the oxide surface layer.
In the potential region where Ni is in the passive state
in solutions more dilute than 1 M, ie 0.61.0 V us nhe,
the current is seen to increase steadily with the
sulphuric acid concentration, whereas in the polishing
region ( - 1.8 Vu), the current density passes through a
maximum value for approx. 8 M concentration.
It was found that there was no dependence of the
current on the rate of mass transport for current
densities below - 10 mAcn_’ for all the concen-
trations studied. A strong diffusion control is observed
for solutions more concentrated than 4 Mat potentials
anodic to 1.7 V,. Figures 2(a)-(d) show the depen-
dence of the current density on rotation rate for some
of the concentrations studied.
It can be seen that the dissolution rate is not entirely
diffusion controlled. In order to establish the existence
of mixed diffusion and kinetic control, i-’ us w- ‘I2
0.1
“:
5
4
1 0.0 I
. .
.
l .
.
. a*=
l -0 l.
I t , I I 1
I.8 1.4 1.0 0.6
V”/V
Fig. 1. Dependence of the current density on potential in the
anodic dissolution of nickel for different concentrations of
sulfuric acid.
‘3.9lU; l 6.5M;= 8M; V9.25M; o 11SM; A12.9M.
Rotation speed = 1000r.p.m. Potentials are referred to the
nhe.
 Mass transfer on electropolishing of nickel 839

.-
__*- I I I
Fig. Z(a). “’ I I 1 0. I 0.2
10 20
Fig. 3(a). “-‘/2,sP2
,h , s -92

Fig. 2(b). La*’

0 1.95

a3 c 0
0 o”
. . l * . I.80

A A AA * 1.55

lx 0.2
Fig. 2(c). /” I Fig. 3(c). _-$2, $ Lz
I I
10 20
wLa,p'a

Fig. 2(d). \*” I I I 1 I I 1

IO 20
Fig. 3(d). 0.1 0.2
###-bz,.+
,h ,*-v+

Fig. 2. Dependence of the current density on rotation speed Fig. 3. Dependence of i- ’ on w - f for nickel in sulfuric acid
at different potentials for nickel in sulfuric acid at different at different concentrations and potentials.
concentrations. (a) 6 M; V 1.75 VH; l 1.80 VH: o 1.85 VH; A 1.90 VH.
(a)6 M; V 1.75 VH; . 1.8OVH: 0 1.85VH; 0 1.90VH. (b) (b) 7.5 M; o 1.80 VH; A 1.55 VH. (c) 10 M; o 1.80 VW;
7.5 M;o 1.80 V,; A 1.55 VH. (c) 10 M; A 1.55 V,; l 1.80 V,; o 1.95 VH. (d) 12.5 M; V 1.45 V,; A 1.65 V,; o 1.75 V,;
o 1.95 VH. (d) 12.5 M; V 1.45 VH; A 1.65 VH; o 1.75 VH; . 1.80 V,.
. l.SOVH.

graphs were constructed, and the results are shown in where i is the current density, D is the diffusion
Figs. 3(a j(d) for the same concentrations. coefficient of the metal ion, v is the kinematic viscosity
The simple first order equation for the anodic of the solution, I; is the Faraday constant, w is the
dissolution of a rotating disc metal electrode in the rotation rate in rads-‘, and kr, kb are the elec-
absence of its own ions in the bulk of the solution and trochemical rate constants for the electrode process:
with excess of indifferent electrolyte, is given by[28]:
kF
i-1 1 1.61D-2’3v’/bkb
_w-‘/l, (1)
MeM”+ +ne-. (2)
nFkr flF kf kb
840 1. L. ALANISAND
A linear relationship between i-’ and co-‘/‘, with a
potential dependent slope should be observed[28].
This is clearly not the case for the present system, (see
Figs. 3a-d), and there are two well defined regions for
different ranges of rotation rate. A completely dif-
fusionally controlled process, ie the current density
being proportional to WI/‘, seems to occur at low
rotation rates, whereas at high rates of rotation, a
mixed kinetic-diffusional mechanism is operative.
(a) The di#iision conrrol region
A purely diffusional process may be due either to the
presence of a solid salt layer of NiSO, or its hydrated
form on the surface (see below), or to the presence of a
solution saturated with respect to the soluble nickel
salt formed over a wide range of mass transfer
conditions.
Gilli et aI.[29] observed the formation of salt layers
under polishing conditions for stationary nickel elec-
trodes and detected NiS04.6H20 by X-ray
spectroscopy.
The diffusion coefficient for the diffusing species can
be calculated from[23]:
i, = 0.62nFD~i~~v1ia~C~-C’,]w”*, (3)
where iD is the diffusionally controlled current, CS, is
the equilibrium concentration of the diffusing species
at the electrode-solution interface, and Cs, is the salt
concentration in the bulk of the solution.
In order to calculate the value of the diffusion
coefficient of the Ni2 + species diffusing, the value of
the equilibrium concentration C;, must be known. The
simple assumption first made was that the solid phase
which is formed on the electrode, or the corresponding
saturation value, was the equilibrium phase at the
corresponding sulphuric acid concentration. The
values of the solubilities found are shown in Fig. 4.
These measurements were taken after equilibrating the
solutions for more than 4 months, and are comparable
with results in the literature[31] for solutions more
dilute than 7 M. The differences at higher concen-
trations could not be accounted for, and repeat
Fig. 4. Equilibrium concentratioo saturation values for
NiSOL in solutions of sulfuric acid at different wmxn-
trations.
l Present work. I Data from ref. [31]. Temperature
= 20” c.
D.J. SCHJFFRIN
experiments gave similar results. The measurements
for concentrations of sulphuric acid greater than 14 M
were found to be somewhat irreproducible, probably
due to the length, the system takes to reach true
equilibrium.
The values of the diffusion coefficients calculated
From equation (3) using the solubility values shown in
Fig. 4 and the limiting slows di/dwl’z in the dif-
fuGona1 region, are sh&n in Fig. 3. The values of the
kinematic viscosity were taken from reference[31] for
pure sulphuric acid solutions. It can be seen from Fig. 5
that the apparent diffusion coefficient varies over
several orders of magnitude. This effect cannot be
accounted for by changes in viscosity in the diffusion
layer due to the dissolution of NiS04, as has been
shown to occur in the electrapolishing of copper in
phosphoric acid solutions. The reason for the apparent
failure ofequation (3) in the calculation of DNi,+ is due
to the use of the equilibrium solubility values, as shown
below.
The diffusional character of the process for low
rotation rates can be shown by varying the concen-
tration of NiSO+ present in the solution. The solutions
in this case, were made by dissolving NiS0,.6H20 in
the sulphuric acid solution, and adding sufficient
amount of concentrated HISO, to keep the acid
concentration of the soiution constant. The results for
9.25 and 11.5 M HzS04 solutions are shown in
Figs. 6(a) and 6(b). There is a linear relationship
befween ‘(di/do”“jo + 0 and the NiSO* concen-
tration in solution. as shown in Fig. 7. The extrapo-
lation to zero slopeindicates the value of the safuratjon
quantity Ct for these acid concentrations, These
results are similar to those by Han Chung Kuo[32]
for iron dissolution in contact with FeCI, sol-
utions. Also, Varenko et al.[33] found a decrease in
16’ .rn n
l
l m n
.
t
Fig. 5. The apparent diffusioncoefficinetof Ni2+ ion calcu-
lated from equation (3) for different values of sulfuric acid
concentrations.
wCalculated using the equilibriumconcentration values of
the saturated NiSO, solutioos.
I Ibid but using the C& values from the results of
experiments with NiS0&iH20 added to the solution (see
text).
 Mass transfer on electropoiishing of nickel
Fig. W.
Fig. 6(b)
Fig. 6. Rotation speed dependence of the anodic dissolution
current at 1.8V~ in the presence of dissolved NiSO, in
sulfuric acid solutions. The NiSO, concentrations are in-
dicated in the figures. (a) 9.25 M and (b) 11.5 M.
C .,,,./mC-’
Fig. 7. Dependence of the slope di/dw”’ for w + 0 in the
diffusional region for the results shown in Figs. 6(a) and 6(b).
l 9.25 M and I 11.5 M. The arrows indicate the C&values for
these concentrations.
841
the values of the slope (di/dw”‘) for the anodic
dissolution of Zn in solutions of ZnSOo under polish-
ingconditions. If the data presented by these authors is
treated in the same way as the results in Fig. 7, a linear
dependence between (di/do’/‘) and concentration is
found, with a value of Ci of 3.2 M, which corresponds
to the solubility of zinc sulphate at room
temperatureC301.
These results confirm that when polishing occurs,
the dissolution of the metal is controlled by the
diffusion of a metal salt in the solution, and its rate
is determined by the mass transfer conditions
established.
The C; values obtained for nickel are much higher
than the equilibrium solubility, approaching the value
of a saturated solution of NiS04 in water (2.3 M[30]),
for a 9.25 M NzS04 solution. The apparent diffusion
coefficient calculated from (3), using the values of Cb
thus obtained, gives 1.2 x lo-’ cm2 s- 1 for both sol-
utions. Figure 5 also shows the values of the diffusion
coefficient for other concentrations, by estimating the
C$ values from the saturation value in water and the
saturation values obtained from Fig. 7. This approach
gives a fairly constant value for the diffusion coefficient
of nickel ions for different sulphuric acid solutions,
indicating the applicability of equation (3), provided
the correct Cz values are used.
The large difference between the equilibrium sol-
ubility and that of the dissolving anodic layer explains
the reported little dependence of the limiting current
on the equilibrium bulk Ni*+ concentration in the
electropolishing of nickel from aqueous sulpburic
acid[34].
There are two difficulties in the analysis of the actual
values of DNizt obtained:
(a) activities of NiSO, should be used, in particular,
due to the large concentration change occurring
across the diffusion layer, from 2 to 2.3 M to zero
concentration; and
(b) the neglect of electrical migration phenomena.
The estimation of the latter effect[35] shows that it
is not important and cannot amount to an error of
more than 5 0/0 in the estimated diffusion coefficient
due to the small ratio of diffusing salt to sulphuric acid
present in the solutions studied. The very low values
for DWil+obtained, as compared with the usual values
for ionic diffusion in aqueous solution, are reasonable
if it is considered that NiSO, is strongly ion-paired in
solution, and its activity coefficient in water for a 2.3 M
solution is 0.035[36]. No data is available for NiSO, in
the concentrated sulphuric acid solutions employed in
this work, and the quoted value for DNil* must only be
regarded therefore as an apparent quantity.
Nevertheless, these results imply that either the solid
phase that is dissolving on the electrode in the range
where polishing occurs is not the equilibrium phase, or
that the concentration of the saturated solution on the
electrode surface does not correspond to the equilib-
rium value for the given H,S04 concentration. In fact,
the diffusional current in the polishing region for an
electrode in 11.5 M H,SO, is practically unaffected, if
the sulphuric acid solution is changed by an equilib-
rated NiSO, saturated solution for this acid concen-
tration. However, NiSO,. 6H20 is freely soluble at this
acid concentration, to give metastable concentrated
solutions that deposit slowly, after an induction period,
842 I. L. AUNIS AND D. J. SCHIFFRIN

an anhydrous NiS04 phase. Similar results were

obtained with the 9.25 M solution.
The formation of metastable salt layers have also
been observed in the electropolisbing of nickel in
hydrochloric acid solutions[37] and the effect is rather
puzzling. It is clear that in the 10 M H,SOA concen-
tration range, the anhydrous salt is the equilibrium
phase, but the evidence favours the initial formation of
a fully hydrated nickel ion salt. The reason for this is
probably related to the establishment of a concen-
tration gradient of sulphuric acid in the diffusion layer
due to the NiSO, gradient present. The formation of
NiSO, at the dissolving oxide interface, must be
necessarily accompanied by a decrease in the hydrogen
ion concentration; this effect could result in a decrease
of the free sulphuric acid surface concentration of
2.3 M, corresponding to the solubility of NiSO,.
Therefore, the relative surface concentration of water
at the dissolving surface is greater than that cor-
responding to the bulk H,SO,, by an amount which is
sufficient to make feasible the formation of hydrated
nickel sulpbate as the preferential process (see Fig. 4
and data in ref.131 1).
It is curious that contrary to previous suggestions
regarding the formation of an anhydrous layer during
electropolishing from aqueous solutions[38], a water
concentration at the interface greater than that in the
bulk of the solution is apparent. The reason is simply
that the change in the local acid concentration due to
the fast dissolution process must be taken into account
in the steady state mass balance.
It can be concluded then, that the existence of an
extended range of mass transport conditions in which
the electrode behaves as a solid NiSO, phase dissolv-
ing under mass transport control, indicates that there is
a solid layer of a form of NiSO, formed by chemical
attack of the underlying oxide layer by sulphuric acid
covering the oxide layer. The thickness of the NiSO,
layer depends on the rotation rate. When the mass
transport conditions imposed are higher than the rate
of dissolution of the film, an abrupt change in sl0pe in
thei-l/o-‘iv’ lotsindicatesachanaeincontroIoftbe
anodic’processfrom diffusion to ch&ical attack of the
underlying layer. It is not possible at present to
speculate further on its chemical nature.
(b) The activated-diffusion control region
As is seen in Fig. 8, the limiting current density at
infinite rotation rate, il, appears to be directly pro-
portional to the concentration of SO:- ions in the
solution. If this were the case, the dissolution mechan-
ism would be:
0.3
h
7 a2
.--
0.1
C n x) /ml-’
* 4
Fig. 8. Limiting current density (for w + co) for the anodic
dissolutionof nickelin sulfuricacid solutionsat a potential of’
1.8 V,. The dotted line indicates the concentration of SOi-
ion.
mation of absorbed NiSO, is considered. The values
of k, calculated from the limiting currents and
equation (5) are shown in Fig. 9 for different sulphuric
acid concentrations.
The constancy of k, found, is not a good diagnostic
criteria For the mechanism indicated by equation (4).
Activities and not concentrations of SOi- ions should
be used; unfortunately, the single ionic activity is not a
measurable quantity, nor can it be estimated on the
basis of non-thermodynamic assumptions for the
concentrated solutions studied. The only estimation
available comes from the use of acidity functions[39]
but in this case, the concentration range in which the
estimation was considered valid was from 12 to 18 M.
The only justification for the use of concentrations in
the calculation of kl, is the suggestion[40] that the
individual activity coefficients may become constant
for concentrated HZSO, solutions.
A more serious difficulty arising from mechanism (4)
is the concentration dependence of the slopes
P = di-‘/da- ‘I’. This quantity is shown in Fig. IO,
and the results are at variance with the predictions of
equation (5). According to (5), P should be inversely
proportional to Cso2_ and hence, pass through a
minimum value at a concentration of - 8 M, which is
clearly not the case. In fact, P has a fairly constant value
up to a solution concentration of ~8 M, and then
increases for more concentrated solutions, as predicted
by (5).

GO02

where Nit:is
k-1
a nickel ion in the oxide layer. The
possibility of a backward reaction has to be included,
since the process has the characteristics of a mixed
activated-diffusionally controlled reaction at high ro-
i

._Q
r-
;

0.001
I
f

0 OO
0 00
0
0
0
0

tation rates..The dependence of the current on the

rotation rate .corresponding to process (4) is given by: L 1 I I
5 10

1 1 1.61v”6D-.2’
“k_
NP’ 1 Cw’tsO./ m 1-l
-_=
i 2Fk C w- 1,~ . (5)
2Fk&,.+ 1 so:-
Fig. 9. Values of k, at different sulfuric acid concentrations
A similar result is obtained if the intermediate for- calculated from equation (5) at 1.8 V”.
 Mass transfer on electropolishingof nickel 843

Fig. 11. i-l DSU.J-‘I’ plot for the anodic dissolution of nickel
Fig. 10. Values of dim’/dw-“’ in the mixed dif-
in 11.5 M sulfuric acid at 1.8 V, for different concentrations
fusion-activation control region for the anodic nickel dissol-
of NISO, in the solution. The NiSO, concentrations are
ution at 1.8VH for different sulfuricacid concentrations.
indicated in the figure.

Also, experiments performed adding either Na2S04

or NaHSO, to the sulphuric acid solution, resulted in a 0.3
different behaviour for different sulphuric acid con- N
centrations. For solutions more dilute than 7 M, the I5 0.2 -
limiting current density was unaffected, whereas for 2
solutions more concentrated than 9 M, the current -- 0.l’
decreased. The increase in the HSO, concentration
results in an increase of C so;l In
. the first case, whereas 1 I I (
in the concentrated sulphurlc acid range, a decrease 0 0.5 I
occurs. These results and those presented in Fig. 10, CNibO /ml-’
indicate that there is not a single dissolution mechan- L

ism for all the sulphuric acid concentrations studied, Fig. 12. Limiting current density (for w -+ co) for the anodic
and equation (5) describes the behaviour in the high dissolution of nickel in 11.5 M sulfuric acid at 1.8 VH for
concentration range only. different values of NiSO, concentrations.
From the measured slopes and the i, values for
concentrations greater than 10 M, a value of k_,
N lo-4+3.10-5 ems-’ is estimated from equation
(5), taking DNia+= lo-’ cm2s-‘, as was previously
calculated. It is possible now to analyse further the 0.06
an
results for the solutions containing dissolved NiSO*,
to check their consistency. In the presence of NiSO, in
the bulk of the solution, equation (5) becomes:
1 1
~i = 2F[k,Csoi- -k_,CNiSO,-J
1.61 k_,~“~D,,;!s - 1,1
(61
+2Frk,Cso:--~-,cCNiS0.]W *
Figure 11 shows the plot i- ’ us o-1/z for the 11.5 M
case, and Figs 12 and 13 show the variation of the Fig. 13. Values of di-‘/dw-“2 in the mixed dif-
limiting current density and the inverse of the limiting fusion-activation control region for the anodic dissolution
of nickel at 1.8 VH in 11.5 M sulfuric acid for different NiSO.,
slope P at high rotation rates for different NiS04 concentrations.
concentrations respectively.
From (6),
di, sented in Fig. 12 is 2 x 10m4ems-‘, which is in
___ = -2Fk_, (7) reasonable agreement with that calculated from pure
dC NiSO+
sulphuric acid solutions. The value of the diffusion
and coefficient calculated from the results in Fig. 13 and
W/PI 2FD”’ equation (&) is Y lOA6 cm* s- ‘, which is an order of
-‘-m’ 03) magnitude greater than that estimated from the limit-
dC NiSO, ing slopes as CL-~/~+ 0 for pure sulphuric acid
The value of k _ 1 calculated from the results pre- solutions. When the indirect way and the different
844 I. L. ALANISANDD. J. SCHIFFRIN
conditions in which these quantities are obtained is
considered, the agreement must be regarded as satis-
factory; in particular, the diffusion coefficient c&u-
lation will be affected by the change in properties
across the diffusion layer. The results obtained for the
9.25 M case were k-, = 2 x lo-’ cm2s-’ and D,++
2 x 10e6 cm s-l which are in good accord with the
:.5 M solution reiults.
At low acid concentrations, the rate determining
step does not involve the SOi- ion and in this
concentration range, the transpassive dissolution
mechanism indicated by Sate et a!.[273 for dilute acid
solutions, is probably still operative, ie, the rate
determining step is:
kz
NiOHT& + NiOHG, (ads)
k-a
followed by
NiOH&)+ H& -+ Nit&+ Hz0 (fast).
ln this case, there will still be a variation of the current
with rotation rate at sufficiently high current density
values, depending on the thickness of the reaction layer
for the protonation reaction.
(c) The polishing region and the mechanismofelectro-
polishing
The morphological aspects of nickel dissolution,
were studied at different rotation rates and varying
sulphuric acid concentrations, by microscopic obser-
vation. The electrode was first polished with 600 grade
emery paper, and then left for periods of 15-20 min at
a given rotation rate at a potential of 1.8 V,. After the
attack, the electrode surface was observed with a
metallographic microscope.
Five different types of behaviour were observed: (I)
Crystallographic etching; (2) Levelling; (3) Polishing;
(4) Corrosion and (5) Pitting.
The transition to different forms of behaviour for
different rotation rates was not sharp and very often
intermediate forms were present. The results are
summarised in Fig. 14, there is a limited range of
r 12. G. H. Sedahmed,M. 2. El-Abd, I. A. S. Mansour, A. M.
I I I I
5 IO 15
0'4 /S--L
Fig 14. Dependence of the morphology of the attack on the
sulfuricacid concentration and the rotation speed for anodic
dissolutionof nickelat 1.8V,. A = polishing;B = IeveIiin&
C = crystallographic etching and D = levelling, corrosion
and pitting.
concentrations and rotation rates for which elec-
tropolishing is observed. As the rotation rate is
increased, the surface finish changes from polishing to
levelling and finally, to either crystallographic etching
or corrosion and pitting. This result is in agreement
with previous observations on the effect of mass
transfer on electropolishing[25].
The transition of polishing to non-polishing con-
ditions, correlates to the changeover from diffusion to
mixed control, which shows that the presence ofa solid
salt layer on top of the oxide (or contaminated oxide)
layer, is essential for electropolishing to occur.
The main conclusion of this work is, therefore, that
there is a coupling between dausional rates on the
solution and ion transport through the oxide layer
when electropolishing occurs. The increased metal ion
(9) transport in surface areas with high radius of curva-
ture, probably inhibits the dissolution in adjacent
regions by a mechanism similar to that proposed for
the screening effects observed in the nucleation and
(10) electrodeposition of a new phase[41]. In this model,
the ohmic drop generated round a growing nucleus can
be sufficiently large to decrease the potentials in
regions close to it, to values below the critical nuclea-
tion overpotential. In the polishing case, this extreme
situation obviously cannot be real&d, but nonethe-
less, some degree of shielding due to the localised field
is bound to occur.
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