Surface Technology, 11 (1980) 99 - 109 99

,J(:',Elsevmr Sequoia S A, Lausanne Printed m the Netherlands

F U N D A M E N T A L A S P E C T S OF P U L S A T I N G CURRENT METAL
ELECTRODEPOSITION
I: THE E F F E C T OF THE P U L S A T I N G CURRENT ON THE SURFACE
R O U G H N E S S A N D THE POROSITY OF METAL D E P O S I T S

K I. POPOV, M. D. MAKSIMOVI¢ and B M OCOKOLJI~

Faculty of Technology and Metallurgy, Unwers~ty of Belgrade, Belgrade (Yugoslavia)
B J LAZAREVI~
Faculty of Organ~zatmnal Scwnces, University of Belgrade, Belgrade (Yugoslawa)
(Received November 13, 1979)

Summary

T h e m e c h a n i s m of electrode s u r f a c e r o u g h e n i n g m p u l s a t i n g c u r r e n t
m e t a l e l e c t r o d e p o s i t i o n is o u t h n e d . The effect of t h e p u l s a t i n g c u r r e n t on
the p o r o s i t y of t h e m e t a l deposits is discussed on t h e basis of this mech-
anism. G o o d a g r e e m e n t b e t w e e n m a t h e m a t i c a l models, e x p e r i m e n t a l r e s u l t s
a n d h t e r a t u r e d a t a is obtained.

1. I n t r o d u c t i o n

It is k n o w n t h a t good m e t a l deposits c a n be o b t a i n e d u s i n g p u l s a t i n g
c u r r e n t e l e c t r o d e p o s i t l o n . R o m a n o v [1] was the first to c a r r y out an exten-
sive q u a n t i t a t i v e s t u d y by o b s e r v i n g the a p p e a r a n c e of d e n d r i t i c zinc
deposits from a l k a l i n e z i n c a t e s o l u t i o n s u n d e r the influence of v a r i o u s par-
a m e t e r s of the p u l s a t i n g c u r r e n t a n d by c o m p a r i n g this w i t h the a p p e a r a n c e
of d e n d r i t e s m the d.c. e l e c t r o l y s i s of the s a m e system. H e s h o w e d t h a t a
s h a r p i n c r e a s e in t h e t i m e to a p p e a r a n c e is o b t a i n e d at f r e q u e n c i e s b e l o w
500 Hz. H o w e v e r , at v e r y low f r e q u e n c i e s d.c. c o n d i t i o n s are a p p r o a c h e d a n d
h e n c e s h o r t times to a p p e a r a n c e are to be expected. T h e effect of h i g h e r
f r e q u e n c i e s c a n be e x p l a i n e d as follows [2]. T h e p u l s a t i n g c u r r e n t is used
b o t h for d o u b l e - l a y e r c h a r g i n g a n d for the d e p o s i t i o n process. The capacit-
a n c e c u r r e n t of periodic c h a r g i n g a n d d i s c h a r g i n g of the double l a y e r at
f r e q u e n c i e s at w h i c h t h e effect of the double l a y e r c a n n o t be n e g l e c t e d
p r o d u c e s a s m e a r i n g of the f a r a d a i c c u r r e n t wave. H e n c e , as the f r e q u e n c y
i n c r e a s e s , the f a r a d a i c c u r r e n t w a v e flattens a n d a p p r o a c h e s d.c. e v e n
t h o u g h the o v e r a l l c u r r e n t a p p e a r s to be p u l s a t i n g .
T h u s a g e n e r a l d i s c u s s i o n of the effect of a p u l s a t i n g c u r r e n t on the
m o r p h o l o g y of m e t a l deposits should deal w i t h r e l a t i v e l y low frequencies. Ibl
100

et al. [3] h a v e s h o w n t h a t good effects c a n be o b t a i n e d by u s i n g s h o r t pulses

of l a r g e c u r r e n t a m p l i t u d e followed by a r e l a x a t i o n time sufficiently long to
allow c o m p l e t e r e l a x a t i o n of the diffusion layer. In t h e s e c o n d i t i o n s ex-
t r e m e l y t h i n p u l s a t i n g diffusion l a y e r s are o b t a i n e d ; a s i m i l a r s i t u a t i o n
o c c u r s in h i g h f r e q u e n c y p u l s a t i n g o v e r p o t e n t i a l d e p o s i t i o n [4]. Ibl et al. [3]
a n d V l s w a n a t h a n a n d R a u b [5] h a v e s h o w n t h a t deposits o b t a i n e d w i t h a
p u l s a t i n g c u r r e n t are less p o r o u s t h a n deposits o b t a i n e d with a c o n s t a n t
c u r r e n t . R o m a n o v [1], Sun et al. [6] and G u r o v i t c h a n d K r I v t z o v [7] h a v e
r e p o r t e d t h a t a n i n c r e a s e in the pause-to-pulse r a t i o leads to a d e c r e a s e in
the s u r f a c e r o u g h n e s s of m e t a l deposits.
T h e m a s s t r a n s f e r in p u l s a t i n g c u r r e n t e l e c t r o l y s i s h a s also b e e n trea-
ted q u a n t i t a t i v e l y in a n u m b e r of p a p e r s [8 - 10]. In spite of this the mech-
a n i s m of t h e beneficial effects of a p u l s a t i n g c u r r e n t on the m o r p h o l o g y of
m e t a l deposits h a s n o t b e e n clarified yet. H e n c e t h e p u r p o s e of the p r e s e n t
w o r k was to i n v e s t i g a t e the m e c h a n i s m of e l e c t r o d e s u r f a c e r o u g h e n i n g m
p u l s a t i n g c u r r e n t e l e c t r o d e p o s l t I o n a n d the effect of the p u l s a t i n g c u r r e n t
on the p o r o s i t y of the m e t a l deposits.

2. Experimental

The effect of a p u l s a t i n g c u r r e n t on the m o r p h o l o g y of m e t a l deposits

was i n v e s t i g a t e d by d e p o s i t i n g c o p p e r from 0.5 M CuSO 4 in 1 M H2SO 4 o n t o
a p l a t i n u m e l e c t r o d e (for m e a s u r e m e n t of the r e l a t i o n s b e t w e e n the a v e r a g e
c u r r e n t d e n s i t y a n d the m e a s u r e d p o t e n t i a l ) or o n t o c o p p e r wire (for deter-
m i n a t l o n of the q u a l i t y of the e l e c t r o d e p o s i t e d copper). The a v e r a g e c u r r e n t
a n d p o t e n t i a l w e r e m e a s u r e d in s t e a d y s t a t e conditions. E l e c t r o d e p o s i t l o n
was c a r r i e d out at r o o m t e m p e r a t u r e m a n open cell. A c o n t r o l l e d c u r r e n t
was o b t a i n e d by u s i n g a p o t e n t i o s t a t and a f u n c t i o n g e n e r a t o r . T h e counter-
e l e c t r o d e a n d the r e f e r e n c e e l e c t r o d e were of p u r e copper. O v e r p o t e n t i a l
t i m e r e l a t i o n s were r e c o r d e d w i t h a n oscilloscope, a n d the a v e r a g e c u r r e n t
a n d p o t e n t i a l w i t h a p p r o p r i a t e d.c. i n s t r u m e n t s . The s h a p e of the applied
c u r r e n t pulse was the s a m e as t h a t used by Ibl et al. [3]. The r a t i o b e t w e e n
t h e pulse and the p a u s e was v a r i e d from 1:1 to 1:9 and the pulse d u r a t i o n
from 10 ~ to 10 s.
T h e l i m i t i n g diffusion c u r r e n t in this s y s t e m was 0.06 A cm 2. The
q u a n t i t y of c o p p e r (in the d e t e r m i n a t i o n of the q u a l i t y of the deposit) cor-
r e s p o n d e d to a q u a n t i t y of e l e c t r i c i t y e q u a l to 0.18 A h cm 2
T h e p r o c e d u r e for p r e p a r i n g the m e t a l l o g r a p h i c s a m p l e s was the s a m e
as p r e v i o u s l y described [4]. P h o t o m i c r o g r a p h s w e r e m a d e at a m a g n i f i c a t i o n
of 300×.
In o r d e r to i n v e s t i g a t e the effect of the p u l s a t i n g c u r r e n t on the por-
osity of m e t a l deposits nickel was deposited o n t o a steel s h e e t whose s u r f a c e
h a d b e e n p r e p a r e d for e l e c t r o d e p o s l t l o n in the u s u a l m a n n e r . A nickel plat-
ing s o l u t i o n of t h e following c o m p o s i t i o n was used: N i S O 4 7H20, 240 g 1 ~ ;
N1CI~.6H20, 30 g 1 ~ ; H3BO 3, 30 g 1 -~. The e l e c t r o l y t e was p r e p a r e d from
 101

P o d n a r t chemicals for plating and distilled water. The experiments were

c a r r i e d out at room t e m p e r a t u r e . A c o n t r o l l e d p u l s a t i n g c u r r e n t was pro-
vided from a p o t e n t i o s t a t (used as a g a l v a n o s t a t ) driven by a f u n c t i o n gen-
erator. All the e x p e r i m e n t s were performed with a pulse d u r a t i o n of
1 × 10-2 s because this pulse d u r a t i o n seems to be optimal in pulsating cur-
r e n t deposition [1, 6]. The pause-to-pulse r a t i o was varied from 1:1 to 4:1.
Deposition was carried out at a c u r r e n t density of 10 mA cm -2 m constant-
c u r r e n t conditions and at an a v e r a g e c u r r e n t density of 10 mA c m - : in
pulsating c u r r e n t conditions. The deposit was 7.5 ~m think m all experi-
m e n t s ; e a c h porosity value p r e s e n t e d is an a v e r a g e of six i n d e p e n d e n t
m e a s u r e m e n t s . The a d h e s i o n of the deposit was tested by c r a c k i n g and the
p o r o s i t y by the s t a n d a r d m e t h o d (ferroxyl test) [11].

3. R e s u l t s a n d d i s c u s s i o n

3.1. Electrode surface roughening ~n pulsating current metal depositmn

S q u a r e - w a v e pulsating c u r r e n t metal e l e c t r o d e p o s i t i o n can be described
by the e q u a t i o n s [10]
~C D82C
8t - ~x 2 (1)

C(O, x) = Co (2)
C(t, 5) = Co (3)
(OC)x i(t)
~x ~o - z ~ - f(t)
(4)

where
=~g~ for mT< t <~{m+l/(r+l)}T
i(t) [0 for {m+l/(r+l)}T< t ~ ( m + l ) T (5)
m =0,1,2 ....
For i(t) given by eqn. (5) the solution of the problem is o b t a i n e d in the
form

C(x, t) = Co - z -2in
~ = cos { ( 2 k + ~ l ) x xJ~ [Jo
[fr/(r+l)exp{_2k(t_z)}dz +

+fTT+T/(r+l)exp{__)~k(t__z)}dz+...+ [jm~+T/(r+~)exp{__~.h(t__z)}dz]
where (6)
(2k + 1)2xED
2h - 452 (6a)

The solution of the problem given in this form permits a d i r e c t discussion of

102

the effect of pulsation on the morphology of metal deposits.

For t = {m+l/(r+l)}T, i.e. at the end of pulses, eqn. (6) can be re-
written as
86ZA ~ 1 cos{(2k+l)nx
C{(m+rll)T'x}=C° n2~F-Dk=o(2k+l)2 25 }[ exp(-)'kmT)

-exp -2~ T + r + 1 +...+l-exp~ r+llJ (7)

In steady state conditions

C°n= hmf{(m+r 11T'X}

86tA s 1 t ( 2 k + 1)nx] 1 - e x p [ - ) , k T / ( r + 1)]
Co n2zFD ~o (2k+ 1) 2 cos ~ 25 J 1 - exp(-)~kT) (8)
For T--~ ~:~ and x -- 0 eqn. (8) becomes

55A
hm Co. = Co- (9)
T~~ zFD
Hence for sufficmntly long pulses the system behaves as for d.c. conditions.
For T --* 0 eqn. (8) becomes
5tn
lim Con = Co (10)
r~o (r + 1)zFD
Depending on the pause-to-pulse ratio r, larger current amphtudes can be
used in pulsating current conditions than in d c. electrolysis. For
t = (m + 1)T, i.e. at the end of pauses, eqn (7) can be rewritten m the form

8(~iA ~
Co,= Co n2zF 1
Dh:o(2k+l)2cos { ( 2 k25+ l ) n;~exp
x ) [ [ { -),k
( m+l)T+
r+l} 1
T _

-exp{-)~k(m+l)T}+...+exp{-).k(T-~+i)}-exp(-),kT) ) (11)

In steady state condltmns

Cow = hm
rn~)c
C{(m+ 1)T, x}
85iA ~- 1 ~(2k+l)nx~exp[-)~k{T-T/(r+l)}]-exp(-it~T)
:c0 zFD 0(2k ) 25
(12)
It can be seen that for T--* yz
lim Co~ = Co (13)
and for T--~ 0
 103

6iA
lim Coy = Co (14)
T~o (r + 1 ) z F D

From eqns (10) and (14)

lim Con = lim Coy (15)
T~0 T~O
Hence for sufficiently high frequencies the surface concentration of deposit-
ing ions does not vary with time. It ls known that the average current is
given by
tav = tA/(r+ 1) (16)
Substitution of iA from eqn. (16) in eqns. (10) and (14) gives

{~av
hmT~0Con = T~01imCoy = Cs = Co zFD (17)

Hence the surface concentration both during the current pulse and during
the pause is the same as in the case of d.c. deposition with the same average
current density. Thus, regardless of pause-to-pulse ratio, for a sufficiently
small period of pulsation the maximum deposition rate in pulsating current
deposition is equal to the limiting diffusion current m d.c. deposition. This
is m perfect agreement with the results of Viswanathan and Cheh on the
maximum rate of electrolysis with a ramp current [10].
The rate of growth of a protrusion 6 >> h can be rewritten in the form
112- 15]

d h _ M D ( C o - Cs) h (18)
dt p52

or

h = h 0 e x p t M D ( p ~: - Cs)T~} (19)

for an arbitrarily chosen pulse if integration is carried out between 0 and T,

taking the height at the beginning of the ith pulse as the initial height of
the protrusion and assuming that Cs is constant during T~. If the period is T
the pulse duration is given by
T, = T/(r + 1) (20)
Substitution of T, from eqn. (20) in eqn. (19) gives

h = h 0 exp r+l (21)

Thus the largest increase in protrusion height will be obtained in d.c. de-
position. An increase in r for a given average current and quantity of elec-
tricity leads to deposition of a smoother deposit. This is in accordance with
literature data [1, 6, 7].
It should be noted that eqns. (18), (19) and (21) are valid for all real
104

c u r r e n t densities b e c a u s e even in a c t i v a t i o n - c o n t r o l l e d metal d e p o s l t m n

t h e r e is some g r a d i e n t of c o n c e n t r a t i o n n e a r the electrode surface.
The m e a s u r e d o v e r p o t e n t i a l f r e q u e n c y relations for zav = 0.9tL and for
v a r i o u s pause-to-pulse ratios are presented m Fig. 1. At some pulse dur-
ations the system does n o t e n t e r diffusion c o n t r o l and to a first approxi-
m a t r o n it c a n be assumed t h a t eqns. (10), (14) and (15) are valid. It c a n be
seen t h a t diffusional limitations depend on c u r r e n t amplitude as predicted
by eqn. (8). An increase in the c u r r e n t amplitude leads to a decrease in
critical pulse duration.

7 7 ~ |-- --v! Ji |
040- I I J I
I II I
I f~ I

°151-' ] ___ I I 1
-4 -3 -2 I o
[Ogr,--~-

Fig. 1. M e a s u r e d p o t e n U a l - f r e q u e n c y r e l a u o n s for vamous pause-to-pulse ratios ©, r = 1,

A,r=2, D,r=4, O,r=9 The average c u r r e n t w a s 0 9 z L

In Fig. 2 the o v e r p o t e n t i a l - t i m e r e l a t i o n s d u r i n g pulses of c u r r e n t with

t,v = 0.6i a are presented for v a r i o u s pulse d u r a t i o n s and pause-to-pulse
ratios. It c a n be seen t h a t for a pulse d u r a t i o n of 10 s the system enters
diffusion c o n t r o l ; at a pulse d u r a t i o n of 10-4 s diffusion c o n t r o l is avoided
but t h e r e is a double-layer effect. At a pulse d u r a t i o n of 10 2 s at cA = 1.2*L
and at i A = 6, L deposition is a c t l v a U o n c o n t r o l l e d and the effect of the
double l a y e r is negligible.
The cross sections of deposits o b t a i n e d at ~av = 0.6ZL for vamous de-
position c o n d i t i o n s are presented in Fig. 3. R o u g h deposits are obtained at
pulse d u r a t i o n s of 10 and 10 ~ s and in d.c. deposition. As expected, a
s m o o t h deposit is o b t a i n e d at a pulse d u r a t i o n of 10 2 s. A f u r t h e r increase
in the pause and in the c u r r e n t amplitude at a given pulse d u r a t i o n does not
lead to the f o r m a t i o n of s m o o t h deposits, even t h o u g h beneficial effects are
predmted by eqn. (21). This could be due to the e n h a n c e d o v e r p o t e n t l a l
d u r i n g the c u r r e n t pulses w h i c h is g r e a t e r t h a n the o v e r p o t e n U a l at w h i c h
dendrites s t a r t to grow in this system. H e n c e it seems t h a t dendmtes s t a r t to
 105

(a) (b)

(c) (d)

Fig 2 Time dependences of the overpotentlal during the current pulses (a) pulse dur-
ation 10 s, current amphtude 1 2ZL. r = 1, X = 2 s division 1, y = 0 2 V division 1.
( b ) pulse duration 10 ~ s, current amphtude 1 21L, r = 1, X = 5 x 10 -~ s division-I, y =
0.1 V division 1, (c) pulse duration 10 2 s, current amplitude 1 2tL, r = 1, X = 5 × 10 3 s
dlvtslon 1, y = 0 1 V division 1, (d) pulse duration 10-2 s, current amplitude 6ZL, r = 9,
X = 5 × 1 0 3sdlvlslon 1, Y = 0 2 V d l v l s m n 1

g r o w a t s o m e v a l u e of o v e r p o t e n t i a l n o t w i t h s t a n d i n g t h e a b s e n c e of c o n c e n -
tration polarization.

3.2. The effect of the pulsating current on the porosity of metal deposits
E q u a t i o n (19), w r i t t e n for o n e p u l s e u n d e r t h e a s s u m p t i o n t h a t Cs re-
m a i n s c o n s t a n t t h r o u g h o u t t h e p u l s e a n d for ~ >> h, for s u f f i c i e n t l y s m a l l
times can be used in the form

h = h 0 exp (22)

T o a first a p p r o x i m a t i o n it c a n b e a s s u m e d t h a t Cs r e m a i n s c o n s t a n t d u r i n g
t h e d e p o s i t i o n o f t h i n m e t a l films. It is k n o w n t h a t eqn. (22) r e p r e s e n t s t h e
h e i g h t of a p r o t r u s m n w i t h r e s p e c t t o a flat e l e c t r o d e s u r f a c e [2, 12 - 14].
T h u s i t g i v e s t h e d i f f e r e n c e i n t h i c k n e s s of m e t a l d e p o s i t s o n e l e v a t e d p o i n t s
a n d o n a flat s u r f a c e . H e n c e t h e q u a n t i t y of d e p o s i t e d m e t a l a t t i m e t of
d e p o s i t i o n c a n be g i v e n b y [16]
0 iv

or
106

(a) (b)

(c) (d)

(e) (f)

Fig 3 Copper deposits o b t a i n e d u s i n g a c o n s t a n t or p u l s a t i n g c u r r e n t (~av = 0 6lL)

(a) c o n s t a n t c u r r e n t , (b) pulse d u r a t i o n 10 s, c u r r e n t a m p h t u d e 1 2ZL, r = 1, (c) pulse
d u r a t i o n 10 4 s, c u r r e n t a m p h t u d e 1 2~L, r = 1, (d) pulse d u r a t i o n 10 -z s, c u r r e n t amph-
tude 1.2~a, r = 1, (e) pulse d u r a t i o n 10 2 s, c u r r e n t a m p h t u d e 6lL, r = 9, (f) m l t l a l electrode
surface.
t
Q = Vf + B(r + 1)~ (24)

f o r t ~ ( r + 1)r, w h e r e

B =~-=,
K 0 i h0,

At a smooth electrode
 107

i-N

ho~ =O
t 1

and the deposit is umformly, dlstmbuted. A n increase m surface r o u g h n e s s

leads to a decrease in the t h i c k n e s s of the u n i f o r m l y d i s t r i b u t e d deposit and
to an increase in the porosity of the deposit. The porosity of a thinker film
at points w h e r e h > 0 c a n be neglected c o m p a r e d with the porosity of the
flat p a r t of the surface b e c a u s e of an e x p o n e n t i a l decrease m porosity with
i n c r e a s i n g t h i c k n e s s of the deposit [17] Thus the p o r o s i t y of the sample will
be d e t e r m i n e d by the porosity of the fiat p a r t of the electrode surface
It has r e c e n t l y been s h o w n t h a t for sufficmntly fast n u c l e a U o n [17 - 19]
the p o r o s i t y of metal deposits is given by

= exp(- Qf/Qo) (25)

The porosity of nickel on steel obeys this equation, as s h o w n elsewhere [17].
H e n c e we c a n write
Q Bt 1
log ~ - 4 (26)
2.3Qo 2.3Qo r + l
Thus for a given q u a n t i t y of deposited m e t a l (a given a v e r a g e deposit thmk-
ness) for the same Ume of deposition, the same a v e r a g e c u r r e n t density and
the same m l t l a l surface r o u g h n e s s we can expect a decrease m porosity with
i n c r e a s i n g pause-to-pulse ratio. The s t r a i g h t line m Fig. 4 is good con-
firmation of this view.

F I I I I

125

log5

loc I

075 m

050 . . . .
J I r I __ _ _ l
O2 0~ 06 O8 ~0 1

r÷l

Fig 4 The dependence of the porosity of a mckel deposit (7.5 Dm thick, deposited at an
average current density of 10 A cm 2) on the pause-to-pulse raUo
108

Acknowledgments

The authors are indebted to the Research Fund of the Republic of

Serbia whose material support has made this work possible, and to Mr. S
Z e ~ e v i d a n d t o M r . B. P o p o v a d f o r h e l p f u l d l s c u s s m n d u r i n g t h e p r e p a r a t i o n
of this paper.

Nomenclature

C concentratmn
Co bulk concentratmn
Coe c o n c e n t r a t m n at the end of t h e pause
Con c o n c e n t r a t a o n at the end of t h e pulse
C~ surface c o n c e n t r a t i o n
D diffusion coefficmnt
F Faraday constant
h h e i g h t of a p r o t r u s i o n
ho m m a l h e i g h t of a p r o t r u s i o n
h0~ h e i g h t of a protrusaon at rime t = 0
t c u r r e n t density
za a m p h t u d e of the c u r r e n t density
t,,, a v e r a g e c u r r e n t density
q~ h m m n g c u r r e n t density
k integer
K p r o p o r n o n a h t y factor
m integer
M molecular weight
N integer
Q q u a n t i t y of electricity
Qf q u a n t i t y of e l e c t n c l t y c o r r e s p o n d i n g to d e p o s m o n on a flat surface
Q0 q u a n n t y of electncxty c o r r e s p o n d i n g to d e p o s m o n of one m o n o l a y e r of m e t a l
r pause-to-pulse r a t m
t rime
T period
x coordinate m the horizontal dlrectmn
z n u m b e r of e l e c t r o n s

¢~ t h i c k n e s s of t h e dlffusaon layer
overpotentlal
0 f r a c t i o n of t h e surface w h i c h c o r r e s p o n d s to p r o t r u s i o n s
),4 defined by eqn (6a)
porosity
p density of the m e t a l
z p62/MD(Co - Cs), time c o n s t a n t

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