Surface Technology, 4 ( 1 9 7 6 ) 227 - 235 227

© Elsevier Sequoia S.A., L a u s a n n e - - Printed in the N e t h e r l a n d s

INFLUENCE OF POLYACRYLAMIDES ON THE QUALITY OF COPPER

DEPOSITS FROM ACIDIC COPPER SULFATE SOLUTIONS

J. V E R E E C K E N and R. WINAND
Department of Metallurgy and Electrochemistry, Free University of Brussels (Belgium)
(Received J a n u a r y 8, 1976)

Summary

Polyacrylamides have been tested as inhibitors for copper electrowinning

from an acidic copper sulfate bath on a copper cathode. The quality of the
deposit, the structure, the galvanic potential, the current efficiency, the
orientation of the texture and the a m o u n t of occluded inhibitor are determined
as functions of the anionic or cationic character and of the viscosity of the
polyacrylamide solutions. All the results are compared with those obtained
with the c o m m o n l y used guar gum.

1. Introduction

It is well known that the presence of organic molecules (inhibitors)

in an electrolyte can change the structure and properties of the deposits
obtained by the electrochemical reduction of metal cations. Although quite
a lot of research has been devoted to the behaviour of these inhibitors in the
electrolytic bath and their influence on the different steps of the electro-
crystallization processes, no systematic correlation has been found so far
between the nature of the organic molecule and its effect on the characteristics
of the deposit.
Important contributions to the knowledge of the mechanism of
electrocrystallization of copper have been summarized recently [1, 2].
Numerous publications give details about the influence of some specific
groups of organic molecules on the appearance and properties of deposits,
contributing to the understanding of the mechanism [ 3 - 22].
The purpose of this paper is certainly not to give an extensive review of
all these works, but only to summarize the data gathered through our own
experiments concerning the influence of polyacrylamides in an acidic copper
sulfate bath.
Polyacrylamides are made of very long chains (monomolecular weight
between 500,000 and 12,000,000). Their general formula may be written as
follows:
228

H H H H
--C C C C--
i i L i
H C=O H C=O
i L
NH2 NH2

These non-ionic polyacrylamides are weakly hydrolysed in aqueous

solution to polyacrylic acids which, in part, have very low dissociation
constants. The percentage of anionic polyacrylamides is thus very low.
It is also possible to prepare cationic polyacrylamides by copolymerization,
for instance dimethyl-aminoethyl methacrylate (DMAEMA)/acrylamide
copolymers with different ratios of DMAEMA in the range 5 - 20%:

O=C NH2
H CH3 H H
l I | I
--C C C---C C--
I I I J 1
H I H H H
O=C O (CH)2--N(CH3)2

Polyacrylamides belong to the second class of inhibitors. They interact

with water molecules in the Helmhotz double layer and form a viscous film
near to the electrode. We must, moreover, mention that they are used as
flocculants in water treatment plants.
Polyacrylamides can be characterized by their molecular weight, by the
viscosity of an aqueous solution containing a certain concentration in
polyacrylamide and by the percentage of their anionic or cationic conversion.
In a study concerning the influence of organic molecules with amino
groups on the properties of copper deposits from acidic copper sulfate
baths, Hansel and Resch [23] found that very smooth and hard deposits
could be obtained in the presence of polyacrylamides. Couvreur [24]
investigated the role of polyacrylamide additions to a copper sulfate solution
(Cu 2÷ 40 g/l, H2SO4 200 g/l) at 50 °C on the structure of copper deposits.
He f o u n d that when the concentration in polyacrylamides increases the crystals
are thinner, the deposit is harder, and the orientation of the texture of the
deposit, which is (110) in a pure solution, becomes (100). He observed no
dendrites, even with current densities as high as 4 A/dm 2.
Taking into account the recent developments in electrocrystailization
and our own experience in this field [25 - 28], a certain number of cationic,
anionic and non-ionic polyacrylamides were tested in connection with their
possible use in industrial electrowinning plants.
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viscosity
cps.
.30 R
FG
St

'10 R
FG
R
FG
St St

5
R R 5t R
FG FG FG

R
FG
i
"/o caHonic 20 ~5 1~0 5 "/o anionic

Fig. 1. Superficial appearances o f the deposits as f u n c t i o n s o f the percentage o f anionic

or cationic c o n v e r s i o n o f the p o l y a c r y l a m i d e and o f the viscosity o f its 0.5% a q u e o u s
s o l u t i o n at pH 3. ( R . F . G . = rough with fine grains; S t = striated.)

2. Experimental conditions

"Industrial" copper sulfate solution (Cu 2÷ 50 g/l, Mn 2. 10 g/l, Mg+

4 g/l, Co 2÷ 1.5 g/l, PO4~-10 g/l, H2SO4 50 g/l) was electrolyzed for 48 h at
50 °C between a passivated lead anode and a copper cathode/area 1 dm2).
The volume of the electrolytic cell was 500 cm 3 and the flow of the solution
100 cm3/min. The current density was held constant at 2 A/dm 2. The con-
centration in Cu 2. ions and the pH of the solution were maintained constant
by addition of concentrated copper sulfate solution and sodium hydroxide.
To the electrolyte was added 1 mg/1 of different polyacrylamide solutions
characterized by their viscosity {viscosity of a 0.5% aqueous solution at pH 3)
and their percentage in cationic or anionic conversion*. We assumed a prob-
able consumption of 1 mg/1 of the inhibitor solution in 12 h in each case and
on this basis held the concentration constant during the electrolysis. How-
ever, it should be pointed out that this probable consumption is based on
experimental measurements made at laboratory scale by Couvreur [24] and
that data axe lacking for the equivalent industrial scale.
During these electrolysis, the cathodic galvanic potential and the cell
voltage were recorded and the current efficiency determined. The superficial
appearance of the deposits was observed with a scanning electron microscope

*These p r o d u c t s are e x p e r i m e n t a l l y p r o d u c e d by D o w Chemical Co.

230

Fig. 2. Rough deposit with fine grains (1 mg/l anionic polyacrylamide, 4 cP, scanning
electron microscope, 225 x ).
Fig. 3. Nearly smooth deposit with very fine grains (1 mg/1 20% cationic polyacrylamide,
4 cP, scanning electron microscope, 225 X ).

( J E O L 5 0 X A ) . T h e s t r u c t u r e o f t h e d e p o s i t s was d e t e r m i n e d b y o p t i c a l
m e t a l l o g r a p h y on cross sections, and t h e c r y s t a l l o g r a p h i c o r i e n t a t i o n o f t h e
d e p o s i t t e x t u r e b y X-ray d i f f r a c t i o n . T h e p o l a r i z a t i o n curves o f t h e r e d u c t i o n
o f Cu 2 ÷ ions in the p r e s e n c e of t h e d i f f e r e n t i n h i b i t o r s w e r e also r e c o r d e d .
As a basis o f c o m p a r i s o n f o r all m e a s u r e m e n t s we t o o k t h e results ob-
t a i n e d with guar gum, w h i c h is a c t u a l l y used in several c o p p e r e l e c t r o w i n n i n g
plants.

3. E x p e r i m e n t a l results

3.1. Quality o f the deposit

Figure 1 s u m m a r i z e s t h e d i f f e r e n t a p p e a r a n c e o f t h e d e p o s i t s as f u n c t i o n s
of t h e p e r c e n t a g e o f anionic or cationic c o n v e r s i o n o f t h e p o l y a c r y l a m i d e
and t h e viscosity o f t h e i r a q u e o u s solutions. Mainly t w o t y p e s o f d e p o s i t s
were observed: s t r i a t e d ones a n d r o u g h ones w i t h fine grains (Fig. 2). This
r o u g h n e s s d i s a p p e a r s progressively w i t h increase in t h e p e r c e n t a g e o f c a t i o n i c
c h a r a c t e r o f t h e i n h i b i t o r at viscosities ranging f r o m 4 t o 8 cP (Fig. 3).
H o w e v e r , we did n o t s u c c e e d in o b t a i n i n g a d e p o s i t as s m o o t h as w i t h guar
g u m (Fig. 4).
 231

Fig. 4. Smooth deposit (1 mg/l guar gum, scanning electron microscope, 225 X).

3.2. Structure o f the deposit

Using Fischer's classification [ 3], Fig. 5 gives the deposit structures
for the different polyacrylamides as a function of their viscosity. For nearly
all the inhibitors tested, the crystals were orientated in the electric field,
but changes were observed in the diameter of these crystals. With cationic
polyacrylamides (10 - 20%) with a viscosity of about 4 cP, it was possible
to obtain nearly the same very thin and elongated crystals as with guar gum
(Figs. 6, 7). It must be noted, however, that with polyacrylamides with a
very high cationic constituent content and a viscosity of 8 cP, the deposit
is nodular (Fig. 8).

3. 3. Current efficiency
Addition of polyacrylamides does not significantly change the current
efficiency of the electrolysis.

3.4. Incorporation o f the inhibitors in the deposit

Polyacrylamides do n o t seem to be incorporated in the deposit, since
the carbon concentration does not exceed 0.05 p.p.m, in the deposit after
48 h electrolysis, and is normally in the range 0.02 - 0.05 p.p.m.
232

viscosity
CF~.

30 BRT

0 BRT

FT FT

-5

FT FT FT BR FT
BRT

FT FT
BR
I
'/o c~lionic J~
.~ 15 10 5 0 5 O/o anionic

Fig. 5. S t r u c t u r e o f the d e p o s i t s as f u n c t i o n s o f the p e r c e n t a g e o f anionic or c a t i o n i c

c o n v e r s i o n o f t h e p o l y a c r y l a m i d e and o f the viscosity o f its 0.5% a q u e o u s s o l u t i o n at
p H 3. ( F T = field o r i e n t e d t y p e ; BR = basis o r i e n t e d r e p r o d u c t i o n t y p e ; T = t w i n n e d
t r a n s i t i o n t y p e ; BRT = basis r e p r o d u c t i o n t w i n n e d t y p e . )

i~
' 7a "'~ ';i z,:

Fig. 6. S t r u c t u r e o f the d e p o s i t (1 mg/1 20% cationic p o l y a c r y l a m i d e , 4 cP, o p t i c a l

m i c r o g r a p h y , 73 X ).

3.5. Orientation o f the texture o f the deposit

With t h e c o n c e n t r a t i o n w e used (1 mg/1), w e o b s e r v e d n o m o d i f i c a t i o n
o f t h e o r i e n t a t i o n o f t h e t e x t u r e o f t h e d e p o s i t . In all t h e e x p e r i m e n t s , w e
f o u n d t h e well k n o w n ( 1 1 0 ) t e x t u r e , as in t h e case o f a pure acidic c o p p e r
sulfate s o l u t i o n .
 233

Fig. 7. Structure of the deposit (1 mg/1 guar gum, optical micrography, 73 x ).

Fig. 8. Structure of the deposit (1 rng/l 90% cationic polyacrylamide, 8 cP, optical
micrography, 73 X ).

3. 6. P o l a r i z a t i o n c u r v e s
The p o l a r i z a t i o n curve was r e c o r d e d f o r the r e d u c t i o n o f Cu 2÷ ions o n
a c o p p e r c a t h o d e with 1 mg/1 o f the d i f f e r e n t inhibitors. This low c o n c e n t r a -
t i o n does n o t significantly change the o v e r p o t e n t i a l o f t h e c a t h o d i c r e d u c t i o n .
This c o n f i r m s the results o b t a i n e d d u r i n g t h e electrolysis: t h e c a t h o d i c
galvanic p o t e n t i a l in all t h e e x p e r i m e n t s was equal t o +200 m V / N H E (the
cell voltage was a b o u t 2V).

4. Conclusions

A d d i t i o n o f p o l y a c r y l a m i d e s t o p u r e acidic c o p p e r sulfate b a t h s improves

the q u a l i t y o f t h e deposit. In particular, with c a t i o n i c p o l y a c r y l a m i d e s
(10 - 20% cationic c o n v e r s i o n ) t h e deposits are s m o o t h e r and c o n t a i n t h i n
234

e l o n g a t e d c r y s t a l s o r i e n t e d i n t h e e l e c t r i c field. T h e v i s c o s i t y o f t h e 0 . 5 %
p o l y a c r y l a m i d e a q u e o u s s o l u t i o n a t p H 3 also s e e m s t o p l a y a n i m p o r t a n t
r b l e : we f o u n d a n o p t i m u m a t a b o u t 4 cP.
On the other hand, the presence of polyacrylamides does not change the
cathodic galvanic potential, the current efficiency and the orientation of
t h e t e x t u r e o f t h e d e p o s i t . T h e s e i n h i b i t o r s are n o t i n c o r p o r a t e d i n t h e
d e p o s i t . H o w e v e r , it s h o u l d b e n o t e d t h a t f o r all o u r e x p e r i m e n t s t h e q u a l i t y
o f t h e d e p o s i t s o b t a i n e d w i t h p o l y a c r y l a m i d e s was n e v e r as g o o d as w i t h
guar gum.

Acknowledgement

T h e a u t h o r s e x p r e s s t h e i r t h a n k s t o t h e D o w C h e m i c a l Co. f o r t h e i r
co-operation and financial support.

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