JOURNAL OF APPLIED ELECTROCHEMISTRY 15 (1985) 107-112

Electrodeposition of cobalt-nickel alloys from

Watts-type baths
S. S : ! ~ B D E L - R E H I M A. M. ABD E L - H A L I M , M. M. O S M A N
Chemistry Department, Faculty of Science, Ain Shams University, Cairo, Egypt
Received 22 March 1984

The electrodeposition of cobalt-nickel alloys was carried out from Watts-type baths of composition
5 - 6 0 g 1-1 COSO4" 7H20, 100-300 g 1-1 NiC12" 6H20 and 25 g 1-1 H3BO3 at a pH of 4.4. The cathodic
polarization during electrodeposition and the alloy composition were greatly influenced by the concen-
trations of the depositable metal ions; whereas, the cathodic efficiency was only slightly affected. Under
the examined conditions, the electrodeposition of the alloys belonged to the anomalous type. X-ray
diffraction studies revealed that the alloys were deposited in the face-centred cubic structure and con-
sisted of a mixture of the two phases a(Co) and t3(Ni). Sound, smooth and bright alloy deposits were
obtained and their properties were improved by increasing the nickel content of the bath.

1. Introduction 2. Experimental details

Electrodeposition of cobalt-nickel alloys is of The deposition baths were freshly prepared in

practical importance because the alloys have high distilled water using highly pure chemicals (BDH);
protective and decorative values, besides a wide their symbols, numbers and compositions are given
range of industrial applications. As an example, in Table 1. The pH of each bath was 4.4.
the alloy is used in the electroforming of moulds The experimental set-up for the electrodepo-
for die-casting and plastics [I] and in electro- sition process consisted of a Perspex cell fitted
typing [2]. The magnetic properties of the with a copper cathode and two plane-parallel
cobalt-nickel alloy are of interest in electronic anodes. The cathode was positioned midway be-
applications such as memory drums, discs, cards tween the anodes and the cell was filled with the
and tapes particularly in the computer industry appropriate solution. The cathode and both anodes
[3, 41. were of equal area. In cobalt and cobalt-nickel
Recently, comprehensive studies have been alloy deposition, the anodes were surrounded by
carried out on the electrodeposition of cobalt- asbestos diaphragms to preclude oxidation of Co 2+
nickel alloys from simple and complex-ion baths. ions and errors in the measured potentials caused
The simple baths include chloride [5], sulphate by the oxygen evolved at the anodes.
[6, 7] and sulphamate [8, 9] solutions. However, The cathodic potentials were measured relative
insufficient research was carried out on the de- to the saturated calomel electrode (SCE) and the
position of the alloy from simple sulphate- efficiency was determined coulometrically. The
chloride baths (Watts-type) baths. composition of each deposited alloy was deter-
Accordingly, we felt it would be interesting to mined by means of an atomic absorption spectro-
investigate the effect of the bath constituents on photometer (Unicam SP 1900). The morphology
the characteristics of the cobalt-nickel alloy depo- of the as-formed deposits was examined with a
sition from Watts-type baths. Such a study is scanning electron microscope (JEOL Model
expected to provide additional quantitative data JSM 35). X-ray diffraction analysis of the cobalt-
concerning the Watts bath composition required nickel alloys was carried out using a Philips
to electrodeposit an alloy of predetermined com- diffractometer (30 kV, 20 mA) with an iron filter
position and, hence, properties. and cobalt radiation.

0021-891X/85 $03.00 + .12 9 1985 Chapman and Hall Ltd. 107

108 S . S . A B D E L - R E H I M , A. M. A B D E L - H A L I M AND M. M. O S M A N

Table 1. Composition o f cobalt, nickel and cobalt-nickel alloy deposition baths

Bath number Concentration o f bath constituents (g1-1)

CoSO 49 7H~O NiCI 296H20 NiSO 4. 6H20 H3BO 3

Co. 1 5 - - 25
Co. 2 15 - - 25
Co. 3 35 - - 25
Co. 4 60 - - 25
Ni. 1 - 100 - 25
Ni. 2 - 150 - 25
Ni. 3 - 200 - 25
Ni. 4 - 300 - 25
(Co-Ni) 1 5 200 - 25
(Co-Ni) 2 20 200 - 25
(Co-Ni) 3 35 200 - 25
(Co-Ni) 4 60 200 - 25
(Co-Ni) 5 35 100 - 25
(Co-Ni) 6 35 150 - 25
(Co-Ni) 7 35 300 - 25
(Co-Ni) 8 35 - 221 25

3. Results and discussion curves o f individual cobalt and nickel d e p o s i t i o n

f r o m baths Co. I - 4 and Ni. 1 - 4 , respectively. The
3.1. Polarization curves curves are characterized by a gradual increase o f
polarization w i t h increasing d e p o s i t i o n current
Cathodic polarization curves are helpful in pro- density. Y a n n a k o p o u l o s and Brenner [10] con-
viding useful i n f o r m a t i o n in the field o f m e t a l cluded that in practical deposition f r o m solutions
and alloy e l e c t r o d e p o s i t i o n . This is due to the fact o f simple ions such a cathode polarization is
that the deposition potentials o f the parent metals mainly o f the activation-type. Increasing the con-
and the alloy affect the current efficiencies and tent o f cobalt (Fig. 1) or nickel (Fig. 2) in the
provide an efficient way o f predicting the possi- deposition baths causes a polarization decreasing-
bility o f c o d e p o s i t i o n , as well as determining the effect over the whole range o f current density
c o m p o s i t i o n s o f the e l e c t r o d e p o s i t e d alloys. used. These effects could be a t t r i b u t e d to the
Figs. 1 and 2 show the cathodic polarization decrease in the c o n c e n t r a t i o n polarization [11 ]. A
c o m p a r i s o n b e t w e e n Figs. 1 and 2 shows that the

4
"1800 -1800

E E

-1400 t.t.I -1400

-iooo .~ -lOOO

~ -600 -600

-zoo -ZOO
0 , i i 0 t I I

0 0.6 12 I B 0 2.0 4.0 6.0

Current density(A dm-2) Current density (A dm"2)

Fig. 1. Polarization curves for cobalt electrodeposition Fig. 2. Polarization curves for nickel electrodeposition
from baths Co. 1-4. from baths Ni. 1-4.
ELECTRODEPOSITION OF C O B A L T - N I C K E L ALLOYS 109

I
-1800 F " 1 1001- = = -- 9

~ -1400 2
I A
Co
- (Co-NO

i.ooo ~= 60

40 11t"

o 20
-20~'~ , , ,
0 I r I ! I --I
0 2.0 4.0 6.0
0 20 40 60
Currentdensity [ Adm-2)
CoS04.7HzO(g 1-11
Fig. 3. Polarization curves for cobalt-nickel alloy electro-
deposition from baths (Co-Ni) 1-4. Fig. 5. Current efficiencies of cobalt from baths Co. 1-4,
cobalt-nickel alloys from baths (Co-Ni) 1-4 and the
electrodeposition of cobalt is attended b y a greater partial efficiencies of cobalt and nickel in the alloys
(broken lines). Plating time was 15 rain at a current
polarization than nickel and this could be corre- density of t A dm -~ for cobalt and 5 A din-2 for the
lated to the low concentrations o f Co 2* in the alloys.
Co. 1--4 baths.
The data of Figs. 1 and 2 indicate that the results are also observed for increasing the concen-
static potentials of cobalt and nickel are about tration o f Ni 2§ in baths ( C o - N i ) 5, 6, 3 and 7 at
200 mV apart and that the individual deposition of a constant concentration o f Co 2* (see Fig. 4).
each metal is accompanied b y a different over- These results could be attributed to the decrease
potential. This means that the electrodeposition o f of the concentration polarization of the metal ion
a c o b a l t - n i c k e l alloy is not an equilibrium process with increasing concentration in the bath [11 ].
and will be governed by the operation of several
factors. For this reason, the cathodic polarization 3.2. Current efficiency
curves o f c o b a l t - n i c k e l alloy deposition from the
Watts ( C o - N 0 1 - 7 baths were recorded and the The influence o f increasing concentrations o f Co 2+
results are given in Figs. 3 and 4. Inspection o f the and Ni 2§ on the percentage cathodic current
curves of these figures shows, in general, that efficiencies ( f % ) o f the individual deposition of
the cathodic polarization increases with increasing cobalt and nickel are illustrated in Figs. 5 and 6,
current density. Moreover, at a constant concen- respectively. The same figures show also the influ-
tration o f Ni 2§ the cathodic polarization shifts to
more noble values by increasing the concentration 100 Ni
(Co-Ni)
o f Co 2+ in baths ( C o - N i ) 1 - 4 (see Fig. 3). Similar
o~ 80
_o Ni
.o -~
6o
-1BOO - o.~-

E ~-. 40
-1400 -
.... -o CO
g, 20
_e;--Ioooi
R O0
~!
400
I ..... { - -
200
I
300
f I-- I

:m -600
NiCI2.6H20 (g 1-I)
t~
o -200
,~
Fig. 6. Current efficiencies of nickel from baths Ni. 1-4,
--I i I
0
2.0 2.0 6,0
cobalt-nickel alloys from baths (Co-Ni) 5,6, 3 and 7
0
Currentdensity ( Adm"2) and the partial efficiencies of cobalt and nickel in the
alloys (broken lines). Plating time was 15 min at a current
Fig. 4. Polarization curves for cobalt-nickel alloy electro- density of 3 Adm -2 for nickel and 5 A dm -2 for the
deposition from baths (Co-Ni) 5, 6, 3 and 7. alloys.
 110 S.S. ABD EL-REHIM, A. M. ABD EL-HALIM AND M. M. OSMAN

ence of the above-mentioned variables on the t00

efficiency of the deposition of cobalt-nickel
alloys and the partial efficiencies of both cobalt 80 ....... --*Ni
and nickel in each alloy (broken lines).
Inspection of Fig. 5 reveals that the f % of 60
cobalt in individual deposition is relatively small,
at a low concentration of Co 2+, and increases 8 40
gradually with increasing concentration of Co 2§ s- 20 ~ ---'<'Co
in baths Co. 1-4. This result could be ascribed to
the fact that at a low concentration of Co 2+ the
0
I
0~ ~ . ~ _ _ L ~
20 40
........ f....
60
electrodeposition of cobalt is attended by a large
CoSO4. 7H20 ( g 1-1)
polarization term (see Fig. 1) and therefore, hydro-
gen is discharged preferentially resulting in a lower
Fig. 7. The percentages of cobalt and nickel in the alloys
f% of cobalt deposition. However, on increasing deposited from baths (Co-Ni) 1 - 4 (solid lines). The
the concentration of Co2+ the observed decrease of broken lines represent the metal percentages in the alloy
the concentration polarization (see Fig. 1) leads to baths. Plating time was 15 rain at a current density of
7 A dm-2.
an improvement of the f % of cobalt. Fig. 5 illus-
trates also that the increasing concentration of
Co2+ in the alloy baths (Co-N0 1-4 has no signi- ence (broken line) which represents the Co % in
ficant effect on the f% of the alloy, whereas the the deposition baths, whereas the composition
partial f % of cobalt in the alloy increases at the curve of nickel in the alloy lies below its compo-
expense of the partial f % of nickel which almost sition reference (broken line). These data show
decreases in the same proportion. that cobalt, the tess noble metal, is preferentially
Similarly, Fig. 6 shows that on increasing the deposited, since its percentage in the deposit is
concentration of Ni 2+ in baths Ni. 1-4 and baths always higher than its metal percentage in the
(Co-Ni) 5, 6, 3 and 7 there is correspondingly a bath; and thus it may in some way hinder nickel
slight increase of the f % of the individual nickel from assuming its normal deposition potential.
and the alloy deposition, respectively. However, Consequently, the data depict that under the
each approaches a maximum efficiency of 100%. present conditions the electrodeposition of
On the other hand, the partial f % of nickel in the cobalt-nickel alloys belongs to the anomalous-
alloy increases markedly and that of cobalt type [12]. However, numerous studies were carried
decreases sharply on increasing the concentration out to explain this phenomenon [13-16].
of Ni2+ in the alloy plating baths. These results
could be explained on the basis that increasing
the content of a metal ion in the bath increases 100
its deposition efficiency through the correspond- A
....... -,, Ni
ing decrease of the concentration polarization at 801 o-"
_....___o Ni
the cathode [11 ].
60
3.3. Compos#ion of the alloy

The effects of increasing concentrations of Co2+

in baths (Co-Ni) 1-4 and Ni 2+ in baths (Co-Ni)
5, 6, 3 and 7 on the composition of the electro-
deposited cobalt-nickel alloys were determined
and the results are presented in Figs. 7 and 8,
20

0 I
0
I

100
---.o..---.o-. . . . . . . .
I

200
,I ....... I

NiCt2.6H20 ( g t -'1)
-o Co
I

300

respectively. Fig. 8. The percentages of cobalt and nickel in the alloys

The outstanding feature of both figures is that deposited from baths (Co-Ni) 5,6, 3 and 7 (solid lines).
The broken lines represent the metal percentages in the
the composition curve of the less noble metal in alloy baths. Plating time was 15 rain at a current density
the alloy, cobalt, lies above its composition refer- of 7 A d m - L
ELECTRODEPOSITION OF COBALT-NICKEL ALLOYS 111

Fig. 9. Electron micrographs of (a)

cobalt from bath Co. 3, (b) nickel from
bath Ni. 3, (e) and (d) cobalt-nickel
alloys from baths (Co-Ni) 3 and 8,
respectively (magnificationsat 3880 X).

Fig. 7 shows that as the Co% in the bath Co. 3 consists of elongated dihedral grains leaving
increases slightly, there is a considerable increase no holes between them and oriented at random
of the Co % in the alloy. This is a reasonable result (Fig. 9a). A similar structure was observed for
and could be correlated to the fact that the cobalt deposits from a chloride bath [17]. The
cathode diffusion layer becomes relatively more nickel deposit from the chloride bath Ni. 3 shows
depleted with respect to the preferentially deposit- a finer-grained texture and an increased nucleation
able Co 2+ ions. Therefore, increasing the Co% in density (Fig. 9b). Fig. 9c shows that the cobalt-
the bath tends to oppose the depletion o f the Co 2+ nickel alloy from Watts bath (Co-Ni) 3 consists
ion in the cathode layer and accordingly increases of nodular grains having an intermediate size
the Co% in the electrodeposited alloy. On the between those of the parent cobalt and nickel
other hand, Fig. 8 establishes that the Ni% in the deposits from the corresponding individual baths.
alloy increases in a parallel manner to increasing Inspection of Figs. 9a, b depicts that although the
the Ni% in the bath. This indicates that the test overpotential of cobalt deposition (see Fig. 1) is
system seems to be in equilibrium with respect greater than that of nickel (see Fig. 2) the grain
to Ni 2+ ions which are present in a high concen- size of the cobalt deposit is larger. This could be
tration. referred partly to the specific properties of the
metals and partly to the difference in adsorb-
3.4. Surface morphology abilities of the SO~- and C1- anions on the surface
of the copper cathode [18]. This suggestion was
The structures of cobalt, nickel and cobalt-nickel confirmed by replacing NiC12 in bath (Co-Ni) 3
alloys deposited from the present baths at a by NiSO4, containing an equal Ni content, in
current density of 1 A dm -2 and duration of bath (Co-Ni) 8 where a coarser grained alloy
10 min, were examined by a scanning electron deposit was obtained (Fig. 9d). It is worth noting
microscope. Some of the electron micrographs that chemical analysis revealed that cobalt-nickel
taken are shown in Fig. 9 at a magnification of alloys from baths ( C o - N 0 3 and 8 have almost the
3880 • same composition and contain 59.2% and 60%
The cobalt deposit from the sulphate bath cobalt, respectively. In addition, our results agree
1 12 S . S . ABD EL-REHIM, A. M. ABD EL-HALIM AND M. M. OSMAN

Table 2. Characteristics o f X-ray diffraction patterns of cobalt-nickel alloys. Sample I deposited from bath (Co-Ni) 1
and contains 93. 7% nickel. Sample H deposited from bath (Co-NO 4 and contains 45.1% nickel

Sample d (~) I/I o Phase hk l a {~1) Average value o f a (A)

(fce)
a(Co) #(Ni)

I 2.042 100.00 a(Co) 111 3.536 3.529 3.625

1.812 53.71 /3(Ni) 20 0 3.624
1.764 22.86 cffCo) 200 3.528
1.282 42.85 /~(Ni) 220 3.626
1.246 21.14 ~(Co) 220 3.524
II 2.050 100.00 ~(Co) 111 3.550 3.530 3.623
1.812 70.00 /3(Ni) 20 0 3.624
1.751 28.42 a(Co) 200 3.502
1.282 34.21 /3(Ni) 220 3.626
1.251 15.79 ~(Co) 220 3.538
1.091 38.95 /3(Ni) 311 3.618

with those o f Young and Struyk [15] who References

reported that the c o b a l t - n i c k e l deposit from an
all-chloride bath was finer-grained than the one [ 1] J. Spiro and F. Wohlgemuth, US Patent 2 519 858
from a corresponding all-sulphate bath. (1950).
[2] R.F. Ledford, Plating 36 (1949) 560.
C o b a l t - n i c k e l alloys deposited from the [3] E. Toledo and R. Mo, ibid. 57 (1970) 43.
present Watts baths have a white colour and are [4] F.R. Morral, ibid. 59 (1972) 131.
sound, smooth and bright. The smoothness and [5] H. Imanaga, K. Yoshino and H. Hattori, Denki
Kagaku 43 (1975) 318.
brightness o f the deposits increase with an increas- [6] A.I. Zhikharev, I. G. Zhikhareva and M. S.
ing nickel content in the bath. Zakharov, Elektrokhim. 16 (1980) 187.
[7] D.R. Srivastava and K. S. Nigan, Surf. Technol.
10 (1980) 343.
3.5. X-ray diffractometry [8] K.C. Belt, J. A. Crossley and A. Watson, Inst.
Metal Finish 48 (1970) 133.
X-ray diffraction analysis was carried out on the [9] R.J. Walter, Amer. glectroplat. Soc. 66 (1979)
3.
c o b a l t - n i c k e l alloys prepared from the Watts [ 10] T. Yannakopoulos and A. Brenner, J. Electroehem.
bath under test, at a current density o f 5.3 A dm -2 Soc. 103 (1958) 521.
and duration o f 10 rain, and some examples of the [11] A.M. Abel EI-Halim, J. Appl. Electrochem. 14
(1984) 587.
results are given in Table 2. [12] A. Brenner, 'Electrodeposition of Alloys', Vol. II
The data indicate that, irrespective of the bath (Academic Press, New York, 1963) p. 297.
or alloy composition, the c o b a l t - n i c k e l alloys are [13] S. Glasstone and J. C. Speakman, Trans. Faraday
Soc. 28 (1932) 733.
deposited in the face-centred cubic structure and [14] Idem, ibid. 29 (1933) 426.
consist of a mixture of a(Co) and/3(Ni) phases. [15] C.B.F. Young and C. Struyk, Trans. Electrochem.
Moreover, it is observed that the lattice parameter Soc. 89 (1946) 383.
[ 16] Y.M. Marikar and K. I. Vasu, Eleetrodepos. Surf.
a of nickel increases from 3.52 h as a result o f the Treat. 2 (1974) 281.
formation o f the alloy in the t3(Ni)-phase. On the [17] J. Scoyer and R. Winand, Surf. Technol. 5 (1977)
other hand, the lattice parameter of cobalt 169.
[18] A.M. Abd E1-Halim, M. I. Sobahi and A. O.
(3.54 A) was not affected b y the formation o f the Baghlaf, ibid. 18 (1983) 225.
a(Co)-phase alloy which almost has the same [19] A. Brenner, 'Electrodeposition of Alloys', Vol. I
lattice parameter (3.53 A). These results are in (Academic Press, New York, 1963) p. 191.
[20] R. Weil and H. J. Read, Metal Finish 53 (1955) 60.
good agreement with those reported earlier in [21] R.C. Newman, Proe. Phys. Soe. B 69 (1956) 432.
literature [ 1 9 - 2 1 ].