Electrochimica Acta, Vol. 43, Nos 12±13, pp.

1721±1728, 1998
# 1998 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: S0013-4686(97)00322-8 0013±4686/98 $19.00 + 0.00

Kinetics of the autocatalytic deposition of Ni-P

alloys in ammoniacal solutions
M. Ebn Touhami,a,b E. Chassainga* and M. Cherkaouib

a
Centre d'Etudes de Chimie MeÂtallurgique-CNRS, 15 rue G. Urbain, 94407 Vitry-sur-Seine, France
b
Faculty of Sciences Ibn Tofail, Kenitra, Morocco

(Received 28 May 1997; in revised form 23 July 1997)

AbstractÐAiming at a better knowledge of the kinetics of the Ni-P electroless processes we have carried
out a steady-state polarization investigation and electrochemical impedance measurements, not only at the
deposition potential but also in the cathodic and anodic ranges. We studied the e€ect of solution pH,
nickel sulfate and hypophosphite concentrations. A reaction path is developed, which accounts for the
main features observed. It also explains the interqactions between the anodic and cathodic processes.
# 1998 Elsevier Science Ltd. All rights reserved.

Key words: autocatalytic, electroless, Ni-P coatings, electrochemical impedance, kinetics.

INTRODUCTION and cathodic processes. The reaction paths devel-

The deposition kinetics of electroless Ni-P layers
has been widely investigated due to the interesting
properties of Ni-P alloys, such as corrosion and
wear resistances [1]. The Ni-P layers are also used
as non-magnetic undercoats in the electronic indus-
try. Despite the large number of investigations, the
deposition kinetics is so far not well established.
Several reaction paths have been proposed, which
were developed from plating rate measurements,
alloy composition dependency as a function of ex-
perimental parameters, dc polarization studies,
chronoamperometric and chronopotentiometric in-
vestigations and electrochemical impedance
spectroscopy [2±7].
It is well-known that the autocatalytic deposition
is the result of (i) anodic processes (oxidation of
hypophosphite), (ii) cathodic processes (reduction
of the Ni2+ species and hypophosphite, evolution
of hydrogen and possibly its incorporation into the
growing NiP alloy). Kinetic investigations based on
mixed potential theory have been applied [8].
However mixed potential theory does not account
for the interactions observed between the anodic
*Author to whom correspondence should be addressed.
E-mail: chassaing@glvt-cnrs.fr
1721
oped so far do not account for all the experimental
results [9]. According to some authors, the process
is essentially electrochemical [5], whereas others
consider the participation of direct transfer between
nickel ions and hypophosphite [6].
In the present work to gain information on the
in¯uence of the anodic and cathodic partial reac-
tions, we have investigated the steady-state polariz-
ation not only at the deposition potential but also
in the anodic and cathodic ranges. In addition elec-
trochemical impedance was carried out which may
provide information on the elementary steps of the
reactions [10]. The in¯uence of the various exper-
imental parameters (hypophosphite and nickel sul-
fate concentrations, pH) was studied.
In a previous voltammetric investigation we
showed that during the oxidation process three
peaks were observed corresponding to the oxidation
of hypophosphite and the dissolution of two nickel
phases, a nickel-rich and a phosphorus-rich one [11].
Interactions between the cathodic process and the
oxidation of hypophosphite were shown to occur:
the presence of Ni2+ species increases the hypopho-
sphite oxidation rate, the presence of hypophosphite
enhances the nickel discharge [11].
1722 M. Ebn Touhami et al.

Table 1.
Electrolyte compositions, Mdmÿ3. All solutions also contained 0.2 M sodium citrate and 1 M ammonium acetate. The
pH was adjusted by the addition of ammonia
Electrolyte NiSO4, 7H2O NaH2PO2, H2O pH

1a 0.05 0.1 9
1b 0.05 0.1 10
2a 0.05 0.2 9
2b 0.05 0.2 10
3a 0.05 0.5 9
3b 0.05 0.5 9.5
3c 0.05 0.5 10
3d 0.05 0.5 10.5
4 0.1 0.5 9
5 0.16 0.5 9

EXPERIMENTAL

A classical three-electrode cell (200 ml) was used.

The auxiliary electrode was a platinum coil. The
reference electrode was a saturated calomel elec-
trode (sce) against which all potentials were referred
and corrected for ohmic drop. The working electro-
des were mild steel or copper discs rotating up to
1000 rev minÿ1, on which Ni-P layers had been pre-
viously plated.
The electrolytes were made up of analytical grade
chemicals. The electrolytes were held at 78 2 28C
and deaerated by nitrogen bubbling. The solutions
contained sodium hypophosphite as reducing agent
and nickel sulfate. Sodium citrate (0.2 M) and am-
monium acetate (1 M) were added as complexing
agents (Table 1). Electrolyte 3a, which acts as a
reference in the work, was deduced from the sol-
ution developed at the laboratory for the autocata-
lytic deposition of Ni±Cu±P alloys [12]. The pH
was varied between 9 and 10.5 by the addition of
ammonia. The e€ects of nickel sulfate concentration
(0.05 to 0.16 M) and sodium hypophosphite con-
centration (0.1 to 0.5 M) have been investigated.
The steady-state polarization curves have been
recorded galvanostatically in the cathodic range and
potentiostatically in the anodic range. They were
corrected for ohmic drop. The composition of the
Ni-P layers, plated at the deposition potential or in
the cathodic range, was determined by X-ray energy
dispersion in the scanning electron microscope. The
Faradaic eciency was calculated, in the cathodic
range, taking account of the deposit composition.
In the cathodic range, phosphorus incorporation is
supposed to occur according to the following
reaction [1]:

H2 POÿ ‡ ÿ
2 ‡ 2H ‡ e ! P ‡ 2H2 O
i.e. one electron per deposited phosphorus atom is
needed.
The partial nickel, phosphorus and hydrogen dis-
charge curves were then calculated taking account
of the deposit composition and Faradaic eciency.
Fig. 1. Impedance plots recorded at the deposition poten-
tial, Electrode rotation speed: 500 rev minÿ1. AÐ
Electrolyte 3a (0.05 M NiSO4, pH = 9) (tP=12.5 wt%)
BÐElectrolyte 3d (0.05 M NiSO4, pH = 10.5) (tP =5.4
wt%) CÐElectrolyte 5 (0.16 M NiSO4), pH = 9) (tP=7.4
wt%).
 Kinetics of the autocatalytic deposition of Ni-P alloys in ammoniacal solutions
Table 2.
Charge transfer resistance as a function of hypophosphite concentration and pH
Electrolyte 1a 2a
pH 9 9
NaH2PO2, H2O 0.1 0.2
Mdmÿ3
Rt, Ocm2 23 21 1021
The electrochemical impedance was recorded
between 60 kHz and 10 mHz using a 1250
Solartron and a 1186 Schlumberger electrochemical
interface, monitored by a MacIntosh microcom-
puter. The perturbation signal was 15 mV. The line-
arity of the potential and current responses was
checked using a Enertec-Schlumberger 5023 oscillo-
scope.
RESULTS
1. Investigation at the deposition potential, Ed (open-
circuit potential)
The deposition potential is characterized by a net
current equal to zero, resulting from two simul-
taneous anodic (oxidation of hypophosphite) and
cathodic processes (reduction of nickel species and
hypophosphite, and evolution of hydrogen) [1].
Figure 1 shows typical impedance diagrams
recorded at the plating potential, for various pH
values and nickel sulfate concentrations. As pre-
viously observed [11], it was checked that the phos-
phorus content decreases when the pH or the nickel
sulfate concentration is increased. The impedance
plots exhibit several characteristic features. In the
high frequency domain a capacitive loop appears
which is related to the relaxation of the double
layer capacitance whose value ranges between 75
and 100 mFcmÿ2, in parallel with the charge transfer
resistance, Rt.
Fig. 2. Steady-state cathodic polarization curves corrected
for ohmic drop. Electrode rotation speed: 500 rev minÿ1.
1ÐElectrolyte 3a (0.05 M NiSO4, 0.5 MNaH2PO2,
pH = 9) 2ÐElectrolyte 3d (0.05 M NiSO4, 0.5
MNaH2PO2, pH = 10.5) 3ÐElectrolyte 4 (0.1 M NiSO4,
0.5 MNaH2PO2, pH = 9) 4ÐElectrolyte 1a (0.05 M
NiSO4, 0.1 MNaH2PO2, pH = 9).
1723
3a 1b 2b 3b
9 10 10 10
0.3 0.1 0.2 0.3
72 1 9.521 721 8.5 21
A small inductive loop is observed with a charac-
teristic frequency around a few Hz. Its size
increases, for low hypophosphite or large nickel sul-
fate concentrations and high pH values (Fig. 1(B),
(C)).
At lower frequencies, a capacitive loop appears
whose size increases with pH. It increases with
hypophosphite concentration and with nickel sulfate
concentration. This feature is oberved whatever the
anion nature, ie chloride or sulfate.
In a previous work we showed that the charge
transfer resistance does not depend on the rotation
speed between 500 and 1000 rev minÿ1 [11]. Hence
in the following all the impedance diagrams have
been recorded at 500 rev minÿ1. Rt, which is inver-
sely proportional to the plating rate, decreases
when the nickel sulfate concentration increases [11].
When the hypophosphite concentration is increased,
Rt decreases markedly for a pH value of 9, for
which the plating rate is maximum. The variatons
are much less pronounced at pH of 10 (Table 2).
This behaviour shows that interactions between H+
species and hypophosphite oxidation exist leading
to an inhibition of the plating process.
2. Investigation in the cathodic range
2.1 Steady-state polarization behaviour. Figure 2
shows the steady-state polarization curves, corrected
for ohmic drop, for four electrolyte compositions
(see Table 1). The e€ect of pH (9 and 10.5), of
hypophosphite and nickel sulfate concentrations
have been investigated. Curve 1 corresponds to elec-
trolyte 3, reference electrolyte, at pH = 9. When
the pH is increased to 10.5 the polarization curve
(curve 2) is shifted towards more negative values.
The increase in nickel sulfate concentration (curve
3) depolarizes the discharge whereas a decrease in
hypophosphite inhibits the global process (curve 4).
More precise conclusions can be obtained from
the partial polarization curves shown in Figs 3±5.
When the pH is increased the hydrogen discharge is
markedly shifted towards more negative values
(Fig. 3, curves 1 and 2), the nickel discharge is
enhanced, especially at large polarizations (Fig. 4,
curves 1 and 2), no e€ect on the phosphorus incor-
poration is observed (Fig. 5, curves 1 and 2). At
low polarization, the nickel discharge is the main
reaction; the activation coecient with potential for
this reaction is of the same order as for the phos-
phorus incorporation (6.52 0.5 Vÿ1). For hydrogen
evolution the coecient is much higher (25 2 2
1724 M. Ebn Touhami et al.

Fig. 3. Partial polarization curve for hydrogen discharge.

Electrode rotation speed: 500 rev minÿ1. 1ÐElectrolyte 3a
(0.05 M NiSO4, 0.5 MNaH2PO2, pH = 9) 2ÐElectrolyte
3d (0.05 M NiSO4, 0.5 MNaH2PO2, pH = 10.5) 3Ð
Electrolyte 4 (0.1 M NiSO4, 0.5 MNaH2PO2, pH = 9) 4Ð
Electrolyte 1a (0.05 M NiSO4, 0.1 MNaH2PO2, pH = 9).

Fig. 4. Partial polarization curve for nickel discharge.

Electrode rotation speed: 500 rev minÿ1. 1ÐElectrolyte 3a
(0.05 M NiSO4, 0.5 MNaH2PO2, pH = 9) 2ÐElectrolyte
3d (0.05 M NiSO4, 0.5 MNaH2PO2, pH = 10.5) 3Ð
Electrolyte 4 (0.1 M NiSO4, 0.5 MNaH2PO2, pH = 9) 4Ð
Electrolyte 1a (0.05 M NiSO4, 0.1 MNaH2PO2, pH = 9).

Fig. 6. Impedance plots recorded at i = 10 mA cmÿ2.

Fig. 5. Partial polarization curve for phosphorus incorpor-
ation. Electrode rotation speed: 500 rev minÿ1. 1Ð
Electrolyte 3a (0.05 M NiSO4, 0.5 MNaH2PO2, pH = 9)
2ÐElectrolyte 3d (0.05 M NiSO4, 0.5 MNaH2PO2,
pH = 10.5) 3ÐElectrolyte 4 (0.1 M NiSO4, 0.5
MNaH2PO2, pH = 9) 4ÐElectrolyte 1a (0.05 M NiSO4,
0.1 MNaH2PO2, pH = 9).
Electrode rotation speed: 500 rev minÿ1. A: Electrolyte 3a
(0.05 M NiSO4, 0.5 MNaH2PO2, pH = 9). E = ÿ 980
mV/sce, tP=12 wt% B: Electrolyte 3d (0.05 M NiSO4, 0.5
MNaH2PO2, pH = 10.5). E = ÿ 1025 mV/sce, tP=8.5
wt% C: Electrolyte 1a (0.05 M NiSO4, 0.1 MNaH2PO2,
pH = 9). E = 1010 mV/sce, tP=10.5 wt% D: Electrolyte
4 (0.1 M NiSO4, 0.5 MNaH2PO2, pH = 9). E = ÿ 920
mV/sce, tP=9.5 wt%.
 Kinetics of the autocatalytic deposition of Ni-P alloys in ammoniacal solutions
Fig. 7. Rt.i product of the charge transfer resistance with
the current density. Electrode rotation speed: 500 rev min-
ÿ1. 1ÐElectrolyte 3a (0.05 M NiSO4, 0.5 MNaH2PO2),
pH = 9 2ÐElectrolyte 3d (0.05 M NiSO4, 0.5
MNaH2PO2), pH = 10.5 3ÐElectrolyte 4 (0.1 M NiSO4,
0.5 MNaH2PO2), pH = 9 4ÐElectrolyte 1a (0.05 M
NiSO4, 0.1 MNaH2PO2), pH = 9.
Vÿ1). Hence for large polarizations, the hydrogen
evolution becomes preponderant.
When the nickel sulfate concentration is increased
from 0.05 M to 0.1 M, all partial currents, even the
phosphorus incorporation reaction, are increased
(curves 3 compared to curves 1).
When the hypophosphite concentration is
decreased from 0.5 to 0.1 M (curves 4 compared to
curves 1), no e€ect on hydrogen discharge is
observed. The global and partial phosphorus polar-
ization curves are inhibited. In addition the nickel
discharge is also inhibited.
This polarization investigation clearly points out
that interactions exist between the hypophosphite
and the Ni2+ reductions.
Fig. 8. Potential dependency of the characteristic fre-
quency of the inductive feature. Electrode rotation speed:
500 rev minÿ1. 1ÐElectrolyte 3d (0.05 M NiSO4, 0.5
MNaH2PO2, pH = 10.5) 2ÐElectrolyte 1a (0.05 M
NiSO4, 0.1 MNaH2PO2, pH = 9) 3ÐElectrolyte 4 (0.10
M NiSO4, 0.5 MNaH2PO2, pH = 9).
1725
Fig. 9. Rp/Rt ratio of the maximum of the real part of the
impedance and the charge transfer. Electrode rotation
speed: 500 rev minÿ1. 1ÐElectrolyte 3d (0.05 M NiSO4,
0.5 MNaH2PO2, pH = 10.5) 2ÐElectrolyte 1a (0.05 M
NiSO4, 0.1 MNaH2PO2, pH = 9) 3ÐElectrolyte 4 (0.10
M NiSO4, 0.5 MNaH2PO2, pH = 9).
2.2 Electrochemical impedance investigation.
Figure 6 shows the impedance diagrams recorded
for various electrolyte compositions, for an elec-
trode rotation speed of 500 rev/minÿ1, at 10 mA
cmÿ2. Similar relaxation features as those recorded
at the deposition potential are observed.
In the high-frequency range a capacitive feature
related to the relaxation of the double layer capaci-
tance, whose value ranges between 50 and 100
mFcmÿ2, in parallel with the charge transfer is
observed. The Rt.i product, product of the charge
transfer resistance and the current density, increases
with polarization (Fig. 7). This may be explained by
the participation of the anodic reactions and by the
reversibility of the discharge reactions of the Ni2+
species. It is nearly independent of the electrolyte
pH (curves 1 and 2), it slightly increases when the
hypophosphite concentration is reduced (curve 4)
and decreases when the nickel sulfate concentration
is increased (curve 3).
In the medium frequency range an inductive loop
is observed, which is more visible when the nickel
sulfate concentration or the pH is increased
(Fig. 6(B) and (D)). Its characteristic frequency
increases quasi-exponentially with polarization
(Fig. 8). It is slightly a€ected by the pH or the
hypophosphite concentration but increases with
nickel sulfate concentration (curve 2). A similar
inductive feature is observed in the deposition of
nickel and attributed to the two-step discharge of
the Ni2+ species through the intermediate NiIads
adion [13].
At still lower frequency a capacitive feature
appears. Its size is appreciated by the ratio Rp/Rt of
the maximum of the real part of the impedance, Rp,
by the charge transfer resistance (Fig. 9). For the
reference electrolyte this ratio is close to unity, the
capacitive loop is not much pronounced. Its size
1726 M. Ebn Touhami et al.
Fig. 10. Steady-state anodic polarization curves corrected
for ohmic drop. Electrode rotation speed: 500 rev minÿ1.
1ÐElectrolyte 3a (0.05 M NiSO4, 0.5 MNaH2PO2,
pH = 9) 2ÐElectrolyte 3d (0.05 M NiSO4, 0.5
MNaH2PO2, pH = 10.5) 3ÐElectrolyte 4 (0.10 M NiSO4,
0.5 MNaH2PO2, pH = 9) 4ÐElectrolyte 1a (0.05 M
NiSO4, 0.1 MNaH2PO2, pH = 9).
increases when the pH is increased (curve 1) or
decreases when the nickel sulfate concentration is
increased (curve 2). Its characteristic frequency
increases from 0.1 Hz to 4 Hz with polarization. A
similar capacitive feature has been previously
observed in the nickel deposition in acidic solutions
and attributed to interactions with adsorbed
hydrogen [14].
3. Anodic range
3.1 Steady-state polarization behaviour. Figure 10
shows the polarization curves for the various elec-
trolytes. A Ni-P layer was electrolessly deposited on
the substrate prior to the anodic polarization inves-
tigation. The current density exhibits a maximum.
The current decay after the maximum has been
attributed to the deactivation of the nickel surface
due to the adsorption of hydroxyl ions [15±17], or
of phosphorus atoms [18]. The curves are shifted
towards less negative potentials when the nickel sul-
Fig. 11. Impedance plots recorded for electrolyte 3,
E = ÿ 865 mV/sce, i = 5.3 mA cmÿ2. Electrode rotation
speed: 500 rev minÿ1.
Fig. 12. Rti product of the charge transfer resistance with
the current density for electrolytes 3a (curve 1) and 4
(curve 2).
fate concentration is increased (curve 3 compared
to curve 1) and towards more negative potentials
when the pH is increased (curve 2 compared to
curve 1). In a previous investigation, carried out by
cyclic voltammetry, we showed that the current
density at this maximum, Ia, increases markedly
with hypophosphite concentration, slightly with
nickel sulfate concentration. It exhibits a maximum
for a pH value of 9; this behaviour con®rms the
existence of interactions between the hydroxyl ions
and the hypophosphite oxidation [11].
Electrochemical impedance investigation
The impedance plots recorded in the rising part
of the polarization curve show two small features
(inductive and capacitive) in addition to the large
high-frequency capacitive loop (Fig. 11).
The charge transfer resistance decreases markedly
when the hypophosphite and the nickel sulfate con-
centrations are increased, especially at low current
density. It increases with polarization, probably as
a result of the blockage of the electrode area
(Fig. 12). The characteristic frequency decreases
with polarization, or with increasing nickel or hypo-
phosphite concentration. The small inductive fea-
ture has a characteristic frequency which increases
with the nickel sulfate concentration, it is indepen-
dent of the hypophosphite concentration and is
nearly constant when the polarization is increased.
The in¯uence of nickel sulfate concentration points
out the existence of interactions between the hypo-
phosphite oxidation process and the presence of
NiII species.
DISCUSSION
Despite the large number of investigations the
kinetics of electroless deposition is so far not well
understood. According to Jusys et al., the overall
process is electrochemical: electrons are transferred
via the nickel surface. The rate of the hypopho-
 Kinetics of the autocatalytic deposition of Ni-P alloys in ammoniacal solutions
sphite oxidation depends on the electrocatalytic
properties of the nickel surface [4, 5]. Hwang et al.,
also con®rm through investigations by atomic force
microscope, that the mechanism of electroless depo-
sition is electrochemical [19]. However according to
Abrantes et al. the reaction would be only partly
electrochemical. The participation of a direct chemi-
cal transfer between the Ni2+ species and hypopho-
sphite would explain the large deposition rates [6].
The experimental results can be explained accord-
ing to the following reaction path. In agreement
with other authors [2, 6, 7, 11, 20] we consider that
the oxidation process starts from the deprotonation
reaction of the hypophosphite anion. It occurs only
on catalytic surfaces such as nickel. It has been
shown that the adsorption of the hypophosphite
anion and its change into a reactive species
occurred with a good eciency on etched nickel [21].
The intermediate anion, NiIads, generated in the two-
step discharge reaction of the Ni2+ species would
be the catalyst which helps the adsorption of the
hypophosphite anion:
NiIads ‡ H2 POÿ
2 ! Ni ÿ H2 PO2 …1†
This NiH2PO2 compound gives rise to a radical
anion, HPOÿ 2 , to a hydrogen species, Hads adsorbed
on a fraction y1 of the electrode area. The NiIads
adion is regenerated, hence acting as a catalyst.
NiH2 PO2 ! HPOÿ I alytic sites for the deprotonation of hypophosphite
2 ‡ Niads ‡ Hads …2†
These two reactions are a development of the
deprotonation reaction of hypophosphite. They
demonstrate the role of the nickel species.
In the anodic domain, the main reaction is the
oxidation of hypophosphite. Indeed the radical
anion HPOÿ 2 is known to be a strong reducing
agent [22]:
HPO2 ‡ OHÿ $ H2 POÿ
3 ‡e
ÿ
…3†
According to literature data [16], the oxidation of
hypophosphite leading to several hydrolyzed com-
pounds would be responsible for the current
decrease observed on the polarization curves (see
Fig. 10). Indeed the formation of a hydroxide com-
pound such as [HPO2(OH)2]ads, would adsorb and
block a fraction y2 of the electrode area, inhibiting
reaction (2):
HPOÿ ÿ ÿ ÿ be separately discharged [23]. It accounts for the in-
2 ‡ 2OH $ ‰HPO2 …OH†2 Šads ‡ 2e …4†
The relaxation of this adsorbate is responsible for
the capacitive additional loop observed in the
anodic range, whose size increases with polariz-
ation. The reaction rates of reactions 3 and 4
depend on the solution pH and on the surface con-
centration of the HPOÿ 2 radical. Both reactions will
be enhanced when the hypophosphite concentration
or the surface coverage by NiIads adion will increase.
In addition, it has been shown that in parallel
with reactions 1±3, the following reactions
1727
occur [2, 6, 7, 17]:
OHH
ads ! H2 O ‡ e
ÿ
…5†
The evolution of hydrogen may come from the
recombination of the adsorbed hydrogen (reaction
(6)) and from the reduction of the protons from the
solution (reaction (7)). For simplicity, reaction (7) is
considered as a global two-electron process:
2Hads ! H2 …6†
2H‡ ‡ 2eÿ ! H2 …7†
The cathodic processes lead, in addition to the
hydrogen evolution, to the nickel discharge and the
incorporation of phosphorus. The discharge of
nickel is usually considered as a two-step
process [13, 14] according to:
Ni2‡ ‡ eÿ ()NiIads …8†
NiIads ‡ eÿ ! Ni …9†
The relaxation of the surface coverage by the inter-
mediate adion NiIads is responsible for the inductive
feature, always observed in the nickel deposition
process, whose characteristic frequency increases
with polarization [13].
The reversibility of reaction (8) explains the pre-
sence of the adion NiIads at the deposition potential
and in the anodic polarization range, leading to cat-
(reactions 1 and 2) [5].
The lower frequency capacitive feature, whose
size increases with polarization, with pH, with Ni2+
and hypophosphite concentrations, may be related
to the relaxation of the coverage by the adsorbed
hydrogen, Hads, resulting from the deprotonation
reaction (2). This adsorbate will inhibit the hydro-
gen evolution and interact with the nickel discharge
as already observed for the nickel deposition [14],
according to:
NiIads Hads ‡ eÿ ! Ni ‡ Hincl: …10†
The incorporation of phosphorus occurs according
to:
Ni2‡ ‡ H2 POÿ ÿ
2 ‡ 3e ! Ni ÿ P ‡ 2OH
ÿ
…11†
The reaction explains the role of nickel in the
`induced' codeposition of phosphorus, which cannot
teractions observed between phosphorus and nickel
during the codischarge, leading to a nearly constant
phosphorus content in the alloy. It also explains the
increase in the phosphorus content with an increase
of the nickel sulfate concentration in the electrolyte.
As a consequence the nickel deposition results from
the four reactions 8 to 11.
The reaction path accounts for the interaction
between the anodic and cathodic processes: the
deprotonation reaction is catalysed by NiIads adions
and it generates adsorbed hydrogen species, Hads.
1728 M. Ebn Touhami et al.
The Hads adatom partly blocks the nickel and the
hydrogen discharges.
An increase in the nickel sulfate concentration in
the electrolyte will increase the coverage by NiIads
adions. This will enhance reaction (1), facilitate the
deprotonation reaction and as a consequence
increase the rates of reactions (3) and (4). In turn
the coverage by Hads adatom will increase.
A decrease in hypophosphite concentration will
slow down the deprotonation reaction and as a con-
sequence decrease the rates of reactions (3), (4) and
(11). The slowing down of reaction (11) will result
in a decrease of nickel deposition.
A pH increase will favour reactions (13) and (4),
ie both the oxidation of hypophosphite and the
blocking reaction. Hence it explains why the plating
rate exhibits a maximum for a certain pH value
(here pH = 9) [11]. Reaction (5) will be enhanced,
resulting in a decrease in the Hads adatom coverage.
This will result in an increase of the rate of reac-
tions (8) and (9). The nickel discharge will be
increased.
CONCLUSION
The present electrochemical investigation, carried
out in the anodic and in the cathodic ranges, allows
better understanding of the electroless deposition
mechanism. The interactions between the anodic
and cathodic processes stem from the deprotonation
reaction: it is catalysed by the NiIads adions and gen-
erates Hads adatoms which will partly block the
nickel discharge. This reaction scheme accounts for
the main features observed on the impedance dia-
grams as well as their dependencies with polariz-
ation.
ACKNOWLEDGEMENTS
This investigation was carried out as part of a
French-Moroccan Interuniversity Cooperation
Grant (94/786).
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