Surface and Coatings Technology 88 (1996) 70-78

Microstructural evolution in pulse plated nickel electrodeposits

A.M. El-Sherik as*, U. Erb a, J. Page b
aDepartmentof Materials and Metallurgical Engineering, Queen’s University, Kingston, Ontario, Canada K7LN36
b Chemistry Department, Queen’s University, Kingston, Ontario, Canada K7L3N6
Received10May 1995;acceptedin final form 30April 1996

Abstract

Square-wavecathodic current modulation wasusedto electrodepositultra-fine-grainednickel from an additive-freeWatts bath.

The influenceof pulseparameters,namely,pulseon-time,off-time and peak current density on the grain size,surfacemorphology
and crystal orientation was determined.The study showed that an increasein peak current density resultedin considerable
refinementin crystal sizeof the deposit.The crystal orientation progressivelychangedfrom an almostrandom distribution at the
lowest peak current density of 400 mA cm-’ to a strong (200) texture at a peak current density of 1600mA cm-‘. At constant
peak current densityand off-time, the crystal sizeof the depositwasfound initially to decreasewith pulseon-timebeforeit started
to increasewith further increasein on-time.The crystal orientation progressivelychangedfrom an almostrandomdistribution at
the shorteston-time of 1 ms to a strong (200) fibre texture at an on-time of 8 ms. An increasein the pulseoff-time at constant
on-time and peak current density resultedin a progressiveincreasein crystal size. However, the crystal orientation remained
unaffectedwith increasingoff-time.

Keywords: Nickel electrodeposition;Microstructure

1. Introduction higher instantaneous current density in comparison to

The grain size, surface morphology and preferred
orientation of thick nickel electrodeposits depend on
both the electrolysis conditions and the electrolyte com-
position [I]. It has been shown [2-4] that nickel
electrodeposits produced from an organic-free Watts
bath under DC conditions develop (200), (220), (420)
or (422) preferred orientations. This textural develop-
ment in nickel deposits has been attributed to the
existence or formation of different interfacial inhibitors
such as Hz, Had8 or Ni(OH),, in the nickel-electrolyte
interface during the deposition process [ 1,5]. These
interfacial inhibitors were also found to affect the surface
morphology of electrodeposits [6]. It was argued that
the selective adsorption of these species on the metal
surface can affect the growth mode of the crystals
CL5,61.
Pulse electrodeposition has been found to be an
effective means of perturbing the adsorption-desorption
processes occurring at the nickel/electrolyte interface
and hence offers an opportunity of controlling the micro-
structure of nickel electrodeposits [5]. Because of the
* Corresponding author.
0257~8972/96/$15.00 0 1996 Elsevier Science S.A. All rights reserved
PII SO257-8972(96)02928-3
direct current plating [7], pulse plating has received
considerable attention in recent years as an economically
viable processing technique for producing nanocrystal-
line materials [8]. These materials with grain sizes in
the order of 10 nm are of considerable interest due to
their unique and, in many cases, improved properties
over their coarser-grained counterparts [9].
In general, the results of pulse-plating experiments
obtained by different researchers are difficult to compare
and, in many cases, contradictory. This is because of (1)
the complexity of the electrodeposition process, (2) the
rather large number of experimental variables involved
in pulse plating and (3) the lack of a standardized
procedure in investigating the general effect of a particu-
lar pulse-plating parameter. Regarding the last point,
most researchers (e.g., [ 10,111) usually cite the influence
of duty cycle, y, where y = To&& + T,,,), or pulse fre-
quency, J; where f= l/(Ton+ Ton), on deposit structure
and morphology. However, these are extracted mathe-
matical quantities from the actual pulse parameters,
namely, pulse on-time (Z&J and pulse off-time (T,,,), and
therefore do not reflect the effects of 7’&, or 7&r sepa-
rately. For example, Tai-Ping Sun et al. [lo] and also
Kim et al. [ 1 l] studied the effect of pulse on- and off-
 A.M. El-Sherik et aL/Surface and Coatings Techrzology 88 (1996) 70-78 11

time on electrodeposition of nickel, by varying the pulse
frequency at constant duty cycle and peak current
density. However, by varying the pulse frequency in
this manner, both the on-time and off-time change
simultaneously and hence it is difKcult to ascertain the
influence of on-time or off-time separately.
Similarly, the effect of peak current density on the
crystal size of the deposit is commonly investigated in
two ways [ 121: one way is to increase JP at a constant
on-time and constant average current density, J, , where
J,=J, . y, as represented in Fig. 1. This method has
the disadvantage that the off-time cannot be kept con-
stant, and hence the observed effect on the microstruc-
ture of the deposit could be due to increased off-time
and/or higher JP [ 121. One can also increase Jr, at a
constant pulse charge (i.e., the number of coulombs per
pulse is kept constant) and at a constant average current
density, J, ClZ]. Although the Z’& is then only very
slightly changed, To, changes considerably, as can be
seen in Fig. 2, and hence it becomes difficult to ascertain
the effect of J, on the microstructure.
The aim of this paper is two fold: (1) to investigate
the structural and morphological modifications of nickel
? . TO, :: Toff * acterization.
JP
------------ -_ ___ 1
nr
:_ ’ tJm
0 t
electrodeposits prepared under well-defined pulse
parameters and (2) to produce ultra-fine-grained nickel
electrodeposits from organic-free Watts bath.
2. Experimental procedure
A conventional Watts-type solution, as shown in
Table 1, in a standard 2-l reaction kettle was used to
produce approximately 300~urn thick nickel electro-
deposits. Analytical grade chemicals and distilled water
were used to prepare the solutions. The bath temperature
was maintained at 60 5 O.lo”C and its pH was adjusted
to 4.5 by adding nickel carbonate.
A high purity (99.99%) electrolytic nickel sheet con-
tained in a titanium mesh basket was used as the soluble
anode. Its surface area was approximately 10 times
greater than that of the cathode to ensure that there
were no problems arising from anode polarization, par-
ticularly at high current densities [13]. The cathode
substrate was made of titanium sheet with an exposed
surface area of 1 or 2 cm2, which was ground on 600
grit SiC paper. The anode was placed at a distance of
6 cm from the cathode. The nickel electrodeposits were
electroplated onto the Ti cathode and subsequently
mechanically stripped for microstructural char-
Electrodeposition was carried out galvanostatically
_
using square-wave pulsed current with current cut-off
during the interval between the pulses. The plating
parameters were varied within a range which has pre-

I r viously been shown [14] to produce extremely fine-

Fig. 1. Scheme for investigating changes in Jp with
on-time and constant average current density (adapted
J,, average current density; Jr,, peak current density;
tion; and T,, pulse off-time. Waveform as generated
supply.
grained (i.e., nanocrystalline) deposits from a Watts’ bath
containing saccharin. These parameters are summarized
in Table 2. It is clear from this table that the plating
times and the ,average current densities varied as a
function of the plating duty cycles so that electrodeposits
constant pulse
from Ref. [ 121): of 300-urn thicknesses were produced. This was necessary
T,,, pulse dura- to eliminate possible thickness effects on morphology
by pulse power and preferred orientation. The peak current densities
were computed based on the geometric cathode area
and no corrections were made for the actual surface

w_) Ton
_‘ +&yg?, JP
TOE l -
roughness of the deposit.
The pulse parameters were selected such that in all
cases the pulse on-time was less than the transition time,

I- I’----- ;+pg 41 ---------A-- z (the time required for the interfacial concentration to
reach zero [15J) and much longer than the charging
tJm
0 t
Table 1
Bath composition and plating conditions for Ni deposition from
Watts-type baths

NiS04. 7Hz0 300 g/l

NiC1,.6H,O 4.5g/l
Boric acid 45 g/l
PH 4.5
Fig. 2. Scheme for investigating changes in Jp with constant (J; T,,,) Temperature 60°C
and T,, The shaded areas are equal (adapted from Ref. [ 121).
72 A.M. El-Sherik et al./Surface and Coatings Technology 88 (1996) 70-78

Table 2
Range of pulse-plating parameters investigated in this study

T,, W T,ff bs) Current density, (mA cm-‘) Duty cycle (%) Plating time (min)

JP Jl?i
1 15 400 2.5 6 194
3 15 400 68 17 71
5 15 400 100 25 48
8 15 400 140 35 35
1 5 400 68 17 71
1 15 400 25 6 194
1 22 400 17 4 215
1 32 400 12 3 403
1 42 400 9 2 537
1 15 400 25 6 194
1 15 800 75 6 64
1 15 1600 100 6 48

time, t, in microseconds, of the double layer as calculated
from Eq. (1) and Eq. (2), respectively [ 16,151.
z = {~D(C,)Z(ZF)2)/4(5,)2
t, = 17/J,
where J, is the peak current density (A/cm2), z is the
number of electrons (2, for the case of nickel), F is
Faraday’s number (96,500 coulombs), C, is the bulk
concentration of Ni2” ions (mol/L) and D is the diffusion
coefficient of Ni2+ (cm2/sec). In addition, the pulse off-
time was selected such that the shortest pulse off-time
was several orders of magnitude longer than the dis-
charge time, td, of the double layer as calculated from
equation (3) I: 161.
td = 120/J, (3)
where td and Jp are as defined above in @s) and
(A mm2), respectively.
In calculating z, a bulk concentration (C,=
1.26 mall-I) of nickel ions as calculated from the
total Ni content given in Table 1 was used. In addition,
for the diffusion coefficient of nickel ions in solution the
value of D=0.76 x 10m5 cm2 s-i was used [ 171. The
limitation pertaining to the transition time is important
so that the depletion of Ni2+ cations in the pulsating
diffusion layer at the end of the pulse is small [ 121.
The range of current densities shown in Table 2 was
selected such that the highest average value (140
mA cm-“) was well below the limiting current density
for the bath used in the present work. Although a
measurement of the limiting current density was not
conducted in the present study, it is safe to assume that
its value is higher than 240 mA crnm2 as previously
measured for d.c. plating using a Watts’ bath with similar
composition and operated at 52°C and a pH of 4 [ 171.
The limitation on the average current density is impor-
tant so that the depletion in the stationary diffusion
layer is small and the microstructural changes, therefore,
are not due to the influence of mass transport phen-
omena [ 121.
Macrographs of all nickel electrodeposits were taken
(1) using a 35-mm camera equipped with a macrolens
(2) attachment. Scanning electron microscopy was used for
the observation of the surface morphology of the
as-plated surface of the electrodeposits. SEM micro-
graphs were taken normal to the as-plated surface at
magnifications up to 10 000 x . For fine-grained electro-
deposits dark-field transmission electron micrographs
were taken for the examination of the structure. Thin
foils for transmission electron microscopy (TEM) exami-
nation were prepared by electropolishing using an
electrolyte comprising 6% perchloric acid, 15% methanol
and 79% acetic acid at a temperature of -10°C and a
voltage of 15 V d.c. The grain size of these electrodeposits
was determined directly from dark field transmission
electron micrographs by measuring approximately 250
grains. X-ray diffraction patterns were obtained using
Cu-Ka radiation (A= 1.54184 A) on a standard 8-20
diffractometer.
3. Results and discussion
3.1. Effect of on-time
Table 3 illustrates the pulse-plating parameters and
average current densities, J,, used to investigate the
effect of pulse on-time on crystal size, surface morphol-
ogy and crystal orientation of these deposits. Fig. 3
shows the surface morphologies and the macrographs
(insets) of the nickel deposits obtained at pulse on-times
of 1, 3, 5 and 8 ms. The pulse off-time and the peak
current density were kept constant at 15 ms and 400
mA cmm2, respectively (see Table 3). It is obvious from
the optical insets that at the shortest on-time (Fig. 3a)
 A.M. El-Sherik et al./Swface and Coatings Technology 88 (1996) 70-78 73

Table 3 a Watts-type bath. Similarly, the increase in hydrogen

Plating parameters used to investigate the influence of pulse on-time evolution was explained in terms of an increase in
T,ff (m4 Current density (mA cm-“) overpotential for longer on-times [19].
Closer examination of the deposit surface in the SEM
JP J, revealed subtle changes in the deposit morphology. It
1 15 400 25 can be seen that for the shortest on-time (Fig. 3a), the
3 15 400 68 surface morphology of the deposit consists of large
5 15 400 100 (1-5 pm) well-facetted pyramidal-shaped crystal&es sur-
8 15 400 140 rounded by unfacetted finer grains. The pyramidal
growth is typical of a field-oriented texture, which exhib-
its preferential growth habit in the direction of the
electric field [20]. Increasing the pulse on-time led to a
decrease in size of the large pyramidal-shaped crystallites
and, ultimately, to their complete disappearance and
replacement with the finer unfacetted structure at an
on-time of 5 ms (Fig. 3~). However, a further increase in
the on-time to 8 ms resulted in the reappearance of the
larger crystallite structure (Fig. 3d).
The initial change in the deposit surface structure
from large and facetted crystallites at the shortest
on-time (Fig. 3a) to a finer structure for pulse on-time
of 5 ms (Fig. 3c) supports our argument that the depos-
ition overpotential may have increased, leading to finer
crystal size deposits [12]. The increase in deposition
overpotential at longer on-times may, in part, be attrib-
uted to the fact that at longer on-times a decreasing
portion of the on-time is used for charging the double
layer resulting in an increase in the faradaic current and
thus higher (more negative) cathode overpotential [ 191.
Fig. 3. Influence of T,, on surface morphology of 30091 thick nickel The larger concentration polarization resulting from the
deposits with constant T& of 15 ms and Jr of 400 mAcme2: (a) increased thickness of the pulsating diffusion layer at
T,,,=l ms; (b) To,=3 ms; (c) Z&,=5 ms; and (d) T,,=S ms.
longer on-times can also lead to higher deposition
overpotentials [ 213. Another plausible explanation for
the deposit surface was smooth with no apparent pits. the refinement in crystal size with increased on-time is
However, longer on-times resulted in an increase in the that longer on-times lead to an increase in the amount
number and size of pits on the deposit surface. It is of hydrogen evolved. This in turn shifts the pH of the
believed that these pits are the result of hydrogen gas nickel/electrolyte interface toward more basic values,
bubbles which remain attached to the cathode surface enhancing the adsorption and co-deposition of basic
for extended periods of time [6,18]. Increasing densities insoluble compounds such as Ni(OH)2. The adsorption
of hydrogen gas bubbles at the cathode surface at longer or incorporation of these insoluble species at the active
on-times is indicative of a higher (m&e negative) overpo- growth sites is believed to have growth-inhibiting effect,
tential for nickel deposition. This is consistent with the leading to a finer-grained equiaxed structure [ 191.
work by Abdulin et al. [19] who reported that the The re-appearance of large grain structure at the
amount of evolved hydrogen increased with increasing longest on-time of 8 ms (Fig. 3d) may be explained in
on-time during pulsed electrodeposition of nickel from terms of the redistribution of the partial currents for
reduction of nickel and hydrogen ions. At such a long
Table 4
Plating parameters used to investigate the influence of off-time on-time, it is believed that a larger portion of the applied
current is consumed by the hydrogen ion reduction
T, @s) Gf (ms) Current density (mA cmM2) reaction leading to lower efficiency for nickel deposition
and coarser grains [ 191. Yoshimura et al. [21] reported
JP Jnl such a decrease in the current efficiency for palladium
1 5 400 67 deposition and a corresponding increase in co-deposited
1 15 400 25 hydrogen at longer on-times.
1 22 400 17 The influence of on-time on the crystal orientation of
1 32 400 12 the nickel deposits at constant peak current density of
1 42 400 9
400 mA cmm2 and off-time of 15 ms is illustrated in
 A.M. El-Sheiik et al.JSurfuce and Coatings Technology 88 (1996) 70-78

111)(200)
Fig. 4a. For comparison purposes, an X-ray diffraction
(220) (311)(222)
pattern for a standard Ni powder showing peak inten-
sities for a random grain distribution is also represented
in Fig. 4b. It is clear from Fig. 4a that longer pulse
on-times lead to a progressive change in the crystal
orientation from an almost random texture to a strong
(200) fibre texture. The observed transition in crystal
orientation may be attributed to the effect of increased
8msec
pulse on-times on: (1) the depletion of cations at the
cathode film; (2) the overpotential; (3) the thickness
of the pulsating diffusion layer; (4) hydrogen
adsorption/evolution; and (5) other adsorption pro-
b 1 1 . 5msec cesses. However, it is difficult to assess how these
variables separately or in combination could have caused
the observed transition in crystal orientation.

3.2. Efect of off-time

j/J ~ h _ 3msec
Fig. 5 shows nickel deposits obtained at pulse off-
times of 5, 15, 22, 32 and 42 ms with constant on-time
of 1 ms and a peak current density of 400 mA cm-’ (see
Table 4). The low magnification optical insets clearly
show that hydrogen gas cavities are apparent on the
surface of the deposits produced at the shortest off-time
(Fig. 5a). It is reasonable to assume that in this case the
40 60 80 100

(4 2 THETA (DEG.)

:lll)(Boo) (220) (311)(222)

I / / I ,

60 80 100

(b) 2 THETA (DEG.)

Fig. 4. (a) XRD patterns showing the influence of T,, on the crystal Fig. 5. Influenceof T&r on surface morphology of 300qm thick nickel
orientation of nickel deposits with constant JP of 400 mA crnm2 and deposits at constant T,, of 1 ms and J, of 400 mA cm-*: (a) &=5
TOEof 15 ms. (b) XRD pattern of a random nickel powder sample. ms; (b) T,,= 15 ms; (c) Z&= 22 ms; (d) Tan= 32 ms; and (e) T,,= 42 ms.
 A.M. El-Sherik et al./Swface and Coatings Technology 88 (1996) 70-78 75

Table S
Plating parameters used to investigate the influence of peak current 111)(200) (220) (311)(222)
density

T,, W T,fi W Current density (mA cmW2)

JP J,
1 A n R - ‘42msec
1 15 400 25
1 15 800 75
1 15 1600 100

off-time was too short for sufficient replenishment of 32msec

the Nizi- cations at the cathode surface. This resulted in A c

a significant drop in the concentration of these cations

at the pulsating diffusion layer leading to a side reaction,
in this case hydrogen evolution. A further increase in
the off-time led to the relaxation of the pulsating diffu-
sion layer and, in turn, to increased replenishment of
Nizf. The reduced hydrogen evolution reaction is
believed to lead to the disappearance of the hydrogen
gas cavities on the deposits surface [6].
SEM micrographs of these deposits (Fig. 5a-e) show
microstructures with grain sizes in the micrometer range.
Fig. 5a shows that at the lowest o&time the deposit
surface consisted of very few well-facetted crystallites
surrounded by finer structure. However, further increase
in off-time resulted in a progressive increase in the size
and number of the pyramidal-shaped crystals and a
corresponding decrease in the surrounding fine-struc-
tured matrix. It has previously been suggested that
longer off-time leads to some sort of a desorption
process, most likely Ni(OH)2 crystals and/or Hz mole-
cules which result in an activation of growth centres and
thus larger grain sizes [5]. Another plausible explana-
tion for the coarser grains with well-defined facets is
that, during longer off-times, the nickel adatoms have
more time to migrate over the crystal surface prior to
their incorporation into the solid.
Fig. 6 and Fig. 7 show the influence of off-time on the
crystal orientation of the deposits produced at two
different pulse on-times of 1 and 8 ms, respectively but
with a constant peak current density of 400 mA cmm2.
These XRD patterns show that in case of the shortest
on-time (Fig. 6) the crystal orientation is almost random;
however, the crystal orientation changed to (200) at the
longest on-time (8 ms) tested (Fig. 7). This is consistent
with the XRD patterns (Fig. 4a) and the arguments
presented in Section 3.1. Furthermore, Fig. 6 and Fig. 7
show that at each on-time, the increase in off-time had
no effect on the crystal orientation of the nickel deposits.
Therefore it may be ,reasonable to conclude that the off-
time is a “dead time” with respect to changes in crystal
orientation of nickel deposits. Under these electrodeposi-
tion conditions (constant on-time and peak current
density), the increase in off-time is expected to increase
( 1) the replenishment of Ni2’ cations in the pulsating
I 22msec
40 60 80 100
2 THETA (DEG.)
Fig. 6. XRD patterns showing the influence of TO, on the crystal orien-
tation of nickel deposits with constant Jp of 400 mA cmT2 and T,, of
1 ms.
diffusion layer and (2) the desorption or the retrodiffu-
sion of colloidal Ni(OH), and/or hydrogen away from
the cathode surface [ 51. Then it may be concluded that
the electrodeposition conditions induced by both
on-times predominated over any effects due to longer
off-time. As a result, the crystal orientation attained at
the shortest off-time remained unchanged with further
increase in off-time.
3.3. Effect ofpeak current density
Fig. 8 is a schematic representation showing the
method used in the present study to increase J,. It is
clear from this figure that while J, increased, both To,
and Toff remained constant. Therefore, the microstruc-
tural and textural modifications can solely be attributed
to changes in JP. It should be noted that at lower J,,
the total plating time had to be longer as compared to
the time required at higher J,. This was necessary so
that deposits of equal thicknesses were produced.
Fig. 9 shows the influence of the pulse peak current
density on the macrostructure and surface morphology
of nickel deposits obtained at peak current densities of
 A.M. El-Sherik et al./Surfuce and Coatings Technology 88 (1996) 70-78

:111)(200) (220) (311)(222)

J # a :42mec

d _ h _ 3211x.x

‘)I L I\ -22msec
Fig. 9. Influence of J, on surface morphology of 300~pm thick nickel
deposits with constant &r of 15 ms and T,, of 1 ms: (a)
J,=400mAcm-2; (b) J,=800mAcm-2; and (c) JP=1600mAcm-2.

nickel from Watts bath. The higher magnification SEM

micrographs show that increasing the peak current den-
sity led to larger colony size but finer grain structure.
60 80 100 The reduction in crystal size is due to the higher overpo-
tential and the accompanying increase in ndcleation rate
2 THETA (DEG.) [ 121. Fig. 10 shows further refinement in grain structure
Fig. 7. XRD patterns showing the influence of T,, on the crystal orien- obtained at a peak current density of 1600 mA cmm2
tation of nickel deposits with constant JP of 400 mA cm-’ and Ton of but with on-times of 3 and 5 ms. For comparison
8 ms. purposes, the SEM micrograph of the deposit obtained
at a pulse on-time of 1 ms is also shown here (Fig. lOa).

-i l Ton : 1 0 .
It is clear that further reduction in grain size was
obtained with increasing on-time. The increased refine-
ment in grain size further supports the argument that

jl ’ J ------ ---- _- ‘p--L-/r

O -:--~-.~-~---~
Fig. 8. Scheme for investigating changes in JP with constant z, and
T ore
400,800 and 1600 mA cm-‘. The pulse on-time and off-
time are constant at 1 and 15 ms, respectively, as seen
in Table 5. Close examination of the optical insets reveals
that basically the same surface appearance was obtained
at peak current densities of 400 and 800 mA cmm2.
However, further increase in peak current density
(Fig. SC) caused the deposit to curl and tear which is
indicative of high internal
the results obtained by Kim et al. [ 111 for pulse-plated
stress. This is consistent
the electrode potential must have increased with
increased on-time.
Fig. 11 shows XRD patterns illustrating the crystal
orientation of these deposits. It can be seen from this
figure that higher peak current densities resulted in a
change in the crystal orientation from an almost random
texture at the lowest peak current density (400
mA cmm2) to a strong (200) fibre texture at 1600
mA cmm2. This may be attributed to the fact that higher
peak current density may lead to (1) higher electrode
overpotential and (2) reduced concentration of Ni2+ at
the electrode surface.
Fig. 12 shows a high magnification SEM micrograph
for the deposit obtained at an on-time of 3 ms. Due to
deposit curling, it was not possible to obtain 3-mm discs
for further TEM studies. However, from Fig. 12, the
grain size may be estimated to be around 150-200 nm,
visible as fine nodules in each colony. Grain size meas-
urements using transmission electron microscopy was
with only possible for the deposit obtained at 5 ms on-time
due to reduced deposit curling and tearing. Fig. 13 shows
 A.M. ELSherik et aL/Surface and Coatings Technology 88 (1996) 70-18 77

Fig. 10. Further refinement in grain structure obtained at a peak current density of (a) 1600 mA cm-’ but with (b) T,,=3 ms and (c) To,=5 ms.

(11 l)(ZOO) (220) (311)(222)

Fig. 12. High magnification SEM micrograph for ultra-fine-grained

nickel electrodeposit.

40 60 80 100

2 THETA (DEG.)
Fig. 11. XRD patterns showing the influence of Jr on the crystal orien-
tation of nickel deposits with constant T,e of 15 ms and T,, of 1 ms.

a TEM darkfield image micrograph of this deposit.

Grain size distribution measurements of approximately
250 grains showed an average grain size of approxi- Fig. 13. Transmission electron darkfield image of ultra-fine-grained
mately 110 nm. Table 6 summarizes the plating condi- nickel electrodeposit.
78 A.M. EI-Sherik et al./Sutface
Table 6
Plating conditions used to produce extremely fine-grained nickel
electrodeposits
Parameter Optimal value
On-time (ms) 5 coarsening. However, the crystal orientation
Off-time (ms) 15
Peak current density (mA cm-‘) 1600
Temperature (“C) 60
PH 4.5
tions used to produce these extremely fine-grained
deposits. X-ray diffraction pattern studies on these
samples were not possible due to the curling of these
deposits.
3.4. Production of nanocrystals by pulseplating
It may be inferred from electrocrystallization theory
that high negative overpotential, high adion population
and low adion surface mobility are prerequisites for
massive nucleation rates and reduced grain growth [22];
conditions ideal for nanograin production. Pulse plating
can satisfy the former two requirements but calculations
by Conway and Bockris [23] showed that surface
mobility is not rate-limiting under high overpotentials
for nickel. Inhibitors are required to reduce surface
diffusion of adions on the cathode surface in order to
produce nanograins in the order of 10nm. This is
consistent with our previous work [ 141 where we have
reported the production of nanocrystalline nickel with
grain sizes in the order of 10 nm from saccharin-contain-
ing Watts’ baths. In this case, saccharin acted as an
inhibitor limiting the surface mobility of adions on the
cathode surface resulting in nanosized grains. In contrast,
the present results have shown that when using an
organic-free Watts’ bath and similar pulse-plating condi-
tions, the grain size can only be refined down to about
100 nm.
4. Conclusions
Ultra-fine-grained nickel electrodeposits with grain
size down to about 100 nm were produced from an
organic-free Watts’ bath using pulse plating. Increasing
pulse on-time in the range l-5 ms resulted in grain
refinement which is attributed to increased overpotential.
The crystal orientation progressively changed from an
and Coatings Technology 88 (1996) 70-78
almost random distribution to a strong (200) fibre
texture with increasing on-time and peak current density.
The grain size of these deposits, as expected, became-
smaller with increasing pulse peak current density.
Longer pulse off-time was found to result in grain size
was
unaffected by changes in off-time.
Acknowledgement
The authors acknowledge financial support from the
Natural Sciences and Engineering Research Council of
Canada, Energy, Mines and Resources of Canada and
the School of Graduate Studies at Queen’s University.
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