REVIEW

Electrodeposition of nanocrystalline nickel–

cobalt binary alloy coatings: a review
C. Ma1, S. C. Wang*2 and F. C. Walsh2,3
The history of Ni–Co alloy deposits is summarised and recent developments are highlighted.
Electrodeposition of nanocrystalline Ni–Co binary alloys and, briefly, Co–Ni–P ternary coatings is
considered, including chemical composition, phase composition and crystalline nature.
Nanostructure, morphology, physical and mechanical properties (including corrosion resistance)
vs bath type and composition (including pH and electrolyte additives) and plating conditions,
including current density, temperature and agitation are summarised. Applications range from
wear and corrosion resistant coatings, particularly as a hard chromium replacement to speciality
hydrogen evolution electrodes in water electrolysis. Following this extensive review, future
research needs are briefly listed.
Keywords: Alloy deposits, Corrosion resistance, Electrocrystallisation, Electron diffraction, Electroplating, Hardness, Nanostructure, Transmission electron
microscopy

Introduction nanostructured alloy deposition plating by

Part 1 of this series of reviews considered the electro-
deposition of nanocrystalline nickel and cobalt as single
metals.1 In this paper, the authors focus on the
importance of nanocrystalline Ni–Co alloy deposits.
The advantages of electroplating compared to other
techniques such as physical vapour deposition, chemical
vapour deposition, high velocity oxygen fed flame
spraying, plasma spraying, laser cladding and weld
facing, etc., were summarised in Part 1. In summary,
direct electroplating offers versatility, reasonable speed,
relatively low costs together with the ability to control
thickness and structure of the deposits, even on complex
shapes. Further research is needed to better understand
the microstructure and properties of Ni–Co coatings and
to develop novel Co–Ni–P coatings (to be discussed in
Part 3 of this series) with improved wear and corrosion
resistance to replace hard chromium. The key require-
ments of research in this area involve:
(i) the role of tribofilms and debris on the
tribological behaviour of Ni–Co coatings of
different cobalt contents needs clarification
(ii) current methods such as compositionally
graded coatings and application of pulsed
current have limitations including complex
equipment and high costs. Moreover, the
microhardness needs to be further increased.
There is a clear case to realise simple, direct
1 To provide more competitive coatings and improve the
Crown Packaging UK plc, Downsview Road, Wantage, Oxon OX12 9BP,
UK
2
National Centre for Advanced Tribology at Southampton and Materials
Engineering Research Group, University of Southampton, Highfield,
Southampton SO17 1BJ, UK
3
Electrochemical Engineering Laboratory, University of Southampton,
Highfield, Southampton SO17 1BJ, UK
*Corresponding author, email wangs@soton.ac.uk
selecting and optimising bath additives and
plating conditions
(iii) despite the studies on coarse-grained deposits,
there have been few comparable investigations
of nanocrystalline Ni–Co coatings. Numerous
mechanisms have been proposed to explain the
deviation from the conventional Hall–Petch
relationship for nanocrystalline materials when
the grain size is reduced to a threshold value.
However, none of these is focused on the
influence of surface porosity, which is common
in thin electrodeposited coatings. Deviation
from the Hall–Petch relationship may partly
derive from the porosity
(iv) few studies on the tribological properties of Co–
Ni–P coatings have been reported in the
literature, despite their attraction for anti-wear
applications. The novel ternary alloys are
expected to combine the lubricity of cobalt-rich
Co–Ni coatings and the precipitation hardening
achieved by heat treatment of Ni–P alloys
(forming nickel–phosphide phases) to achieve
comparable or superior wear resistance to hard
chromium. The composition gradient and
microstructure changes from nanocrystalline
to amorphous structure with thickness of Co–
Ni–P coatings also require study. Electro-
deposited Co–Ni–P coatings will be considered
in the third of this series of reviews.2
technology of Ni–Co alloy coatings, it is important to
consider the electrodeposition of Ni–Co nanocrystalline
deposits in some detail together with structure–property–
plating conditions interrelationships. Hence this review
considers structure and crystal phase composition in detail
then considers the effect of electroplating conditions on

ß 2015 Institute of Materials Finishing

Published by Maney on behalf of the Institute
Received 12 December 2013; accepted 3 October 2014
104 DOI 10.1179/0020296714Z.000000000218 Transactions of the IMF 2015 VOL 93 NO 2
 Ma et al.
the structural and physical properties along with the
corrosion resistance and tribology of the deposits.
Nanocrystalline Ni–Co electrodeposits have the
potential to be used in aerospace, automobile and
general industries as an alternative to hard chromium
coatings due to their high hardness, wear-resistance and
anti-corrosion resistance.3 As with nickel or cobalt
coatings, the Ni–Co alloys can be deposited from
sulphamate baths, Watts type baths and chloride baths.
Tury et al.4 reported that the coatings plated from the
former two baths were homogeneous in the whole cross-
section, but had much lower microhardness than those
produced from chloride baths. In the past few years, the
preparation and optimisation of the coatings have
drawn extensive attention, especially the relationship
among experimental parameters, microstructure and
properties.
Deposit properties
Microstructure
The surface morphology of Ni–Co alloys strongly
depends on their cobalt content as shown in Fig. 1.2 It
changed from large polyhedral crystallites to small
spherical clusters as the cobalt content increased from
7 to 66 wt-%Co. The 81 wt-%Co–Ni coating exhibited
the branched structure as shown in Fig. 1f. The phase
structure gradually changed from fcc to hcp as the
cobalt content increased.2 As shown in Fig. 2e, the
66 wt-% Co–Ni coating contained the mixture structure
of fcc and hcp, while the 81 wt-% Co–Ni in Fig. 2f had a
strong hcp (002) texture with pronounced (100) and
(101) peaks, similar to the structure of the pure cobalt
coating shown in the first of this review series.1 Myung
and Nobe5 reported that the transition from fcc to hcp
structure occurred when the cobalt content was in the
range of 72–78 wt-%.
Microhardness
Generally, the microhardness of nanocrystalline Ni–Co
coating with different grain sizes electrodeposited by
direct current was in the range of 300–500 HV depend-
ing on the cobalt content as shown in Fig. 3.2 It was
found that the microhardness of Ni–Co alloys increased
initially with Co content from 0 to approximately 49 wt-
%, then gradually decreased with a further increase the
cobalt content. The similar evolution of microhardness
as the function of cobalt content was also reported by
Golodnitsky et al.6 and Srivastava et al.7 Wang et al.3
claimed that the Ni–Co alloys exhibited a nearly
constant Hall–Petch gradient. It is inappropriate to
apply the Hall–Petch relationship to different materials,
however, since k in equation (1) is a material dependant
constant.8 Srivastava et al.7 attributed the decrease in
hardness with the cobalt content higher than 50 wt-% to
the formation of fibrous structure and the transforma-
tion from fcc to hcp crystal structure. Li et al.9 reported
that the Ni–Co coatings produced by pulse current
plating had higher hardness (400–600 HV) than the
coatings plated by direct current depending on the
composition and grain size due to different peak current
densities, as shown in Fig. 4.
Tribological behaviour
Research conducted by Wang et al.3 showed that the
cobalt-rich alloy has excellent friction–reduction behaviour
Electrodeposition of nanocrystalline nickel–cobalt binary alloy coatings
against a stainless steel ball under dry sliding conditions
compared to nickel-rich alloys. As shown in Fig. 5, the
coefficient of friction of Ni–Co alloys with cobalt content
lower than 49 wt-% was higher than 0.6, which is similar to
that of the pure nickel coating. It started to decrease when
the cobalt content was 66 wt-% and the 81 wt-% Co–Ni
exhibited a dramatic reduction of coefficient of friction,
which was approximately 0.25 (less than half the value of
Ni and Ni-rich alloys). The friction reduction seen using
cobalt-rich alloys was attributed to the change of crystal
structure from fcc to hcp. Figure 6 illustrates the improve-
ment of wear resistance with increasing cobalt peak current
density9 content in the Ni–Co deposits.
When the cobalt content was lower than 49 wt-%, the
wear rate gradually decreased due to the increase in
microhardness. In spite of its lower hardness, the wear
rate of 81 wt-% Co–Ni was over one order of magnitude
lower than that of pure Ni and Ni-rich alloys. The
difference in the wear behaviour of Ni–Co alloys can be
verified by the worn surface morphologies shown in
Fig. 7. The wear tracks on deposits of pure nickel
(Fig. 7a) and 27 wt-% Co–Ni (Fig. 7b) with fcc structure
exhibited the larger extent of adhesion wear and severe
deformation in the sliding direction under the combined
stresses of compression and shear. However, smooth
surfaces with smaller damaged regions, and only light
grooves and scars, were observed on the worn surface of
the 81 wt-% Co–Ni with hcp structure (Fig. 7c). The hcp
structure of cobalt-based alloys (Co–Re, Co–Mo and
Co–Cr) leads to a lower coefficient of friction and wear
rate than their counterparts with fcc structure.10,11
The tribological behaviour of electrodeposited nano-
crystalline Ni–Co coatings having controlled cobalt
content has been considered in a recent paper.12 The
worn surfaces and wear debris were characterised by
surface analysis techniques following dry sliding tests
against a stainless steel ball. The tribofilms containing
iron from the stainless steel counterpart were formed on
the worn surface of the coatings (less than 60 at.-%Co),
which exhibited high coefficients of friction and wear
rates. No tribofilm or iron transfer from the pin were
found on the Co-rich coatings (more than 70 at.-%Co),
but there was a dramatic reduction of 50% in friction
and an improved wear resistance was reported.
Corrosion behaviour
Myung and Nobe5 investigated the corrosion resistance
of Ni–Co alloys plated from chloride baths having
different cobalt contents in 0.5M NaCl after 1 h
immersion. As shown in Fig. 8, the corrosion resistance
increased slightly with increasing cobalt content until it
reached the maximum at 70%Co and then sharply
decreased. The nickel-rich deposits with fcc structure
had an order of magnitude higher corrosion resistance
than cobalt-rich coatings with hcp structure. Srivastava
et al.7 found that Ni–20%Co alloy plated from
sulphamate baths exhibited better corrosion resistance
in 3.5% NaCl in comparison to other Ni–Co alloys with
higher cobalt content, which was attributed to its dense
surface and fcc structure. Hassani et al.13 reported that
the nanocrystalline 5 wt-% Co–Ni alloys with smoother
surface deposited from a bath containing saccharin had
higher corrosion resistance in 10 wt-% NaOH compared
to coatings with the same composition plated from
additive-free baths.
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Ma et al. Electrodeposition of nanocrystalline nickel–cobalt binary alloy coatings

1 Surface morphologies of Ni–Co alloy deposits with Co contents of a 0 wt-%, b 7 wt-%, c 27 wt-%, d 49 wt-%, e 66 wt-%, f
81 wt-%, and g high magnification image of Ni–49 wt-%Co alloy3

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 Ma et al. Electrodeposition of nanocrystalline nickel–cobalt binary alloy coatings

4 Microhardness of Ni–Co coatings as a function of peak

current density during pulsed current plating9

2 XRD patterns of Ni–Co alloy deposits with Co contents

of a 0 wt-%, b 7 wt-%, c 27 wt-%, d 49 wt-%, e 66 wt-%
and f 81 wt-%3

Importance of experimental parameters

In order to optimise the properties of nanocrystalline
Ni–Co electrodeposition, the electroplating variables, 5 Coefficient of friction as a function of Co content in
such as cobalt ion concentration, current density, Ni–Co alloys3
additive, bath temperature and bath agitation, should
be appropriately adjusted. Previous studies showed that in Fig. 9.3 It was found that the percentage of cobalt in
these factors had different effects on the microstructure alloys was higher than the Co2z/(Co2zzNi2z) molar
and composition of Ni–Co coatings and consequently ratio in the electrolyte.3,14 The less noble metal (Co) was
led to different hardness, tribological and electrochemi-
preferentially deposited. Bai and Hu15 considered the
cal properties, which are now discussed.
anomalous deposition to be attributable to the higher
Effect of cobalt ion concentration in electrolyte adsorption ability of Co(OH)z compared to Ni(OH)z
on the cathode surface. The suggested reaction mechan-
With a fixed concentration of nickel ions, the cobalt
ism of Ni–Co electrodeposition is15
content in alloy deposit increased gradually with the
increasing Co2z concentration in electrolytes as shown

3 Microhardness as a function of Co content3 6 Wear rate as a function of Co content in Ni–Co alloys3

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Ma et al. Electrodeposition of nanocrystalline nickel–cobalt binary alloy coatings

8 Corrosion resistance of Ni–Co alloys in 0.5M NaCl after

1 h immersion5

has been discussed in the section on ‘Corrosion

behaviour’.
Effect of current density
Fan and Piron16 reported that the current efficiency for
Ni–Co codeposition in chloride baths increased with
increasing current density, and reached 96–98% at
current densities from 0.5 to 10 A dm22. It decreased
with the further increase in current density. The coating
deposited with the current density of l00 A dm22 was
porous and fragile, and detached partially from the
electrode due to vigorous hydrogen evolution during
deposition. High current density can be applied to
produce nanocrystalline Ni–Co alloys by jet electro-
deposition14 and pulsed current deposition.9 The cobalt
content decreased as the peak current density increased
as shown in Fig. 1014 and Fig. 11,9 respectively. The
increase in cathodic current density leads to the cathodic
overpotential which favours the activation-controlled
nickel deposition, whereas diffusion-controlled cobalt
deposition has fewer responses. Therefore, higher
current density results in lower cobalt content in the
deposits.16 As shown in Fig. 12, the grain size of Ni–Co
coatings electroplated by pulsed current deposition
decreased rapidly with the increasing peak current
density to around 20 nm at l00 A dm22 then slowly

7 Worn surface of a pure nickel and Ni–Co alloy deposits

containing b 27 wt-% Co–Ni and c 81 wt-% Co–Ni3

{
2H2 Oz2e{ ~H2 z2OH (2)

M2z zOH{ ~M(OH)z (3)

M(OH)z ~M(OH)z
ads (4)

M(OH)z {
ads z2e ~MzOH
{
(5)
where M indicates a nickel or cobalt atom. The
deposition of cobalt is promoted by the surface
enrichment of adsorbed metal hydroxide cations
(Co(OH)zads). The cobalt content has a significant
influence on surface morphology, phase structure, 9 Composition of Ni–Co alloys as a function of ratio of
microhardness, wear and corrosion resistance, which Co2z/(Co2zzNi2z) in electrolytes3

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 Ma et al.
10 Effect of cathodic current density on composition of
Ni–Co deposits produced by jet electrodeposition a
without saccharin and b with 2.5 g dm23 saccharin14
reduced to 10 nm at l60 A dm22. The reduction of grain
size can be attributed to the higher overpotential gk,
which is related to the probability of crystalline nucleus
formation, W expressed by17
b The deposits from saccharin-containing baths inevi-
W ~B exp{ (6)
gk
where B and b are constants. The overpotential increases
with the increasing current density as described by the
cathodic Tafel equation9
gk ~a{blog j (7)
where a and b are constants and j is the current density.
Increasing current density leads to increasing over-
potential, which promotes the formation of a crystalline
nucleus and reduction in grain size.
Electrolyte additives
Organic compounds (e.g. saccharin, sodium dodecyl
sulphate and 2-butin-1,4-diol in small concentrations
can be added to Ni–Co plating baths to modify the
process of electrocrystallisation for a variety of pur-
poses, including obtaining a mirror-like surface, increas-
ing hardness and improving corrosion resistance.18 The
effects of peak current density on the grain size of Ni–Co
deposits produced by pulsed electrodeposition9 on the
composition, grain size, microstructure and properties
of Ni–Co deposits have been investigated. Compared
11 Effect of peak current density on composition of Ni–
Co deposits produced by pulsed current plating9
Electrodeposition of nanocrystalline nickel–cobalt binary alloy coatings
12 Effect of peak current density on grain size of Ni–Co
coatings deposited by pulsed current plating9
with the coating obtained from additive-free baths, the
addition of saccharin resulted in a slight reduction of
cobalt content due to the increasing deposition over-
potential as shown in Fig. 10, which is in favour of
activation-controlled Ni deposition.3 Li et al.19 also
reported that by increasing the concentration of
saccharin from 3 to 5 g dm23 in electrolytes containing
6 g dm23 cobalt sulphate, the cobalt content slightly
decreased from 8.5 to 6.1 wt-%.
tably contain certain amounts of sulphur impurities,19,20
which may lead to poor ductility21 and corrosion
resistance.22 Saccharin has a significant effect on the
reduction of grain size. The grain size of 5 wt-% Co–Ni
alloys decreased from 44 nm for the coating plated from
the additive-free bath to 22 nm by adding 1 g dm23
saccharin.13 At the same time, the texture changed from
(200) to (111) and the surface was much smoother.
These changes led to higher microhardness and
improved anti-corrosion properties of coatings. The
addition of sodium dodecyl sulphate led to a compact
surface morphology, which improved the corrosion
resistance. Marikkannu et al.18 investigated the role of
additives in Ni–Co deposits from acetate baths contain-
ing single additives, including saccharin, dextrin, cou-
marin, formaldehyde, glycine and crotonaldehyde.
Some corrosion characteristics of Ni–Co deposits in
5 wt/vol.-% NaCl at 25uC are shown in Table 1.18 The
corrosion resistance of Ni–Co deposits with a cobalt
content of 42–47% in 5 wt./vol.-% NaCl solution was
improved by adding these additives. Furthermore, the
microhardness of these coatings was higher than that of
deposits from the additive-free bath. Saccharin and
formaldehyde produced a mirror finish deposit.
Recent studies have examined saccharin and 2-butin-
1,4-diol as bath additives, in a modified Watts solution,
to electrodeposited high-quality nickel–cobalt alloys
(78¡2 at.-%Co) as a protective coating on steel
substrates for tribological applications.23 These addi-
tives allow controlled electrodeposition of nanocrystal-
line coatings. The surface morphology, grain size,
crystalline texture, hardness and performance against
stainless steel in a reciprocating ball-on-disc tribometer
were studied. Microstress in the coating could be
manipulated from tensile to compressive and the texture
could be modified from hexagonal closed-packed
structure (1010)
- structure to a face centred cubic (111)
or a hexagonal closed-packed (0002) structure. The
effect of absorbed species on the nanocrystalline coating
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Ma et al. Electrodeposition of nanocrystalline nickel–cobalt binary alloy coatings

13 Variation of internal stress with cobalt content in Ni–

14 Distribution of cobalt content with thickness of graded
Co alloys26
Ni–Co nanocrystalline alloys26

is explained via grain size and texture analyses. The
coating from the bath with an optimised additive
content showed a high hardness (500 HV) due to its
reduced grain size (11¡2 nm) and improved tribological
properties due to the high proportion of hcp structure.
Bath agitation and temperature
The common methods used for bath agitation include
air agitation, overhead impeller,24 magnetic stirring,3
high speed jet3 and peristaltic pumping25 in order to
maintain the flow of electrolyte at a constant and stable
level. An increase in bath agitation results in a higher
cobalt content in deposits due to the reduction of the
diffusion layer thickness accompanied by the rising
metal ion concentration in it. As discussed above,
diffusion controlled cobalt is preferentially deposited.14
In addition, the agitation can increase the limiting
current density jL by reducing the thickness of the
Nernst diffusion layer, d in the equation17
jL ~zFD(cb {cs )=d
where F is the Faraday constant, D is the diffusion
coefficient of the metal ion, cb is the metal ion
concentration in the bulk solution and cs is the metal
ion concentration at the electrode surface. The increas-
ing current density results in higher overpotential to
produce coatings with finer grain size. Qiao et al.14
reported that with the increasing temperature from 30 to
50uC, the cobalt content in Ni–Co deposits decreased
from 77 to 69 wt-%, since a higher temperature favoured
activation-controlled Ni deposition.
Approaches to reduce internal stress
Wang et al.26 reported that the internal stress of Ni–Co
electrodeposits depended on the cobalt content. As
shown in Fig. 13, the internal stress gradually decreased
with increasing cobalt content. It changed from com-
pressive to tensile as the cobalt content exceeded 49 wt-%.
A very high tensile stress in the range of 40–70 MPa was
obtained for the cobalt-rich coatings. The high internal
stress can result in lower ductility and adhesion between
coatings and substrates,27 which restricts their applica-
tions for anti-wear and anti-corrosion purposes. In
order to decrease the internal stress, the Ni–Co coating
with continuously graded composition and structure
were produced by controlling the cobalt ion concentra-
tion in baths during the electrodeposition process.26 As
shown in Fig. 14, the composition gradually changes
from the Ni-rich region to the Co-rich region as a
function of distance from the interface between the
coating and the AISI-1045 steel substrate. The phase
(8) structure gradually changed from fcc to hcp with
thickness due to the increase in cobalt content. As
shown in Fig. 13, the internal stress of the graded Ni–Co
coating was reduced to a much lower level, around
5 MPa. The graded coating with the microhardness of
550 HV exhibited a much lower coefficient of friction
and improved wear resistance compared with ungraded
nickel-rich coatings.
Based on this, Wang et al.28 developed nanocrystalline
Ni–Co/CoO graded coatings by a subsequent cyclic
thermal oxidation at 300uC and quenching. As shown in
Fig. 15, the graded Ni–Co/CoO coating consisted of six

Table 1 Corrosion characteristics of Ni–Co deposits plated from acetate baths having different additives in 5% NaCl at
25uC18

Additives Concentration/g dm23 Ecorr/mV(SCE) jcorr/61024 A cm22 Microhardness/HV

(None) 0 2449 3.5 349

Saccharin 2 2501 1.7 385
Dextrin 3 2648 2.5 365
Coumarin 1 2684 2.3 375
Formaldehyde 2 mL dm23 2460 1.9 379
Glycine 2 2593 3.1 371
Crotonaldehyde 2 mL dm23 2585 2.9 367
1,4-butyne diol 1–2 mL dm23 2668 49.8 372
1,3-naphthalene sulphonic acid 3 2457 2.0 360

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 Ma et al.
15 a SEM image of cross-section of graded Co–Ni/CoO coating. Corresponding b nickel and c cobalt element distribution
maps across coating28
sublayers of controlled composition varying from 0 to
81 wt-%Co. The Co level in the coating was controlled
by careful control of post-plating temperature and time
during heating then quenching. The coating was
approximately 100 mm thick with an oxide layer of
3–4 mm. Compared to as-deposited Ni–Co graded coat-
ings, the graded Ni–Co/CoO composite coating exhib-
ited significantly enhanced wear resistance under dry
sliding conditions and improved corrosion resistance in
both 10 wt-% NaOH and 3.5 wt-% NaCl solutions due
to the formation of the dense and protective oxide layer.
Electrochemical applications of
electrodeposited Ni–Co alloy
nanostructured coatings
As indicated in previous sections, major driving forces
for the development of Ni–Co electrodeposits have been
increasingly arduous service requirements for corrosion
resistant (the section on ‘Corrosion behaviour’) and
wear resistant (the section on ‘Tribological behaviour’)
coatings, often as an alternative to nickel or a possible
replacement for chromium coatings. The attractions of a
directly produced nanostructured alloy coating having a
high surface area and catalytic activity for oxygen and
hydrogen electrodes has additionally given rise to use in
water electrolysis and energy conversion in advanced
batteries and supercapacitors, which are briefly consid-
ered in this section.
Electrodeposited Ni–Co coatings may find use as
electrocatalytic coatings for hydrogen or oxygen evolu-
tion in advanced water electrolysers.29 Hydrogen evolu-
tion catalysts are commonly ‘activated’ nickel, which
consists of finely divided nickel, or Ni-alloy deposits;30
nanostructured Ni–Co is a possible material although
Ni–Mn is often superior. In the case of oxygen electrodes,
a facile route to such coatings is to carefully anodise
electrodeposited Ni–Co alloys to form mixed metal
oxides, such as NiCo2O4 spinels which are established
oxygen evolution catalysts.31 High surface area, nickel-
based oxygen evolution electrodes, including Ni
Co(OH)2, have been examined at high current densities
and elevated temperature, 353 K in 4M KOH.32
NiCo2O4 spinels have also been suggested as bifunctional
(oxygen evolution and oxygen reduction catalysts in 4M
KOH electrolytes at 333 K for secondary Zn-air flow
batteries33 and as electrode surfaces for supercapacitors.34
Electrodeposition of nanocrystalline nickel–cobalt binary alloy coatings
Among the many electrode materials suggested for
advanced batteries and supercapacitors, a recent paper
from the authors’ laboratory has demonstrated the
electrodeposition of nanostructured Ni–Co layers.35
These studies used an electrolyte of an aqueous solution
of 0.84M NiCl2 and 0.20M CoCl2, at 317 K with
templated deposition through a mesoporous, lyotropic
liquid crystal phase surfactant (cetyltrimethylammo-
nium bromide) layer having ‘toothpaste’ consistency
at a typical current density of 3 mA cm22. Energy
dispersive X-ray spectroscopy analysis showed that the
atomic ratio of Ni/Co (typically 0.20 to 0.26) varied only
slightly with current density. The high surface area Ni/
Co alloy layers with a thickness of 2 mm in 1 mol dm23
NaOH were imaged by helium ion microscopy and
could store y1 C cm22 via the Ni(OH)2/NiOOH
couple. This charge could be cycled .20 times.
Summary
Ni–Co electrodeposition is a preferred substitute for
coatings including hard chromium and nickel from the
point of view of the balance between cost, speed and
coating service performance. Recent studies on electro-
deposited nickel, cobalt, Ni–Co binary alloys and,
briefly, Co–Ni–P ternary coatings have been sum-
marised. Further research is needed in order to better
understand the microstructure and properties of Ni–Co
coatings and to develop further coatings with improved
wear and corrosion resistance to replace hard chro-
mium. Rising environmental pressures on nickel solu-
tions and wastes (and to cobalt in the longer term) mean
that Ni–Co coatings may receive more limitations on
their use, despite their tribological and corrosion
prevention advantages.
Some key remaining questions concerning nanostruc-
tured Ni–Co alloy electrodeposits can be summarised.
1. Recent findings have shown that electrodeposited
nanocrystalline cobalt-rich Ni–Co alloys having an hcp
structure exhibited better tribological properties than Ni
and nickel-rich Ni–Co coatings.12 This may be asso-
ciated with the participation of tribofilms and debris.
However, no studies on the role of tribofilms and the
microstructure of debris have been reported. More
experimental work is needed to fully understand the
tribological behaviour of Ni–Co coatings of controlled
cobalt content. In addition, the corrosion resistance of
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Ma et al. Electrodeposition of nanocrystalline nickel–cobalt binary alloy coatings
Ni–Co alloys in 3.5% NaCl solutions needs to be closely
compared to that of hard chromium, particularly as
nanostructured Ni–Co deposits can be considered as a
possible replacement for hard chromium layers in some
applications.
2. It has been reported that cobalt-rich nanocrystal-
line coatings with improved tribological properties were
difficult to electrodeposit onto steel due to high internal
stress. Current methods (such as graded coatings and
applying pulse current waveforms) have limitations
including complex equipment needs and high cost.
Moreover, the microhardness needs to be further
increased. In recent work, Ni–Co coatings having a
high cobalt content have been realised on steel sub-
strates by selecting and optimising electrolyte additives.23
The effect of additives on the microstructure and pro-
perties deserves extensive study.
3. Although the effect of baths with different nickel
salts on mechanical properties has been studied on
coarse-grained (grain size of the order of microns) nickel
coatings, few comparable investigations on nanocrystal-
line Ni–Co coatings have been carried out. Numerous
mechanisms have been proposed to explain the deviation
from the conventional Hall–Petch relationship for
nanocrystalline materials when the grain size is reduced
to a threshold value. However, none of them focused on
the influence of surface pores, which are common for
electrodeposited nanocrystalline coatings. Deviation
from the Hall–Petch relationship may derive from the
porosity36 and this remains to be clarified.
Acknowledgement
The authors gratefully acknowledge financial support
from ICUK which contributed to the PhD studies of CM.
References
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2. C. Ma, S. C. Wang and F. C. Walsh: ‘The electrodeposition of
nanocrystalline nickel-cobalt-phosphorus ternary coatings: a
review’, submitted to Trans. IMF, 2014.
3. L. Wang, Y. Gao, Q. Xue, H. Liu and T. Xu: ‘Microstructure and
tribological properties of electrodeposited Ni–Co alloy deposits’,
Appl. Surf. Sci., 2005, 242, 326–332.
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pulse currents’, Surf. Coat. Technol., 2006, 200, 6713–6717.
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