Electrochimica Acta 243 (2017) 7–17

Contents lists available at ScienceDirect

Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Formation and characterization of multilayers borohydride and

hypophosphite reduced electroless nickel deposits
V. Vitry* , L. Bonin
Metallurgy Lab, UMONS, 20 place du Parc, 7000 Mons, Belgium

A R T I C L E I N F O A B S T R A C T

Article history:
Received 25 January 2017 Electroless nickel coatings are popular surface treatments for industrial application because they can
Received in revised form 27 April 2017 provide either excellent corrosion protection (in the case of nickel-phosphorus Ni-P coatings) or
Accepted 27 April 2017 excellent wear resistance and superficial hardness (in the case of nickel-boron Ni-B coatings). The
Available online 6 May 2017 properties provided by both types of coatings are thus complementary and recent work has focused on
combining electroless Ni-P and Ni-B in the form of duplex coatings. This work goes further on this
Keywords: research by studying multilayer electroless Ni-P/Ni-B coatings. The Ni–P/Ni–B multilayer coatings were
Multilayer coatings prepared using a commercial bath for the Ni-P coatings and a lab-developed alkaline bath based on
electroless deposition
sodium borohydride for the Ni-B deposits. Single layers of Ni-P and Ni-B as well as multilayers
electroless Ni-B
constituted of 10 layers, alternating between Ni-P and Ni-B electroless bath, were prepared. Scanning
electroless Ni-P
electron microscopy (SEM) observations of the cross-sections of the nickel duplex coatings reveal that
coatings are uniform with proper compatibility between layers. When compared with the single layers of
NiB and NiP the multilayer coatings have better wear and abrasion properties. Scratch test was used to
qualify the adherence between the layers. Hardness and adhesion properties are closer to NiP.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction 22,28,29], coating uniformity [28–30], wear [23–26,31–35] and

Metal deposition from aqueous solution can be classified into
two types, electrolytic and electroless. Electroless deposition has
been extensively studied for many industrial applications. The
most investigated systems by far include nickel [1–9], silver [10,11],
gold [12,13], copper [14,15], platinum [16,17] and related alloys.
Electroless deposition allows to produce homogeneous coatings
with good adhesion on various substrate materials, including
nonconductive substrates, with complex geometries.
Electroless deposition is a chemical reduction process that
involves autocatalytic reduction of metal ions in an aqueous
solution containing a reducing agent. During the plating process,
the electrons, which reduce the nickel ions to metallic nickel, are
provided by a reducing agent and not by an external current source,
which makes the bath itself anodic against the catalytic surface of
the substrate. The deposit also is itself catalytic and this therefore
results in a continuous process [1,3,18,19].
Among various systems of electroless coatings, electroless
nickel coatings have attracted special attention due to their various
interesting properties such as hardness [20–27], adherence [20–
* Corresponding author.
E-mail address: Veronique.VITRY@umons.ac.be (V. Vitry).
corrosion resistance [36–40], as well as the ability to plate non-
conductive surfaces [41–43] that make them suitable for many
applications in the plating industry.
Electroless nickel coating can be divided in 3 main groups: NiP
(nickel-phosphorus alloys), NiB (nickel-boron alloys) and pure Ni.
These three distinct groups are generated by different reducing
agents: hypophosphite for NiP [36–40,44,45], borohydride [20–
23,29,31] or amine-borane [46,47] for NiB and hydrazine [48] for
pure nickel.
Among electroless coatings, NiB is the best candidate for
mechanical and tribological properties when compared to others
such as NiP. NiB coatings present high hardness, close to 900hv100
in the as plated state [22]. In addition, borohydride-reduced
electroless nickel coatings present low friction coefficient and high
wear resistance. Nickel-boron coatings obtained with sodium
borohydride most often contain either lead of thallium because
their salts are the most efficient and popular stabilizers for the
electroless deposition process in the conditions of sodium
borohydride stability [31,49]. Only a few authors have used baths
with organic stabilizers, mainly thiourea [33,50,51]. The mechani-
cal properties of the coatings that have been produced with
thiourea are not as good as those of coatings stabilized with either
lead or thallium and there is no indication that they provide better

http://dx.doi.org/10.1016/j.electacta.2017.04.152
0013-4686/© 2017 Elsevier Ltd. All rights reserved.
8 V. Vitry, L. Bonin / Electrochimica Acta 243 (2017) 7–17
corrosion resistance. In contrast, hypophosphite-reduced electro-
less nickel coatings find extensive applications due to their high
corrosion resistance [36–40].
As presented before, NiB and NiP coatings have complementary
properties. Recently, several studies have been developed to
investigate duplex coatings composed by one layer of NiB and one
layer of NiP. The objective of those was to generate a system that
combines both NiB and NiP to improve globally the mechanical and
corrosion properties [50,52–54]. Different configurations were
tested, in the as plated state and also in the heat treated condition.
However, while the NiB/NiP duplex coatings seem promising, the
results were not completely satisfying.
Hence, the present study focuses on the refinement of
electroless NiB and NiP layers. In the present work, the multilayer
coatings are composed of ten layers, alternating between Ni-P and
Ni-B electroless bath, with an increase of the number of layer but a
conservation of the total thickness of the system, to allow easy
comparison with previous results.
2. Experimental
2.1. Sample preparation
Specimens of mild steel (ST 37-DIN 17100) were cut with a size
of 25 mm  50 mm  1 mm. For convenient handling, a hole of
2 mm in diameter was drilled close to the sample edge. The surface
of the specimens was polished with emery paper up to 1200 grit.
The substrates were prepared for plating by acetone degreasing
and each sample was etched for 3 minutes in a 30 vol.%
hydrochloric acid solution just before plating. This etching step
acted as activation of the substrate. This was possible because mild
steel, like most ferrous substrates, is catalytic for electroless nickel
plating [29,53,55–57]. The plates used for the Taber abrasion tests
were cut with a size of 100 mm  100 mm  1 mm and a hole of
7 mm diameter was drilled in their center to fit the test equipment.
Electroless plating was carried out in on a regulated hot plate
with magnetic stirring with a volume of 1L. In the case of Taber
abrasion test samples, a thermostable teflonized cell with a volume
of 8L under constant mechanical agitation was used.
NiB plating used the formulation developed by Delaunois et al.
[28] and was carried out at 95  1  C. The bath was composed of
nickel chloride hexahydrate (NiCl2.6H2O) as nickel source and
sodium borohydride (NaBH4) as reducing agent. Ethylenediamine
(NH2–CH2–CH2–NH2), Sodium hydroxide (NaOH) and lead tung-
state (PbWO4) were respectively used as complexing agent, pH
adjuster and stabilizer. The coatings obtained with this solution
have been largely described [22,23,31,49,53,56,58–65]. They
present a boron content close to 6 wt. %, a hardness in the as
plated state close to 850 hv100, very good adhesion to the
substrate and high wear resistance with a TWI of 11.4 with CS-10
wheels under a load of 1 kg.
Electroless nickel mid-phosphorus deposition was carried out
at 88  1  C with a commercial bath (Niklad ELV 808A and Niklad
ELV 808 B from Mc Dermid) that produces a nickel coating with 7–
9 wt. % P.
The ten successive layers of the duplex coatings were made in
sequence: two sample were coated simultaneously and were
immersed alternatively in each bath in 6 minutes increments so
that no bath was left without a sample for more than a few seconds
during the plating process. The total deposition time was one hour
(10  6 min). Two samples of single layer NiB and NiP were
produced in the same conditions (plating time: one hour) in order
to obtain a comparison point. The different configurations of
coatings are illustrated in Fig. 1. To simplify understanding,
multilayers were NiB is the first deposited layer will be called NiB
Fig. 1. Summary of the various NiB/NiP coating systems.
\NiP and those where NiP is the first layer (with a NiB top layer) will
be called NiP\NiB.
2.2. Characterization methods
A Scanning Electron Microscope (Hitachi's SU8200) was used to
characterize the surface and cross section morphology of the
samples. Cross sections were prepared by grinding with emery
paper up to 2400 grit, followed by polishing with diamond paste up
to mirror finish and etching with Nital 10%. The elemental
composition and the depth profiles of electroless nickel coatings
were determined by Radio Frequency Glow Discharge Optical
Emission Spectroscopy (RF-GD-OES) using a HORIBA Jobin Yvon
GD-Profiler 2.
The measurement of the surface roughness was achieved by a
method of mechanical contact. The apparatus used, a Zeiss 119
SURFCOM 1400D-3DF, measures the roughness by the displace-
ment of a stylus with a load of 0.01N on the sample surface. The
values of roughness presented are the average of ten measure-
ments. Instrumented Vickers micro hardness testing was per-
formed using a Mitutoyo HM-200 equipment, with the following
test parameters: load of 100 gf applied for 20 seconds, on the
surface of samples. The values presented in this paper are the
average of ten measurements.
The tribological behavior of the samples was investigated using
two different equipment. A pin-on-disk CSM microtribometer
(without the use of lubricants) where the coated samples served as
the disks and the counterparts were 6 mm diameter alumina balls
with hardness of 1400 HV. The sliding speed, sliding distance and
normal load were, respectively, 10 cm/s, 100 m and 10 N. Addition-
ally, to quantify the abrasive wear characteristics of the coatings, a
circular abrader (5155 Taber Industries) equipped with CS-17
abrasive rubber wheels with 1000 g of applied load and a rotating
speed of 72 rpm was used. The abrasion tests were carried out for
10  1000 cycles with weigh characterization and wheel refacing
every 1000 cycles. The abrasion results will be presented as the
Taber Wear Index (TWI), that is the relation between the weight
lost during the entire test duration (mg) and the number of wear
cycles (of 1000 rotations each) that the sample was submitted to.
A CSEM scratch tester machine with a diamond Rockwell stylus
with a radius of 200 mm was used to perform scratch tests. A
linearly increasing load from 0 to 150 N was employed in all cases,
with a scratch velocity of 6.75 mm/min. The scratch distance was
set at 10 mm. The scratched substrate was optically analyzed by a
Hirox KH-8700 Digital Microscope in order to assess in detail the
damage features. A good notion of the deposit adhesion between
distinct layers can be reached with this method.
Corrosion characterization was performed by Potentiodynamic
polarization curves in 0.1 M NaCl solution was obtained with a Bio-
logic SP-50. Before the polarisation analysis, a steeling time of
20 minutes at OCP (Open Circuit Potential) was observed. Platinum
plate and Ag/AgCl (KCl saturated) electrode were used as counter
 V. Vitry, L. Bonin / Electrochimica Acta 243 (2017) 7–17
and reference electrodes, respectively. A potential range of 0.6 V
Vs OCP, at 1 mV/s scan rate, was employed. Additionally, salt spray
tests were realized in a Q-FOG Cyclic corrosion tester, the samples
were suspended in a cabinet and exposed to a 50 g/l  5 g/l NaCl
solution. The air pressure of the atomized saline solution was
maintained in the range of 6–8 Bar. Salt spray were carried out until
80% of the surface of the samples was corroded according to ISO
9227 standard.
3. Results and discussion
3.1. Structural and morphological characterization
Surface morphology of NiP\NiB, NiB\NiP and monolayer coat-
ings is presented in Fig. 2. Monolayer coatings present typical
features for this type of coatings: a uniform surface exempt of
sharp features with faint waviness and conservation of the
substrate topography for NiP (Fig. 2c) and a cauliflower-like
surface texture in the case of NiB (Fig. 2b). The NiB\NiP multilayer
(Fig. 2a) coating presents a morphology very similar to the
cauliflower-like texture of nickel-boron due to the high ability of
nickel-phosphorus to conserve the topography of the underlying
material. The morphology of the NiP\NiB coating (Fig. 2b) however,
is rather different, with the presence of islands that present, when
big enough a tendency towards cauliflower-like appearance.
Cross section observation of the coatings is presented on Fig. 3.
Nickel-boron monolayer (Fig. 3d) presents the typical columnar
morphology, while no features can be distinguished in the nickel-
phosphorus monolayer (Fig. 3c). This is conserved for the
multilayer coatings, with a sharp delimitation of the successive
layers (Figs. 3a and b): all NiB layers present columnar features and
all NiP is featureless. All layers are continuous and only the final
Fig. 2. Surface morphology of electroless Ni–P/Ni–B multilayer and monolayer coatings.
9
NiB layer deposited on the NiP\NiB sample appears to present
significant thickness variation.
The thickness of the full coatings as well as individual layers
was measured by image analysis, and is presented on Table 1. The
average thickness of all the coating systems is similar (there is less
than 1.5 mm difference between the thicker and thinner coating). It
appears that the average plating rate of the nickel-boron deposit
was slightly higher (19.5 mm/h) than that of nickel-phosphorus
(18.5 mm). The multilayer coatings present thus expectedly an
intermediate thickness.
Observation of the evolution of layer thickness brings
interesting information about the plating process. As shown on
Fig. 4 (Fig. 4a and b), the thickness of individual NiP layers is close
to 1.5 mm throughout the plating process and shows only limited
variation (a decrease of 15%) after the first half our of plating. This is
typical of an industrial bath where constant plating rate is a
demand of the users. This is due to a very strong complexation and
stabilization typical of commercial baths. In the case of NiB, the
evolution is much more significant, with thickness higher than 2.5
microns for the first four layers and a final layer of only one micron
(which represents a 60% decrease). The decrease of plating rate
observed in the case of nickel-boron has been documented on the
specific bath used in this study [29,66] and is linked with decrease
of reactive concentration with time due to consumption in a non-
replenished bath. The strongly decreased plating rate at the end of
the deposition process explains the presence of an island
morphology on the surface of the NiP\NiB coating: this kind of
morphology is observed for thin NiB coatings [66].
3.2. Profile chemistry
Depth profile chemical analysis of all layers, obtained by
GDOES, is presented in Fig. 5. The average chemistry of the NiP and
10 V. Vitry, L. Bonin / Electrochimica Acta 243 (2017) 7–17

Fig. 3. cross-section morphologies of electroless Ni–P/Ni–B multilayer and monolayer coatings.

Table 1
% at all times while the lead content stays at 0.5 wt.%. This,
Coating thickness of electroless Ni–P/Ni–B multilayer and monolayer coatings (in compared with the results of the thickness measurement, shows
mm). that the nickel boron-bath was optimized for conservation of
chemistry while nickel-phosphorus was probably optimized for
Sample NiB\NiP NiP\NiB NiP NiB
constant plating rate.
Thickness (mm) 18.4  0.5 18.5  0.5 18.2  0.3 19.5  0.3
This difference of behavior between the two plating baths is
also observed for the multilayer coatings (Figs. 5a and b): the
NiB alloys were derived from the measurements carried out on chemistry of all NiB layers is very similar (except for the top layer of
monolayers. The phosphorus content of the NiP (Fig. 5c) coating the NiP\NiB) but this may be due to the thickness of the coating
tends increase during the plating process and approximately 7 wt. while the phosphorus content of NiP layers tends to increase
% at the beginning of the process to more than 8 wt.% after one during the plating process.
hour. The chemistry of the nickel-boron coating (Fig. 5d) however Depth profile analysis reveals that the NiP\NiB interfaces are
does not change with time and the boron content is close to 6.5 wt. sharper when NiP is underneath NiB than in the reverse

Fig. 4. Thickness of the layers: (a)sample NiB\NiP, (b)sample NiP\NiB.

 V. Vitry, L. Bonin / Electrochimica Acta 243 (2017) 7–17 11

Fig. 5. Depth profile chemical analysis of electroless Ni–P/Ni–B multilayer and monolayer coatings.

configuration. This is due to the textured surface of nickel-boron
coatings, that offer a less planar interface than NiP.
3.3. Hardness
Surface microhardness of all coated systems is presented in
Table 2. The use of surface hardness testing rather than cross
section testing in this study is justified by the need to obtain
information about the composite system rather than about
individual layers. The hardness of single layers was measured in
a similar manner to obtain a reliable comparison point (a value
obtained in the same conditions). Nickel-boron monolayers are
expectedly harder than nickel-phosphorus. The hardness mea-
sured on multilayer coatings is similar to that of nickel-phosphorus
when it constitutes the top layer (NiB\NiB systems) and is
significantly higher when NiB is the top layer (NiP\NiB) systems.
This behavior is linked to the prevailing influence of the first layer
on the hardness testing results.
3.4. Roughness and wear characterization
Roughness of all samples has also been measured and the main
roughness parameters (Ra and Rp) are shown in Table 2. The lowest
Ra value is obtained for the monolayer NiB coating and the
multilayer coatings present higher roughness than both the
monolayers. This is probably due to the presence of several NiB
layers. However, the Rp value (mean of the 5 highest peaks) is
lower for the NiP coating, which suggests a more regular
roughness. Similarly, Rp values are higher for multilayers than
for monolayers and the NiB\NiP coating presents a lower Rp than
NiP\NiB. It is interesting to note than the Ra value of all the coated
systems stays close to that of the substrate (that is close to 0.2 mm)
and never exceeds 0.2 mm, which is a very acceptable value for
most applications.
The friction coefficient after 100 m of sliding wear test of the
coated systems (see Table 2) is slightly lower than that of the
monolayers but stays is a similar ranger (between 0.45 and 0.6).

Table 2
Hardness, roughness, friction coefficient and wear resistance of electroless Ni–P/Ni–B multilayer and monolayer coatings.

Sample NiB\NiP NiP\NiB NiP NiB

Hardness hv100 507  16 630  23 502  7 857  38
Roughness Ra (mm) 0.164  0.008 0.161  0.011 0.145  0.009 0.118  0.012
Roughness Rp (mm) 1.483  0.018 2.205  0.017 0.553  0.015 0.841  0.013
Friction coeficient m (after 100 m) 0.46 0.50 0.60 0.54
TWI 9.6 11.6 34.5 27.3
Ws (mm2/N) 0.17 0.22 1.32 0.63
wear tracks width (mm) 170.5 175.7 271.9 200.7
12 V. Vitry, L. Bonin / Electrochimica Acta 243 (2017) 7–17
This decrease can be explained by the increased roughness of the
multilayer coatings which provide a reduced contact area. This is
confirmed by Fig. 6 on which the evolution of the friction
coefficient during sliding wear test is presented: the friction
coefficient of the rougher samples is lower at the beginning of the
test. The friction coefficient of NiP monolayer increases and
stabilizes for a sliding distance lower than 10 m due to lower
roughness and increased wear. However, that of the other samples
increases continuously during the test and is not fully stabilized
after a sliding distance of 100 m. This behavior is linked with the
cauliflower-like texture of the surface of those samples.
The Taber Wear Index (TWI) values of all samples are shown in
Table 2. A lower TWI is indicative of better wear resistance. The
abrasive wear resistance of NiB monolayer is better than that of
NiP, in accordance to previous results [23]. Likewise, the use of
multilayer electroless nickel coatings induces an important
increase of the wear resistance: the TWI is divide by 2 to 3
compared to monolayers. Both types of multilayers have similar
TWI (close to 10). This decrease of abrasive wear is most probably
linked to alternation of NiP and NiB layers in the coatings and the
presence of interfaces: As shown on Fig. 7, the weight lost during
the first 1000 cycles is more important for multilayer coatings than
for monolayers. On the other hand, after 1000 cycles, the weight
loss measured for multilayers is very much decreased while
monolayers keep wearing at a similar rate.
Sliding wear presents similar evolution to abrasive wear: NiP
monolayers have the highest wear rate and presents a specific
wear rate twice as large as that of NiB monolayer. Those results are
in accordance with published literature [65]. The specific wear rate
of multilayer is much lower than that of monolayers. This is
probably linked to the reduction of friction coefficient linked with
the increased of the roughness and mainly to the increase in peak
height. Wear tracks are shown on Fig. 8. The width of the wear
track formed on monolayer NiP (Fig. 8c) is clearly bigger (271.9 mm,
see Table 2) than on the other samples (170–200 mm) and there are
deep grooves in the wear track. The marks present in the wear
track formed on monolayer NiB (Fig. 8d) are less deep and more
regular than those formed on monolayer NiP, confirming the better
wear resistance. The multilayer coatings (Figs. 8a and b) present
only regular parallel wear marks. Careful observation of the wear
track revealed that no debris were present in the wear track.
Fig. 6. Evolution of friction coefficient during sliding wear test.
3.5. Scratch test
Global aspects of the samples after scratch test are presented on
Fig. 9. As can be seen, there is no evidence of scaling or spallation
for any of the coated systems. Fig. 10 presents the types of damage
observed on the various coatings and the loads at which they
appear. The first thing that can be observed from Fig. 10 is that
critical load for first damage varies depending on the type of
coating, with the first deposited layer being the most influent
parameter. Damage appears from 4 to 9 N on coatings where NiP is
deposited directly on steel (monolayer NiP and multilayer NiP/NiB)
and the critical load increases to more than 27 N when NiB is
deposited directly on steel (respectively 27 N for the multilayer
NiB/NiP and 35 N for NiB monolayer). The higher value obtained for
the monolayer NiB coating can be explained by the absence of NiP
in the system: it has been previously shown that the adhesion of
NiP coatings on steel substrates is lower than that of NiB [23,65].
The type of damage varies also with the type of coating. Fig. 11
presents the three types of damage that were observed on
electroless nickel monolayers and multilayers. Fig. 11a presents
chevron cracks at the edge of the scratch; Fig. 11b presents
transverse tensile cracking, accompanied by chevron cracks at the
edges of the scratch; Fig. 11c presents a combination of transverse
and longitudinal cracks at the bottom of the scratch. It is important
to note that all those failure modes are linked with cohesive failure
[67,68], which is expected because our system presents a coating
much harder than the substrate [69].
In all cases (see Fig. 10), the first type of damage that occurs is
chevron cracks at the edge of the scratch that are due to tensile
cohesive failure of the coating. Afterwards, all coatings present
transverse tensile cracking. Once again, the critical load for this
type of damage varies with the type of coating from 11.5N for NiP
monolayer to nearly 70N for NiB monolayer. Multilayers present
this kind of damage from loads higher than NiP (19 and 33 N for NiB
\NiP and NiP\NiB respectively). Coatings that contain NiP present
increased damage after the transversal cracks: a combination of
transverse and longitudinal cracks that appears for loads in the 40–
55 N range. This type of damage is not observed for monolayer
nickel-boron. The lesser damage observed on this coating is linked
with the columnar microstructure that allows better adaptation of
the coating to the deformation induced by the scratching process.
 V. Vitry, L. Bonin / Electrochimica Acta 243 (2017) 7–17 13

Fig. 7. Samples weight loss evolution as a function of the number of abrasion cycles.

Fig. 8. sliding wear tracks on electroless Ni–P/Ni–B multilayer and monolayer coatings.

3.6. Corrosion
Fig. 12 present potentiondynamic polarization curves for all the
coated systems as well as for the uncoated mild steel substrate. The
corrosion potential of all the coated samples is very similar, close to
0.4 V Vs Ag/AgCl (KCl saturated). Likewise, the cathodic part of
the polarization curve is very similar for all coated systems.
However, there are slight variations in the anodic side. The systems
where NiP constitutes the top layer (Monolayer NiP and NiB\NiP)
present a tendency to passivation to 0.2 V Vs Ag/AgCl (KCl
saturated). Monolayer NiB presets a tendency towards passivation
only up to 0.2 V Vs Ag/AgCl (KCl saturated). The NiP\NiB system
presents an intermediate behavior and presents passive tendency
up to 0 V Vs Ag/AgCl (KCl saturated).
As it is very difficult to differentiate the coated systems in terms
of corrosion resistance from the results of the polarization tests,
salt spray tests were carried out. All coated systems presented an
important increase of salt spray resistance compared to steel, as
can be seen on Table 3. The resistance of monolayer NiB was
500 hours while that of all the other coated systems exceeded
840 hours. The experiment was interrupted after 840 hours (35
days) for technical reasons. The aspect of coated samples after
14 V. Vitry, L. Bonin / Electrochimica Acta 243 (2017) 7–17

Fig. 9. Observation of the scratch tracks up to 150 N on as-deposited electroless Ni–P/Ni–B multilayer and monolayer coatings.

Fig. 10. Critical loads for the damage features of the different coating systems.

Fig. 11. Typical damage observed on electroless nickel coating systems. Examples of a chevron cracks; b transverse cracks; c transverse and longitudinal cracks.

840 hours of salt spray exposure is shown on Fig. 13. The sample
coated with monolayer NiB (Fig. 13d) is completely corroded and
the one coated with monolayer NiP (Fig. 13c) does not present any
sign of corrosion. The multilayer systems (Figs. 13a and 13b)
present traces of corrosion on less than 20% of the exposed area.
The NiP\NiB system (Fig. 13b) appears to have a better corrosion
resistance than NiB\NiP (Fig. 13a).
The difference in corrosion resistance between NiP and NiB can
be explained by the formation of hypophosphite due to the
oxidation of the phosphorus present at the coating surface.
According to Diegle [70], preferential dissolution of nickel occurs in
NiP coatings, even at the open circuit potential, leading to the
formation of a phosphorus-enriched surface layer. This layer then
reacts with water to form a layer of adsorbed hypophosphite
anions that act as a barrier between the electrolyte and the
electrode surface and prevents the hydratation of nickel, which is
the first step in the formation of a passive film.
The intermediate behavior of multilayer coatings can be
explained by the same phenomenon but on a smaller scale. The
presence of multiple interfaces is also a favorable factor because
they decrease the probability of through coating porosity that are
one of the main factors affecting the corrosion resistance of
electroless nickel-boron coatings [60].
4. Conclusions
Multilayer electroless nickel were investigated in this study, as
alternative to monolayer coatings, with the aim of combining the
 V. Vitry, L. Bonin / Electrochimica Acta 243 (2017) 7–17 15

Fig. 12. Potentiodinamic polarization curves, 0.1 M NaCl, of electroless Ni–P/Ni–B multilayer and monolayer coatings.

Table 3 resistance. This is accompanied by a slight decrease of the friction

Time of exposure to salt spray to reach 80% of corroded surface (salt spray resistance
according to ISO 9227 standard).
Exposure time to salt spray
Steel
NiP monolayer
NiB monolayer
Multilayer with NiP on top
Multilayer with NiB on top
good wear resistance of NiB coatings with the corrosion resistance
of NiP coatings.
The morphological features of the multilayer coatings com-
bined those of both kinds of monolayers (dimensional compliance
and cauliflower-like texture). The nickel-phosphorus layers
presented a stable thickness throughout the coating but an
increase in their phosphorus content. The nickel-boron layers
presented a decrease of the thickness from the first deposited layer
to the surface of the coated system but their boron and lead
content were stable throughout the plating operations.
The hardness of the multilayer systems is closer to that of NiP
than to NiB. However, the sliding and abrasive wear resistance of
multilayer systems is much better than that of any of the
monolayers, even nickel-boron that is known for its good wear
coefficient.
The corrosion resistance of the multilayer systems, measured
by salt spray testing, is much better than that of nickel-boron
4 hours monolayer and is nearly as good as that of nickel-phosphorus (mid-
>840 hours phosphorus monolayer).
500 hours The use of multilayer electroless nickel coatings, composed of
>840 hours
mid-boron and mid-phosphorus coatings (respectively 6 wt. % B
>840 hours
and 7–9 wt.% P) allowed to combine wear and corrosion resistance
and even to improve the wear resistance compared to the best
electroless nickel coating used in this study. The use of such
systems will thus open new areas of application to electroless
nickel plating, that require simultaneous resistance to wear and
corrosion.
Acknowledgements
The authors wish to thank M Jules Viaud for his involvement in
the experimental process, as well the Laboratory of Physics of
Surfaces and Interfaces and the Materials Science Laboratory at
UMONS for the use of their equipment. They’re also grateful to
Horiba-Jobin-Yvon who carried out the GDOES experiments and to
INISMa-BCRC for the scratch testing. One of the authors (L. Bonin)
wishes to thank CNPq for funding.

Fig. 13. Surface aspect of electroless Ni–P/Ni–B multilayer and monolayer coatings after 840 h salts spray.
16 V. Vitry, L. Bonin / Electrochimica Acta 243 (2017) 7–17
References
[1] A. Riedel, Electroless nickel plating, Finishing Publication LTD., London, 1989.
[2] D.S. Rickerby, A. Matthews, Advanced Surface Coatings: A Handbook of Surface
Engineering, Blackie, Glasgow, 1991.
[3] G.O. Mallory, J.B. Hajdu, Electroless Plating: Fundamentals and Applications,
AESF, Orlando, 1991.
[4] D. Baudrand, B. Durkin, Automotive Applications of Electroless Nickel, Met.
Finish. 96 (1998) 20.
[5] J.N. Balaraju, K.S. Rajam, Electroless Deposition of Ni-Cu-P Ni-W-P and Ni-W-
Cu-P Alloys, J. Surf. Coat. Technol. 195 (2005) 154.
[6] G.F. Huang, W.Q. Huang, L. Wang, Y. Meng, et al., Electrochemical Study of
Electroless Deposition of Fe-P Alloys, Electrochim. Acta. 51 (2006) 4471.
[7] H. Dai, H. Li, F. Wang, An Alternative Process for the Preparation of Cu-Coated
Mica Composite Powder, J. Surf. Coat. Technol. 201 (2006) 2859.
[8] J. McCaskie, S. Redding, Successful Automotive Applications for Electroless
Nickle, J. Metal Finish. 106 (2008) 25.
[9] R. Parkinson, Properties and Applications of Electroless Nickel, Nickel
Development Institute, 1997.
[10] F.L. Miguel, H. Shen, F. Soldera, T. Fischer, R. Müller, S. Mathur, F. Mücklich,
Electroless deposition of a Ag matrix on semiconducting one-dimensional
nanostructures, Thin Solid Films 536 (2013) 54.
[11] Y. Ye, T.L. Guo, Effect of MWNT electroless Ag plating on field emission
properties of MWNT/Ag nanocomposite cathodes, Appl. Surf. Sci. 264 (2013)
593.
[12] M.N. Álvaro, T.C. Vicente, M.P. Raúl, H.F. Pilar, Á.G. Miguel, F. Kazuhiro, O. Yukio,
M.S. Miguel, Electroless nanoworm Au films on columnar porous silicon layers,
Mater. Chem. Phys. 134 (2012) 664.
[13] D.J. Chen, B.L. Xu, S.G. Sun, Y.Y.J. Tong, Electroless deposition of ultrathin Au
film for surface enhanced in situ spectroelectrochemisrty and reaction-driven
surface reconstruction for oxygen reduction reaction, Catal. Today 182 (2012)
46.
[14] F. Inoue, H. Philipsen, A. Radisic, S. Armini, Y. Civale, P. Leunissen, M. Kondo, E.
Webb, S. Shingubara, Electroless Cu deposition on atomic layer deposited Ru as
novel seed formation process in through-Si vias, Electrochim. Acta 100 (2013)
203.
[15] T. Lim, M.J. Kim, K.J. Park, K.H. Kim, S. Choe, Y.S. Lee, J.J. Kim, The effect of
inducing uniform Cu growth on formation of electroless Cu seed layer, Thin
Solid Films 564 (2014) 299.
[16] Y.Q. Huang, H.L. Huang, Q.Z. Gao, C.F. Gan, Y.J. Liu, Y.P. Fang, Electroless
synthesis of two-dimensional sandwich-like Pt/Mn3O4/reduced-graphene-
oxide nanocomposites with enhanced electrochemical performance for
methanol oxidation, Electrochim. Acta 149 (2014) 34.
[17] J.Y. Lin, Y.T. Lin, Electroless platinum counter electrodes with Pt-activated self-
assembled monolayer on transparent conducting oxide, Surf. Coat. Technol.
206 (2012) 4672.
[18] G.G. Gawrilov, Chemical (Electroless) Nickel Plating, Portcullis Press, Redhill,
England (1979).
[19] M. Paunovic, M. Schlesinger, Chapter 6: Kinetics and Mechanism of
Electrodeposition, in Fundamentals of Electrochemical Deposition, Second
Edition, John Wiley & Sons, Inc, Hoboken, NJ, USA, 2006, pp. 77–112.
[20] F. Delaunois, P. Lienard, Heat treatments for electroless nickel boron plating
on aluminium alloys, Surf. Coatings Technol. 160 (2002) 239.
[21] V. Vitry, F. Delaunois, C. Dumortier, How heat treatment can give better
properties to electroless nickel-boron coatings, Metall. Ital. 101 (2009).
[22] V. Vitry, F. Delaunois, C. Dumortier, Mechanical properties and scratch test
resistance of nickel-boron coated aluminium alloy after heat treatments, Surf.
Coatings Technol. 202 (2008) 3316.
[23] V. Vitry, A. Sens, F. Delaunois, Comparison of Various Electroless Nickel
Coatings on Steel: Structure, Hardness and Abrasion Resistance, Mater. Sci.
Forum. 783-786 (2014) 1405.
[24] Y.N. Bekish, S.K. Poznyak, L.S. Tsybulskaya, T.V. Gaevskaya, Electrodeposited
Ni-B alloy coatings: Structure, corrosion resistance and mechanical properties,
Electrochim. Acta. 55 (2010) 2223.
[25] K.H. Lee, D. Chang, S.C. Kwon, Properties of electrodeposited nanocrystalline
Ni-B alloy films, Electrochim. Acta. 50 (2005) 4538.
[26] K. Krishnaveni, T.S.N. Sankara Narayanan, S.K. Seshadri, Electroless Ni-B
coatings: Preparation and evaluation of hardness and wear resistance, Surf.
Coatings Technol. 190 (2005) 115.
[27] M. Anik, E.K. Eskisehir, Effect of alloy microstructure on electroless NiP
deposition behavior on Alloy AZ91, Surf. Coatings Technol. 201 (2007) 4702.
[28] F. Delaunois, J.P. Petitjean, P. Lienard, M. Jacob-Duliere, Autocatalytic
electroless nickel-boron plating on light alloys, Surf. Coatings Technol. 124
(2000) 201.
[29] V. Vitry, F. Delaunois, Formation of borohydride-reduced nickel-boron
coatings on various steel substrates, Appl. Surf. Sci. 359 (2015) 692.
[30] D. Yan, G. Yu, B. Hu, J. Zhang, Z. Song, X. Zhang, An innovative procedure of
electroless nickel plating in fluoride-free bath used for AZ91D magnesium
alloy, J. Alloys Compd. 653 (2015) 271.
[31] V. Vitry, F. Delaunois, Nanostructured electroless nickel-boron coatings for
wear resistance, Anti-Abrasive Nanocoatings, Elsevier, 2015, pp. 157–199.
[32] F. Madah, A.A. Amadeh, C. Dehghanian, Investigation on the phase
transformation of electroless Ni-B coating after dry sliding against alumina
ball, J. Alloys Compd. 658 (2016) 272.
[33] E. Correa, A.A. Zuleta, L. Guerra, M.A. Gómez, J.G. Castaño, F. Echeverría, H. Liu,
A. Baron-Wieche c, T. Hashimoto, P. Skeldon, G.E. Thompson, Coating
development during electroless Ni-B plating on magnesium and AZ91D alloy,
Surf. Coatings Technol. 232 (2013) 784.
[34] F. Madah, A.A. Amadeh, C. Dehghanian, Investigation on the phase
transformation of electroless Ni-B coating after dry sliding against alumina
ball, J. Alloys Compd. 658 (2016) 272.
[35] S. Kundu, S.K. Das, P. Sahoo, Properties of electroless nickel at elevated
temperature-a review, Procedia Eng 97 (2014) 1698.
[36] J.N. Balaraju, S.K. Seshadri, M.S. Division, N.A. Laboratories, M. Centre,
Electroless Ni P composite coatings, J. Appl. Electrochem. 33 (2003)
807.
[37] F. Bigdeli, S.R. Allahkaram, An investigation on corrosion resistance of as-
applied and heat treated Ni-P/nanoSiC coatings, Mater. Des. 30 (2009) 4450.
[38] M. Zhang, S. Mu, Q. Guan, W. Li, J. Du, A high anticorrosive chromium-free
conversion coating prepared with an alkaline conversion bath on electroless
Ni-P coating, Appl. Surf. Sci. 349 (2015) 108.
[39] M. Sribalaji, P. Arunkumar, K.S. Babu, A.K. Keshri, Crystallization mechanism
and corrosion property of electroless nickel phosphorus coating during
intermediate temperature oxidation, Appl. Surf. Sci. 355 (2015) 112.
[40] Y.N. Bekish, S.K. Poznyak, L.S. Tsybulskaya, T.V. Gaevskaya, Electrodeposited
Ni-B alloy coatings: Structure, corrosion resistance and mechanical properties,
Electrochim. Acta. 55 (2010) 2223.
[41] J.N. Balaraju Praful Radhakrishnan, V. Ezhilselvi, A. Anil Kumar, Z. Chen, K.P.
Surendran, Studies on electroless nickel polyalloy coatings over carbon fibers/
CFRP composites, Surface & Coatings Technology 302 (2016) 389.
[42] H. Zhao, Y. Lu, Comparative study of electroless nickel film on different organic
acids modified cuprammonium fabric (CF), Applied Surface Science 362 (2016)
154.
[43] S. Fujii, H. Hamasaki, H. Takeoka, T. Tsuruoka, K. Akamatsu, Y. Nakamura,
Electroless nickel plating on polymer particles, Journal of Colloid and Interface
Science 430 (2014) 47.
[44] K.G. Keong, W. Sha, S. Malinov, Crystallisation kinetics and phase
transformation behaviour of electroless nickel-phosphorus deposits with
high phosphorus content, J. Alloys Compd. 334 (2002) 192.
[45] J.N. Balaraju, T.S.N. Sankara Narayanan, S.K. Seshadri, Structure and phase
transformation behaviour of electroless Ni-P composite coatings, Mater. Res.
Bull. 41 (2006) 847.
[46] T. Saito, E. Sato, M. Matsuoka, C. Iwakura, Electroless deposition of Ni B, Co
B and Ni Co B alloys using dimethylamineborane as a reducing agent, 28
(1998) , pp. 559.
[47] J. Sudagar, J. Lian, W. Sha, Electroless nickel, alloy, composite and nano coatings
A critical review, Journal of Alloys and Compounds 571 (2013) 183.
[48] E. Ramírez-meneses, A.M. Torres-huerta, M.A. Domínguez-crespo, Synthesis
and Electrochemical Characterization of Ni Nanoparticles by Hydrazine
Reduction using Hydroxyethyl cellulose as Capping Agent, Electrochimica Acta
127 (2014) 228.
[49] F. Delaunois, V. Vitry, Electroless Nickel-Boron Coatings: Process, Composition,
Microstructure, and Properties, in: G.E. Totten, R. Colas (Eds.), Encyclopedia of
Iron, Steel, and Their Alloys, CRC Press, Taylor and Francis Group, 2015.
[50] W.X. Zhang, Z.H. Jiang, G.Y. Li, Q. Jiang, J.S. Lian, Electroless Ni-P/Ni-B duplex
coatings for improving the hardness and the corrosion resistance of AZ91D
magnesium alloy, Applied Surface Science. 254 (2008) 4949.
[51] K.N. Srinivasan, R. Meenakshi, A. Santhi, P.R. Thangavelu, S. John, Studies on
development of electroless Ni-B bath for corrosion resistance and wear
resistance applications, Surf. Eng. 26 (2010) 153.
[52] T.S.N. Sankara Narayanan, K. Krishnaveni, S.K. Seshadri, Electroless Ni-P/Ni-B
duplex coatings: preparation and evaluation of microhardness, wear and
corrosion resistance, Materials Chemistry and Physics 82 (2003) 771.
[53] V. Vitry, A. Sens, A.-F. Kanta, F. Delaunois, Wear and corrosion resistance of heat
treated and as-plated Duplex NiP/NiB coatings on 2024 aluminum alloys,
Surface & Coatings Technology. 206 (2012) 3421.
[54] L. Bonin, V. Vitry, Mechanical and wear characterization of electroless nickel
mono and bilayers and high boron-mid phosphorus electroless nickel duplex
coatings, Surface & Coatings Technology 307 (2016) 957.
[55] V. Vitry, F. Delaunois, Nanostructured Electroless nickel-boron deposition:
initiation mechanism and formation, effect of bath chemistry modification, in:
M. Aliofkhazraei (Ed.), Comprehensive Guide for Nanocoatings Technology:
Volume 3: Properties and Development, 2015, pp. 283–308.
[56] V. Vitry, A.-F. Kanta, F. Delaunois, Influence of local composition on
morphology of electroless nickel-boron deposits on mild steel, Prakt.
Metallogr. 42 (2010) 315.
[57] V. Vitry, A.F. Kanta, F. Delaunois, Initiation and formation of electroless nickel-
boron coatings on mild steel: Effect of substrate roughness, Mater. Sci. Eng. B
Solid-State Mater. Adv. Technol. 175 (2010) 266.
[58] A.F. Kanta, V. Vitry, F. Delaunois, Wear and corrosion resistance behaviours of
autocatalytic electroless plating, J. All.Compds 486 (1-2) (2009) L21.
[59] A.F. Kanta, V. Vitry, F. Delaunois, Effect of thermochemical and heat treatments
on electroless nickel-boron, Mater. Lett. 63 (2009) 2662.
[60] A.F. Kanta, M. Poelman, V. Vitry, F. Delaunois, Nickel-boron electrochemical
properties investigations, J. Alloys Compd. 505 (2010) 151.
[61] A.-F.F. Kanta, V. Vitry, F. Delaunois, Wear and Corrosion Resistance of
Electroless Nickel-Boron Coated Mild Steel, Mater. Sci. Forum. 638 (2010) 846.
[62] V. Vitry, A.F. Kanta, F. Delaunois, Mechanical and wear characterization of
electroless nickel-boron coatings, Surf. Coatings Technol. 206 (2011) 1879.
 V. Vitry, L. Bonin / Electrochimica Acta 243 (2017) 7–17
[63] V. Vitry, A.F. Kanta, A. Sens, F. Delaunois, Tribological Characterization of
Electroless Nickel-Boron Coatings, Adv. Mater. Res. 409 (2011) 808.
[64] V. Vitry, A.F. Kanta, J. Dille, F. Delaunois, Structural state of electroless nickel-
boron deposits (5 wt.%B): Characterization by XRD and TEM, Surf. Coatings
Technol. 206 (2012) 3444.
[65] V. Vitry, F. Delaunois, Electroless nickel-phosphorus Vs electroless nickel-
boron: comparison of hardness, abrasion resistance, scratch test response and
corrosion behavior, in: M. Aliofkhazraei (Ed.), Comprehensive Guide for
Nanocoatings Technology, Volume 1: Deposition and Mechanism, Nova
Science Publishers, 2015, pp. 145–173.
[66] V. Vitry, A. Sens, A.F. Kanta, F. Delaunois, Experimental study on the formation
and growth of electroless nickel-boron coatings from borohydride-reduced
bath on mild steel, Applied Surface Science 263 (2012) 640.
17
[67] C. Subramanian, E. Pallotta, Two-body abrasive wear ofelectroless nickel
composite coatings, Tribol. Lett. 2 (1996) 133.
[68] J. Tomastik, R. Ctvrtlik, Nanoscratch test ?A tool for evaluation of cohesive and
adhesive properties of thin films and coatings EPJ Web of Conferences (2013)
00027 48.
[69] S.J. Bull, E.G. Berasetegui, An overview of the potential of quantitative coating
adhesion measurement by scratch testing, Tribol. Int. 39 (2006) 99–114.
[70] R.B. Diegle, N.R. Sorensen, C.R. Clayton, M.A. Helfand, Y.C. Yu, An XPS
Investigation into the Passivity of an Amorphous Ni-20P Alloy, J Electrochem.
Soc. 135 (1988) 1085.