Chemical Engineering Science 207 (2019) 1299–1308

Contents lists available at ScienceDirect

Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Deposition mechanism of electroless nickel plating of composite

coatings on magnesium alloy
Wei Shang a,1, Xiaoqiang Zhan a,1, Yuqing Wen a,⇑, Yuqing Li a, Zhe Zhang a, Fang Wu a, Chunlei Wang b,⇑
a
Guangxi Key Laboratory of Electrochemical and Magnetochemical Function Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, China
b
Department of Mechanical and Materials Engineering, College of Engineering and Computing, Florida International University, Miami, USA

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Nickel growth was obtained by

changes in morphology and element
at 6 different time.

Change of surface composition is
tested by XRD to infer reaction at 6
plating time.

Deposition mechanism is concluded
by morphology and structure at 6
plating time.

a r t i c l e i n f o a b s t r a c t

Article history: To investigate the deposition mechanism of the outermost electroless nickel plating layer in a three-layer
Received 21 January 2019 composite coatings on the magnesium alloy surface, the electroless nickel plating layers with six different
Received in revised form 11 July 2019 plating times (3, 5, 10, 30, 60, and 90 min) were selected as research targets. The transformations in
Accepted 20 July 2019
microcosmic morphology, element composition and material structure of the samples electrolessly pla-
Available online 22 July 2019
ted at six different plating times were characterized by SEM、EDS and XRD. The changes in corrosion
resistance of samples with different electroless plating times were measured by polarization curve. It
Keywords:
was concluded that the nickel-phosphorus deposition process on the activation composite coatings
Mg alloy
Composite coatings
was a ‘‘cell-like three-dimensional” growth judging from the microscopic morphology of coating surface
Electroless nickel obtained by SEM. The elemental changes obtained from the EDS were consistent with the growth of
Deposition mechanism nickel cells obtained SEM. The XRD results showed that the diffraction peaks of nickel were not detected
on the surface at an electroless plating time of 3 min. Nickel peaks appeared after 5 min of electroless
plating, and the nickel peak width broadened and the intensity increased as the electroless plating time
increased. The corrosion resistance is greatly improved when the electroless plating is performed for
60 min due to the complete nickel coating without defects as shown in the SEM. It can be concluded that
the deposition mechanism of electroless plating on the double-layer active surface is an initial ecological
reduction [H] autocatalytic reduction deposition process according to the micromorphology and struc-
ture of the samples electrolessly plated at six different plating times.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction
⇑ Corresponding authors.
E-mail addresses: 2006027@glut.edu.cn (Y. Wen), wangc@fiu.edu (C. Wang). Mg alloys are known as the ‘‘green engineering materials of the
1
These authors contribute equally. 21st century” and one of the metal materials with the lowest

https://doi.org/10.1016/j.ces.2019.07.048
0009-2509/Ó 2019 Elsevier Ltd. All rights reserved.
1300 W. Shang et al. / Chemical Engineering Science 207 (2019) 1299–1308
density created so far (Correa et al., 2013; Duan et al., 2006). Mg
alloys own many excellent properties, such as good electrical con-
ductivity, excellent electromagnetic shielding, impact resistance,
ease of recycling, and environmental protection (Correa et al.,
2013; Fan et al., 2013; Song et al., 2015; Shang, 2017). In recent
years, Mg alloys have been widely studied in the fields of electron-
ics, chemical engineering, automotive engineering, metallurgy and
aerospace (Guo et al., 2012; Zhang, 2016; Zucchi et al., 2008; Petro
and Schlesinger, 2012). Although Mg alloys have many excellent
properties, its corrosion resistance is extremely poor due to its neg-
ative standard electrode potential, which greatly limits its applica-
tions (Song et al., 2015; Chen et al., 2013; Zeng et al., 2010). At
present, a great deal of research has been conducted on the corro-
sion protection of Mg alloys (Xie et al., 2011; Qi et al., 2018). The
preparation of a composite coatings on the surface of magnesium
alloy using a combination of various methods is considered to be
promising for corrosion protection. In this experiment, three sur-
face treatment technologies, including micro-arc oxidation
(MAO), self-assembly (SAM), and electroless nickel plating (EN)
were combined to successfully prepare a three-layer corrosion
resistant composite coatings on the surface of AZ91D magnesium
alloy.
Micro-arc oxidation (MAO) is a magnesium alloy surface modi-
fication technology with wide application prospects, and the elec-
trolyte can be reused which can reduce the environmental
pollution (Song et al., 2015; Chen et al., 2013). A porous ceramic
oxide coating was formed on magnesium alloys by grown in situ
on its surface treated by MAO. The micropores and microcracks
of the ceramic oxide coating are formed due to the breakdown of
the microarc discharge (Fan et al., 2013; Song et al., 2015). The
bonding strength between the ceramic oxide coating and the mag-
nesium alloy is hard, but the corrosion protection is limited due to
the porous structure and micro cracks on the surface (Guo et al.,
2012; Jian et al., 2016). The poor conductivity of the MAO coating
also constrains the practical application of magnesium alloys.
Self-assembly (SAM) processing is an important surface treat-
ment method in various applications such as electronic devices
and corrosion protection (Zucchi et al., 2008). The self-assembled
film is generally an adsorption effect produced by self-assembled
intermolecular Van der Waals forces and special chemical interac-
tions between specific functional groups spontaneously attached
to some molecular chains to form tightly stable molecular mem-
branes (Zucchi et al., 2008; Luo et al., 2018). Silylation self-
assembly treatment for anti-corrosion applications on the surface
of magnesium alloy is one process that demonstrates the green
environmental advantages. In this work, the self-assembled film
was employed as a barrier to resist the corrosive medium due to
the micro pores from the MAO coating were sealed by the film.
Electroless nickel plating is a surface treatment technology with
a wide range of application prospects, and it has been successfully
applied to the preparation of surface coatings for many metals
(Loto, 2016; Qin et al., 2011; Wang et al., 2013; Georgiza et al.,
2013; Wei et al., 2018). The autocatalytic oxidation-reduction reac-
tion deposits nickel phosphorus by using a potential difference
between a reducing agent and a nickel ion as a driving force
(Tsai and Chao, 2004; Xiang et al., 2017; Gu et al., 2005). The corner
effect issue is totally solved by electroless nickel plating, and the
nickel layer own advantages of uniform deposition, dense plating,
good electrical conductivity, and good solderability (Guo et al.,
2012; Loto, 2016; Elsener et al., 2008). Some researchers have
explored direct electroless nickel plating on the surface of magne-
sium alloy, or added intermediate layers between the magnesium
alloys and the nickel layer to increase the corrosion resistance of
the Mg alloys (Fan et al., 2013; Sudagar et al., 2012). However,
the standard electrode potential difference between magnesium
and nickel is too big, galvanic corrosion would occur once a
through channel was formed between the nickel layer and the
magnesium substrate, which would accelerate the failure of the
coating (Song et al., 2015, 2008). In this experiment, a MAO coating
was firstly prepared on the magnesium alloy surface, and then the
MAO coating was self-assembled to obtain a double-layer compos-
ite coatings. The double-layer composite coatings was then elec-
trolessly plated to obtain a three-layer composite coatings. The
three-layer composite coatings solved the issue of galvanic corro-
sion. The deposition mechanism of the electroless nickel plating
on the double-layer surface was deduced by characterizing micro-
cosmic morphology, element composition and material structure
of samples with electroless plating deposited at different times.
2. Experiment
2.1. Materials and pretreatment
The AZ91D magnesium alloy sheet was cut into
40  40  4 mm sized samples, and a small hole was made in the
middle of the upper end of the sample for connecting the wire.
The substrate was polished with 280#, 600#, 800#, 1000#,
1200# and 1500# metallographic sandpaper in proper order to
make the surface smooth (Gan et al., 2017; Song and Liu, 2012).
The polished magnesium alloy was cleaned with an alkaline
degreasing solution, then the sample was ultrasonically cleaned
with anhydrous ethanol and distilled water. The magnesium alloy
is naturally dried in the air after pretreatment.
2.2. Experiment procedure
The pre-treated magnesium alloy is immersed in electrolyte
solutions, and the sample is connected to the micro-arc oxidation
power source by a wire to carry out the micro-arc oxidation treat-
ment. An acid-free Pd2+ activation method was applied to activate
the coating surface prior to electroless plating (Zhan et al., 2019).
The activated sample is immersed in a self-assembled silane solu-
tion for self-assembly treatment to obtain an activated double-
layer composite coatings. The activated double-layer composite
coatings was immersed in an electroless plating bath to obtain
samples at six different electroless plating times. The composition
and operating conditions of the electroless plating bath are shown
in Table 1.
2.3. Characterization
The microscopic morphology, material composition and proper-
ties of the samples with electroless plating on the activated
double-layer composite coatings surface for six different time peri-
ods were characterized. Scanning electron microscopy (SEM, JSM-
6380L, Japan) was used to observe the micromorphology of the
samples that underwent electroless plating for six different time
periods. The changes in the elemental composition and content
of the coating surface that underwent electroless plating for six dif-
ferent time periods were characterized by an energy-dispersive X-
ray analysis instrument (EDS) associated with the SEM, which rein-
force the nickel-phosphorus growth process concluded from SEM.
Table 1
Electroless plating bath composition and operating conditions.
Electroless plating bath composition Operating conditions
NiSO46H2O 28 g/L
Na2H2PO2H2O 30 g/L Temperature = 70 °C
C6H5Na3O72H2O 25 g/L PH = 6.8
NH4F 15 g/L Medium speed stirring
KI 4 mg/L
CN2H4S 2 mg/L
 W. Shang et al. / Chemical Engineering Science 207 (2019) 1299–1308
An X-ray diffractometer (XRD, X, perPRO, Holland) was used to
detect the nickel diffraction peaks of samples with different elec-
troless deposition times. The hydrophobicity of the surface with
different electroless deposition times is characterized by a static
contact angle meter (XG-CAM, China). The CHI860B (Chenhua,
China) electrochemical workstations was used to carry out polar-
ization curve tests for the samples with six different electroless
deposition times. A classical three-electrode system was employed
in the polarization curve test: a platinum electrode was used as the
auxiliary electrode, a calomel electrode was used as the reference
electrode, and the sample (exposed specimen 1 cm2) was the
working electrode (Zhan et al., 2019). The scan speed of the test
was 1 mV/sec, and the scanning circuit range was ±0.3 V of the
sample open circuit potential.
3. Results and discussion
3.1. Microstructure of composite coatings
It can be seen from the surface morphology of sample with elec-
troless plating for 3 min in Fig. 1(a) that many large flat particles
Fig. 1. Microscopic morphology of electroless plated samples at different times: (a) Electroless plating 3 min (b) Electroless plating 5 min (c) Electroless plating 10 min (d)
Electroless plating 30 min (e) Electroless plating 60 min (f) Electroless plating 90 min.
1301
grow on the surface of the coating, and some particles appeared
in the micropores of the MAO coating. These flat particles are den-
sely distributed on the surface of the coating, but the sizes of these
particles are uneven and vary greatly. Fig. 1(b) shows the micro-
morphology of the sample with electroless plating for 5 min. There
are many tiny particles distributed on the surface of the coating,
and some large cluster-like particles appear in some areas. Many
smaller spherical particles grow on large cluster-like particles,
and it should be noted that the cluster-like particles have not been
completely covered by these smaller spherical particles. Fig. 1(c)
shows the micromorphology of sample with the electroless plating
process lasts for 10 min, which shows many large cluster-like par-
ticles distributed on the surface of the coating, and smaller cellular
clusters on the surface. The continuous growth of the smaller
spherical particles on the cellular cluster caused the entire large
cell cluster to be covered and engulfed, but these large cellular
clusters are not connected to each other. It can be seen from the
micromorphology of the sample with electroless plating for
30 min as shown in Fig. 1(d), that the surface of the coating was
almost covered with a nickel-phosphorous coating, but many
microporous defects remained on the surface of the nickel layer.
1302 W. Shang et al. / Chemical Engineering Science 207 (2019) 1299–1308

The micromorphology conversion of the sample from the electro-
less plating time 10 min to 30 min indicates that large cellular
cluster grow continuously during this time and new smaller cellu-
lar cluster continuously appear and grow. A complete nickel-
phosphorus deposition coating with no defects has been formed
on the coating surface when the electroless plating processing
60 min as shown in Fig. 1(e). The nickel layers are closely packed,
but the size of the nickel cells of the coating are not uniform at this
time. The micromorphology of the sample with electroless plating
for 90 min is displayed in Fig. 1(f). The electroless nickel coatings
have achieved dense deposition coverage for the double-layer
composite coatings as the nickel cells further grow and fuse.
3.2. Elemental composition of composite coatings
Fig. 2 shows the EDS of the coating surface at different electro-
less plating times. The Pd element can be clearly observed in the
EDS curve from the sample with electroless plating for 3 min in
Fig. 2(a), which is the active site formed on the surface of the coat-
ing after activation. O, Mg, Si, F and other elements can be detected
by EDS at electroless plating times of 3 min, 5 min, and 10 min,
which are derived from the inner MAO coating and self-
assembled film. It can be clearly seen that the intensity of the
nickel element peaks continuously increases with the electroless
plating time. It can be concluded that the detectable elements

Fig. 2. EDS of electroless plating samples at different times: (a) Electroless plating 3 min (b) Electroless plating 5 min (c) Electroless plating 10 min (d) Electroless plating
30 min (e) Electroless plating 60 min (f) Electroless plating 90 min.
 W. Shang et al. / Chemical Engineering Science 207 (2019) 1299–1308
are only nickel and phosphorus on the surface of the coating and
the diffraction peaks of the Pd elements in the active sites and
the inner layers of O, Mg, Si, and F have disappeared when the elec-
troless plating conducted for 30 min according to Fig. 2(d). The ele-
ment change indicates that the inner layer has been completely
covered by a nickel layer after 30 min of electroless plating, which
is consistent with the conclusion obtained from the SEM. The peak
intensity of nickel greatly increased between the electroless plat-
ing time of 10 min to 30 min, indicating that this period is a rapid
reaction stage of the electrocatalytic autocatalytic reaction. The
elemental composition of the coating surface is Ni and P after time
of electroless plating 30 min. The peak intensity of nickel during
the plating time between 30 min to 60 min only slightly increased,
indicating that the reaction became more even after 30 min of elec-
troless plating. Similarly, the peak intensity of nickel did not
change significantly during the reaction time between electroless
plating time of 60 min to 90 min. The elemental change process
obtained from the EDS measurements is consistent with the
growth of nickel cells obtained from microscopic morphology of
coating surface.
Fig. 3. XRD curves of electroless plating samples at different times.
Fig. 4. Static contact angles of samples electroless plated at six different times: (a) Electroless plating 3 min (b) Electroless plating 5 min (c) Electroless plating 10 min (d)
Electroless plating 30 min (e) Electroless plating 60 min (f) Electroless plating 90 min.
1303
3.3. Crystallographic structure
Fig. 3 shows XRD curves of electroless plating for six different
times on the active surface of the double-layer composite coatings.
The composition of the coating surface was identified by using
software to characterize the measured curve (Correa et al., 2013;
Zhang, 2016). It can be seen from Fig. 3 that the diffraction peaks
of Mg and MgSiO3 can be detected in the six different electroless
plating time curves, which come from the inner MAO coating
and Mg alloy. No diffraction peak of nickel was detected in XRD
test of the sample with electroless plating time of first 3 min, but
the diffraction peak of MgO was detected, which is a component
of the MAO coating. It can be concluded that the flat particles dis-
tributed on the surface of the sample with electroless plating for
3 min are not nickel unit particles combined with the SEM, which
indicates that the autocatalytic reaction of electroless plating is
still very weak at this time. The broad diffraction peak of nickel
is evidently detected at time of electroless plating 5 min, and the
growth direction of the nickel cell is Ni (1 1 1). The peak intensity
of the nickel diffraction peak at the electroless plating time of
5 min is not very strong. It can be concluded that the small spher-
ical particles grown on the large cluster particles are nickel unit
cells when combined with the micromorphology at the time of
electroless plating 5 min of the sample. At this time point, the
intensity of the electrocatalytic autocatalytic reaction begins to
increase greatly. The material composition after the time of elec-
troless plating 5 min is Mg, MgSiO3, and Ni. It can be concluded
that the width of nickel diffraction peak is broadened and the
intensity is continuously enhanced with the increase in the elec-
troless plating time. This is consistent with the growth of the nickel
unit cells obtained from the SEM.
3.4. Static contact angle test
Fig. 4 shows the static contact angle images of samples electro-
lessly plated for six different times on the active surface, and the
value of the static contact angle statistics obtained by software
analysis is shown in Fig. 5. Fig. 4(a) is a contact angle image of
the coating with electroless plating for 3 min, and its value is
116.87°. It can be seen from the static contact angle test results
that the coating surface has the largest static contact angle value
of 122.45° when the double-layer composite coatings is electroless
1304 W. Shang et al. / Chemical Engineering Science 207 (2019) 1299–1308
Fig. 5. Static contact angles value of samples electroless plated at six different times
obtained by software analysis.
plated for 5 min. As the electroless plating time increased by 2 min,
the contact angle increased by 5.58° of the sample with electroless
plating for 3 min. The reason for the change of contact angle is that
the coating surface adsorbs the active sites of large particles, few
nickel particles grown on the active sites, and the coverage of the
inner layer is not complete when the electroless plating is carried
out for only 3 min. More nickel nucleus particles were grown on
the active sites, and the nickel particle size was also uniform when
electroless plating was carried out for 5 min, which was favourable
for improving the hydrophobicity of the coating surface. Fig. 4(c)
shows the contact angle of the coating surface at an electroless
plating time of 10 min is 111.11°, which is a decrease of 5.76° com-
pared with that of electroless plating time for 5 min. The reason for
the decrease of the contact angle is that a large amount of cellular
nickel particle clusters formed on the surface of the coating when
the electroless plating carried out for10 minutes, and the nickel
layer on the coating surface tends to be intact. The contact angle
of the coating surface continuously decreased with the extension
of the electroless plating time after the time of electroless plating
10 min. It can be seen from the SEM that the coating surface is
basically covered with the interconnected coating, the electroless
plating coating is often complete, and the integrity and flatness
of the coating surface are relatively favourable when the electro-
less plating is performed for 30 min. The coating is also becoming
less rough, the metal properties of the coating surface increased,
and the contact angle of the coating decreases. After the time of
electroless plating 30 min, the metallicity of the coating surface
continuously increases, the integrity of the coating surface contin-
ues to increase, and the contact angle of the coating continuously
decreases. The change in contact angles for the samples with six
different electroless plating times supports the nickel deposition
process data obtained from the surface microtopography.
3.5. Polarization curves
The polarization curves of the samples electrolessly plated for
six different times were tested by a conventional three-electrode
system in 3.5% NaCl solution. To make the sample surface reach
a steady state, the tested sample was immersed in 3.5% NaCl solu-
tion for 30 min (initial delay time) before the electrochemical mea-
surements. The polarization curves obtained are shown in the
Fig. 6. The data of the polarization curve were analysed by the soft-
ware of the Chi860 electrochemical workstation, and the relevant
data obtained are listed in Table 2. It can be seen from Table 2 that
the corrosion potential (Ecorr) continuously shifts and the corrosion
current density (icorr) decreases as the samples’ electroless plating
Fig. 6. Polarization curves of samples electroless plated for six different time.
time increased. The reason for this change is that the nickel parti-
cles are continuously growing, the unit cells are continuously
fused, and the compactness of the nickel layer is continuously
increased as the electroless plating time increased, which is effec-
tive at greatly improve the corrosion resistance of the coating. It is
worth noting that the corrosion potential and corrosion current
density of the four samples electrolessly plated for 3 min, 5 min,
10 min and 30 min change slowly with the increase of electroless
plating time. Nickel coating has been basically achieved on the
coating surface at the electroless plating of 30 min, but the thick-
ness of nickel coating is still very small at this time, and there
are still many defects in the nickel coating. The thin nickel coating
was destroyed by corrosive medium and fell off during the immer-
sion process before the electrochemical measurement, so the cor-
rosion potential and current density of the sample samples
electrolessly plated for 30 min were similar to those of the sample
with the nickel coating incomplete. However, the corrosion
potential and corrosion current density of the sample electrolessly
plated for 60 min varied greatly compared with the previous
four samples. The corrosion potential was rapidly shifted to
0.3612 V, and the corrosion current density dropped to
7.607  107 Acm2, which was a decrease of three orders of mag-
nitude compared to the sample electrolessly plated for 30 min. The
corrosion potential is further positively shifted and corrosion cur-
rent density is further reduced of the sample that electrolessly pla-
ted for 90 min compared with the sample electrolessly treated for
60 min. It is apparent in the polarization plot that a significant step
region appears in the anode branch of the samples electrolessly
plated for 60 min and 90 min, which was not apparent in the pre-
vious four samples electrolessly plated for 3 min, 5 min, 10 min
and 30 min. The reason for the step region is that the surface of
the electroless nickel plating layer is dense, which effectively
blocks the corrosive medium from passing through the coating,
inhibits the anode dissolution and the anodic hydrogen evolution
reaction of the magnesium alloy, and improves the corrosion resis-
tance of the coating. The reason for the absence of the anode step
region in the polarization curve of samples electrolessly plated for
3 min, 5 min, 10 min and 30 min is that the coating is incomplete
or has many defects, and the nickel coating was invalid as the first
barrier to block corrosive media. It can be concluded that nickel
coating with protective performance was formed after 60 min of
electroless plating on the coating surface combining with the
micro-morphology and electrochemical test results of the sample
with different plating time. The growth mechanism and model
for the nickel layer obtained from the SEM can be further verified
from the changes of the polarization curve.
 W. Shang et al. / Chemical Engineering Science 207 (2019) 1299–1308 1305

Table.2
Fitted results of polarization curve of samples electroless plated six different times.

Sample Ecorr Anode slope Cathode slope icorr

(vs.SCE/V) (mV/decade) (mV/decade) (Acm2)
3 min 1.4425 4.661 3.240 1.387  103
5 min 1.3320 4.260 4.643 1.03  103
10 min 1.2612 6.842 5.707 8.142  104
30 min 1.2565 7.077 19.781 2.483  104
60 min 0.3612 4.658 8.282 7.607  107
90 min 0.3495 4.708 10.429 9.777  108

3.6. Deposition mechanism
It can be concluded that the deposition mechanism of electro-
less plating on the surface is an initial ecological reduction [H]
autocatalytic reduction deposition process according the morphol-
ogy and structure test of the samples that were electrolessly plated
for 6 different time periods on composite coatings surface. The ini-
tial ecological reduction [H] autocatalytic reduction deposition
mechanism and process are shown in Fig. 7.
At the beginning of the electroless plating, the Ni2+ chelate in
the electroless plating bath gradually disassociates a large amount
of Ni2+. The dissociated Ni2+ rapidly moves towards the active sur-
face, and a large amount of Ni2+ is adsorbed on the active surface.
The morphology of the sample that was electrolessly plated for
3 min shows that a large number of flattened particles are the
result of adsorption of a large amount of Ni2+ on the active surface.
H2PO 2 in the bath is adsorbed onto the surface of the Ni
2+
to gen-

erate HPO2 and a large amount of the initial reduction [H] (Reac-
tion (1)). This is the reason for why the diffraction peak of nickel
is not detected in the XRD test of the sample that was electrolessly
plated for 3 min, which indicates that the initial ecological reduc-
tion [H] in the bath cannot initiate the autocatalytic reduction
reaction. The degree of autocatalytic reaction of electroless plating
at this stage is still very weak, and the reaction is mainly based on
the generation of a large amount of initial reduction [H]. The
adsorption modes of H2PO 2 and Ni
2+
are shown in Fig. 8 (Liu and
Wang, 2001). One is single H bond adsorption, and the other is
HAH bond adsorption. Only when the single H bond adsorption
is adopted is the initial ecological reduction [H] generated. The
chemical nature of HPO 2 is extremely unstable, and it easily reacts
with water to produce H2PO +
3 , H and free moving e

(Reaction
(2)). The initial ecological reduction [H] contacted the active sur-
face of Ni2+ in large areas and released e. Ni2+ gets e released
by the initial ecological reducing [H] are reduced to metallic nickel
on the active surface (Reaction (3)) when the initial concentration
of reducing [H] reaches a certain level. This stage corresponds to
the SEM microtopography and XRD results obtained the time of
electroless plating 5 min. At this time, many rounded nickel cells
were generated on the active surface, and the diffraction peaks of
nickel were clearly detected in the XRD analysis, indicating that
the nickel autocatalytic reaction in the bath occurred at a faster
rate, and a nickel-phosphorus deposition coating began to form
on the active surface. With the increase of the electroless plating
time, the initial ecological reducibility [H] is continuously added
to the active surface, the nickel unit cells grow and continuously
fuse with each other, and the complete nickel coating on the active
surface is finally obtained.
The nickel layer will be three-dimensionally deposited along
the surface of the active surface after the nickel core is formed.
The nickel layer will be deposited in three ways as shown in
Fig. 9. The growth pattern adopted by the nickel layer will be deter-
mined by the number of free Ni2+ in the bath. The amount of initial

Fig. 7. Deposition mechanism of electroless plating on MAO-SAM composite coatings.

1306 W. Shang et al. / Chemical Engineering Science 207 (2019) 1299–1308

Fig. 8. Two adsorption modes for H2PO 2+

2 and Ni .

Fig. 9. Nickel growth stacking pattern of electroless plating on MAO-SAM double-layer composite coatings.

ecological reducibility [H] is mainly determined by free Ni2+ in the
bath. A large amount of Ni2+ is required to be added to the autocat-
alytic surface when the autocatalytic reaction completes the induc-
tion period. If the concentration of Ni2+ is much lower than the
concentration required for the reaction, the growth rate perpendic-
ular to the interface (V\) is much less than the growth rate in the
parallel direction (Vk), which causes the nickel to grow in a layered
manner along the parallel to the active interface. When the con-
centration of Ni2+ in the solution can meet the required concentra-
tion of the reaction, and within a certain concentration range, the
growth rate perpendicular will be V\  Vk. The nickel layer will
grow in a cell-like three-dimensional manner, the cell structures
will continuously grow and fuse in densely packed fashion, and a
dense deposited layer will be obtained. When the Ni2+ concentra-
tion in the bath is too high, the Ni2+ activity concentration is much
higher than the concentration required for the reaction, resulting
that in a perpendicular growth rate such that V\ > Vk. The nickel
layer will grow in a spherical columnar growth mode, the accumu-
lation rate is too fast and the number of defects increases, resulting
in poor coating density due to the excessive Ni2 concentration. It
can be concluded that nickel grows in a cell-like three-
dimensional manner based on the micromorphology obtained at
different electroless plating times in this work. This growth
orientation is due to the addition of an appropriate amount of a
 W. Shang et al. / Chemical Engineering Science 207 (2019) 1299–1308
complexing agent to the electroless plating bath to form a Ni2+ che-
late, and the gradual dissociation of the Ni2+ chelate controls the
concentration of free Ni2+ in the bath.
The H+ generated in the bath acquires free e and reduced to the
H2 overflow solution (Reaction (4)), which is responsible for the
generation of small bubbles during the reaction. Phosphorus is
the product of H2PO 2 reduced by the initial ecological restoration
[H] (Reaction (5)). It is worth noting that the initial ecological [H]
does not directly react with the H2PO 2 , but it is rather reduced
by the free e released by the initial ecological [H]. Because the ini-
tial ecological reduction [H] can only be produced under the Ni2+
adsorption catalysis, the phosphorus can only be generated on
the nickel surface. Thus, co-deposition of phosphorus and nickel
is achieved.
ðcatalyticÞ
H2 PO2ðadsorptionÞ ƒƒƒƒƒ! HPO2 þ ½H ð1Þ
ðcatalyticÞ
HPO2 þ H2 O ƒƒƒƒƒ! H2 PO3 þ Hþ þ e ð2Þ
þ 2½Hƒƒƒ!Ni þ 2Hþ
2þ
Ni ð3Þ
2Hþ þ 2e ƒƒƒ!H2 ð4Þ
H2 PO2 þ 2Hþ þ e ƒƒƒ!2H2 O þ P ð5Þ
4. Conclusion
1. The electroless plating nickel growth process on the MAO-SAM
active surface is a ‘‘cell-like three-dimensional” growth in
which cellular nickel particles continuously grow and engulf
each other to form a complete nickel-deposited coating, accord-
ing to SEM analysis. The changes in the coating surface mea-
sured by EDS supported the growth process of nickel obtained
from SEM.
2. The sample electrolessly plated for 5 min had the best
hydrophobicity because of its more uniform nickel particle
growth on the active sites, as shown in SEM measurements,
which was favourable for improving the hydrophobicity. The
corrosion resistance of the composite coatings is greatly
improved when the electroless plating is performed for
60 min because the nickel coating is completely without
defects, as shown in the SEM images.
3. The diffraction peaks of the nickel were not detected in the XRD
analysis at time of electroless plating 3 min, indicating that the
electrocatalytic autocatalytic reaction is very weak within the
first 3 min. The broad diffraction peaks of nickel occurred at
after 5 min of electroless plating. The width of the nickel
diffraction peak is broadened and the intensity is continuously
enhanced with the increase of electroless plating time.
4. The deposition mechanism of electroless plating on the surface
is an initial ecological reduction [H] autocatalytic reduction
deposition process according to the morphology and structure
test of the samples that were electrolessly plated for 6 different
time periods on the active surface. The nickel deposits are
grown in a three-dimensional cell-like manner with a growth
rate perpendicular to the interface less than the growth rate
parallel to the interface direction.
Declaration of Competing Interest
We declare that we have no financial and personal relationships
with other people or organizations that can inappropriately influ-
ence our work, there is no professional or other personal interest
1307
of any nature or kind in any product, service and/or company that
could be construed as influencing the position presented in, or the
review of, the manuscript entitled.
Acknowledgements
This work was financially supported by National Natural
Science Foundation of China (No. 51664011 and No.51665010),
and the Project of Guangxi Key Laboratory Foundation of China
(No. EMFM20181106).
References
Chen, M.-A., Cheng, N., Ou, Y.-C., Li, J.-M., 2013. Corrosion performance of electroless
Ni–P on polymer coating of MAO coated AZ31 magnesium alloy. Surf. Coat.
Technol. 232, 726–733.
Correa, E., Zuleta, A.A., Guerra, L., Gómez, M.A., Castaño, J.G., Echeverría, F., Liu, H.,
Baron-Wiecheć, A., Hashimoto, T., Skeldon, P., Thompson, G.E., 2013. Coating
development during electroless Ni–B plating on magnesium and AZ91D alloy.
Surf. Coat. Technol. 232, 784–794.
Duan, H., Du, K., Yan, C., Wang, F., 2006. Electrochemical corrosion behavior of
composite coatings of sealed MAO film on magnesium alloy AZ91D.
Electrochim. Acta 51, 2898–2908.
Elsener, B., Crobu, M., Scorciapino, M.A., Rossi, A., 2008. Electroless deposited Ni–P
alloys: corrosion resistance mechanism. J. Appl. Electrochem. 38, 1053–1060.
Fan, X., Wang, Y., Zou, B., Gu, L., Huang, W., Cao, X., 2013. Preparation and corrosion
resistance of MAO/Ni–P composite coat on Mg alloy. Appl. Surf. Sci. 277, 272–
280.
Gan, R., Wang, D., Xie, Z.-H., He, L., 2017. Improving surface characteristic and
corrosion inhibition of coating on Mg alloy by trace stannous (II) chloride.
Corros. Sci. 123, 147–157.
Georgiza, E., Novakovic, J., Vassiliou, P., 2013. Characterization and corrosion
resistance of duplex electroless Ni-P composite coatings on magnesium alloy.
Surf. Coat. Technol. 232, 432–439.
Gu, C., Lian, J., Li, G., Niu, L., Jiang, Z., 2005. Electroless Ni–P plating on AZ91D
magnesium alloy from a sulfate solution. J. Alloy. Compd. 391, 104–109.
Guo, X., Du, K., Guo, Q., Wang, Y., Wang, F., 2012. Experimental study of corrosion
protection of a three-layer film on AZ31B Mg alloy. Corros. Sci. 65, 367–375.
Jian, S.-Y., Lee, J.-L., Lee, H.-B., Sheu, H.-H., Ou, C.-Y., Ger, M.-D., 2016. Influence of
electroless plating on the deterioration of the corrosion resistance of MAO
coated AZ31B magnesium alloy. J. Taiwan Inst. Chem. Eng. 68, 496–505.
Liu, Y.-J., Wang, Y.-P., 2001. The mechanism of electroless nickel deposition in
sodium hypophosphite bath. J. East China Univ. Sci. Technol. 27, 301–306.
Loto, C.A., 2016. Electroless nickel plating – a review. Silicon 8, 177–186.
Luo, D., Liu, Y., Yin, X., Wang, H., Han, Z., Ren, L., 2018. Corrosion inhibition of
hydrophobic coatings fabricated by micro-arc oxidation on an extruded Mg–
5Sn–1Zn alloy substrate. J. Alloy. Compd. 731, 731–738.
Petro, R., Schlesinger, M., 2012. Direct electroless deposition of low phosphorous Ni-
P films on AZ91D Mg alloy. J. Electrochem. Soc. 159, D455–D461.
Qi, H., Qian, Y., Xu, J., Zuo, J., Li, M., 2018. An AZ31 magnesium alloy coating for
protecting polyimide from erosion-corrosion by atomic oxygen. Corros. Sci. 138,
170–177.
Qin, T.-N., Ma, L.-Q., Yao, Y., Ni, C., Zhao, X.-Y., Ding, Y., 2011. An in situ measure
method to study deposition mechanism of electroless Ni-P plating on AZ31
magnesium alloy. Trans. Nonferrous Met. Soc. China 21, 2790–2797.
Shang, W., 2017. Study on the properties of micro - arc oxidation self - assembled
composite coatings on magnesium alloy. Int. J. Electrochem. Sci., 11875–11891
Song, G.-L., Liu, M., 2012. The effect of surface pretreatment on the corrosion
performance of Electroless E-coating coated AZ31. Corros. Sci. 62, 61–72.
Song, Y.W., Shan, D.Y., Han, E.H., 2008. High corrosion resistance of electroless
composite plating coatings on AZ91D magnesium alloys. Electrochim. Acta 53,
2135–2143.
Song, Z., Xie, Z., Yu, G., Hu, B., He, X., Zhang, X., 2015. A novel palladium-free surface
activation process for electroless nickel deposition on micro-arc oxidation film
of AZ91D Mg alloy. J. Alloy. Compd. 623, 274–281.
Sudagar, J., Lian, J.S., Jiang, Q., Jiang, Z.H., Li, G.Y., Elansezhian, R., 2012. The
performance of surfactant on the surface characteristics of electroless nickel
coating on magnesium alloy. Prog. Org. Coat. 74, 788–793.
Tsai, T.-K., Chao, C.-G., 2004. The growth morphology and crystallinity of electroless
NiP deposition on silicon. Appl. Surf. Sci. 233, 180–190.
Wang, M.-L., Yang, Z.-G., Zhang, C., Liu, D.-L., 2013. Growing process and reaction
mechanism of electroless Ni–Mo–P film on SiO2 substrate. Trans. Nonferrous
Met. Soc. China 23, 3629–3633.
Wei, Y.-K., Li, Y.-J., Zhang, Y., Luo, X.-T., Li, C.-J., 2018. Corrosion resistant nickel
coating with strong adhesion on AZ31B magnesium alloy prepared by an in-situ
shot-peening-assisted cold spray. Corros. Sci. 138, 105–115.
Xiang, Y., Hu, W., Liu, X., Zhao, C., Ding, W., 2017. Initial deposition mechanism of
electroless nickel plating on magnesium alloys. Trans. IMF 79, 30–32.
Xie, Z., Yu, G., Li, T., Wu, Z., Hu, B., 2011. Dynamic behavior of electroless nickel
plating reaction on magnesium alloys. J. Coat. Technol. Res. 9, 107–114.
1308 W. Shang et al. / Chemical Engineering Science 207 (2019) 1299–1308

Zeng, L., Yang, S., Zhang, W., Guo, Y., Yan, C., 2010. Preparation and characterization
of a double-layer coating on magnesium alloy AZ91D. Electrochim. Acta 55,
3376–3383.
Zhan, X., Shang, W., Wen, Y., Li, Y., Ma, M., 2019. Preparation and corrosion
resistance of a three-layer composite coatings on the Mg alloy. J. Alloy. Compd.
774, 522–531.
Zhang, J., 2016. Corrosion behavior of electroless Ni-P/Ni-B coating on magnesium
alloy AZ91D in NaCl environment. Int. J. Electrochem. Sci., 10053–10066
Zucchi, F., Frignani, A., Grassi, V., Balbo, A., Trabanelli, G., 2008. Organo-silane
coatings for AZ31 magnesium alloy corrosion protection. Mater. Chem. Phys.
110, 263–268.