Surface & Coatings Technology 309 (2017) 106113

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Surface & Coatings Technology

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

Surface modication of nickel-aluminum bronze alloy with gradient

Ni-Cu solid solution coating via thermal diffusion
Qin Luo a, Zhong Wu a,b,, Zhenbo Qin a, Lei Liu a,b,, Wenbin Hu c
a
State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, China
b
Collaborative Innovation Center for Advanced Ship and Deep-Sea Exploration, Shanghai 200240, China
c
School of Material Science and Engineering, Tianjin University, Tianjin 300072, China

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

Article history: The surface modication of nickel-aluminum bronze (NAB) alloy was developed by thermal diffusion of Ni coat-
Received 23 April 2016 ing and the alloy matrix. A multilayer coating was designed with the gradient outer layer of the Ni-Cu solid solu-
Revised 2 November 2016 tion and the inner layer of the Ni-Al-Cu intermetallic layer. The evolution of the multilayer was a diffusion
Accepted in revised form 4 November 2016
controlled model. The enhanced corrosion resistance of the Ni-Cu layer could be found in the salt spray test,
Available online 14 November 2016
which exhibited uniform corrosion behavior compared with severe selective phase corrosion of the NAB alloy.
Keywords:
Besides the gradient distribution of the components, it was also attributed to the formation of protective lm,
Nickel-aluminum bronze alloy which mainly consisted of Ni(OH)2 and Cu2O. It has been conrmed by electrochemical impedance spectroscopy
Microstructure evolution (EIS) test and X-ray photoelectron spectroscopy (XPS) results.
Ni-Cu solid solution 2016 Elsevier B.V. All rights reserved.
SKPFM
Corrosion

1. Introduction
Nickel-aluminum bronze (NAB) alloys are extensively applied in
marine engineering, used as propeller, pump, valve etc., which is attrib-
uted to their excellent combination of mechanical properties and corro-
sion resistance [13]. However, the further application is limited by its
inherent susceptibility to selective phase corrosion, which is induced
by the complex structure and the resulting inhomogeneous composi-
tion distribution within the NAB alloys [4,5]. Considerable research
has been devoted to investigating the methods to eliminate the selec-
tive phase corrosion of the NAB alloy. Heat treatment and hot working
have been applied to optimize the structure, but they could only elimi-
nate the eutectoid structure partly, which is susceptible to attacks in
the corrosive media [6]. Friction-stir processing (FSP) was adopted on
as-cast NAB alloys to obtain rened grains within the surface layer,
thus enhancing the erosion-corrosion resistance [7], but it simulta-
neously introduced residual stresses [8]. Besides, the phase was
only rened but still existed. High velocity oxy-fuel (HVOF) coating
was also applied on the NAB alloys, but the porosity of the coating
was harmful to protect against corrosion attack [9]. Other modied
coatings, such as organic coating and electrodeposited metal coating,
faced the critical problem of the low interfacial bonding strength. Such
Correspondence to: Z. Wu, State Key Laboratory of Metal Matrix Composites, Shanghai
Jiao Tong University, Shanghai 200240, China.
Corresponding author.
E-mail addresses: wuzhong2319@163.com (Z. Wu), anodic@sjtu.edu.cn (L. Liu).
low bonding strength and peeling off when applied with alternating
load should certainly be avoided [10]. To date, there is no method to ef-
fectively eliminate the selective phase corrosion of the NAB alloys.
Nickel-copper (Ni-Cu) alloys are extensively used in the saline envi-
ronments because of the formation of the duplex passive lms
consisting of the outer layer of Ni(OH)2 lm and the inner compact
Cu2O enriched Ni lm [11,12]. The corrosion current density of 70Cu-
30Ni is 108 A/cm2 in 3.5 wt.% NaCl solution, while the corresponding
value of the NAB alloy is 106 A/cm2 [3,13]. When serving in seawater,
Ni-Cu alloys exhibit uniform corrosion behavior rather than selective
phase corrosion that existed in the NAB alloys and pitting corrosion in
Ni coating [14]. It can be concluded that Ni-Cu alloys with higher Ni con-
tent are more resistant to corrosion attack in NaCl solution than the NAB
alloys. Therefore, how to prepare the Ni-Cu coating on the NAB alloys is
the focus in this study. Due to the innite solubility of Cu and Ni, Ni-Cu
alloys exist as a homogenous solid solution [15]. Some researchers have
found that the inter-diffusion of Cu and Ni starts at low temperature
around 300 C and the diffusion rate increases with the temperature in-
creasing [16]. As a result, Ni-Cu coatings could be formed by means of
heat treatment when depositing nickel coating on the NAB alloy. It
could not only enhance the interface strength but also relieve stress
concentration due to the formation of a gradient diffusion layer by ther-
mal diffusion [17,18].
In this paper, the surface modication of the NAB alloy was designed
with a gradient Ni-Cu coating by thermal inter-diffusion to eliminate
the selective phase corrosion. The microstructure evolution of the sur-
face layers was analyzed by a scanning electron microscope (SEM)

http://dx.doi.org/10.1016/j.surfcoat.2016.11.013
0257-8972/ 2016 Elsevier B.V. All rights reserved.
 Q. Luo et al. / Surface & Coatings Technology 309 (2017) 106113
and glancing angle X-ray diffraction (GAXRD). The corrosion properties
of the modied layers were characterized by scanning Kelvin probe
force microscopy (SKPFM), electrochemical impedance spectroscopy
(EIS) test and salt spray test, as well as X-ray photoelectron spectrosco-
py (XPS) analysis for the protective lm formed on the Ni-Cu layer.
2. Experimental procedure
2.1. Materials
The NAB alloy used in this work with the chemical composition
(wt.%): Al 9.85, Ni 3.75, Fe 3.86, Mn 1.03 and Cu balance was determined
by X-ray uorescence spectroscopy. A nano-crystalline nickel coating
was electrodeposited on the NAB surface for the nickel source during
thermal diffusion. The electrodeposition solution consisted of
Ni(SO3NH2)24H2O (350 g/L), NiCl26H2O (15 g/L), C12H25-OSO3Na
(0.1 g/L) and H3BO3 (40 g/L). The pH was adjusted at 4.0 0.1 with
NH3H2O and the temperature was kept at 50 2 C in a water bath.
The specimens were metallographically prepared by using successive
grades of abrasive paper up to 1200 grit, ultrasonic cleaned with acetone
and then rinsed with deionized water. Prior to electrodeposition, the
specimens were immersed in alkaline solution to remove the grease
and then activated in 10% H2SO4 solution. After electrodeposition for
20 min, the coated NAB specimens were annealed at 675 C in argon at-
mosphere for 0.5 h, 6 h and 12 h, respectively. The treated temperature
was selected for the industry utilization [2,19].
2.2. Microstructure and characterization
The scanning electron microscope (SEM) equipped with the en-
ergy dispersive spectroscope (EDS) was used to characterize the
cross-sectional morphologies of the specimens. GAXRD (D8 AD-
VANCE DA VINCI, Bruker, Germany) was conducted to investigate
the microstructure of the thermal diffusion layers. The incidence
angle was set at 1 o with Cu-K radiation, working at 30 mA and
40 kV. Generally, adjusting the grazing incidence angle could get
the information of different depths from the surface. The testing
depth of GAXRD, however, is limited to no more than 10 m. In this
work, three different Ni-Cu layers with the Cu content of (wt.%)
3.4, 20.3 and 40.7, respectively, were obtained, as well as the Ni-Al-
Cu intermetallic layer. The chemical composition of the layers was
determined by photoelectron X-ray spectroscopy (XPS).
2.3. SKPFM measurements
Volta potential images of the thermal diffusion layers were
obtained by scanning Kelvin probe force microscopy (SKPFM)
(Dimension Icon, Bruker, Germany) from the mirror-like as-polished
surface. The measurements were accomplished in the air at room
temperature with controlled relative humidity of about 40%. The
Nanoprobe used was SCM-PIT conductive Pt/Ir-coated tips with
the frequency of 75 KHz. The mappings were conducted by the
dual-scan modes. All the Volta potential images are the invert of
the measured potential to exhibit the actual Volta potential [20].
2.4. Salt spray test
Corrosion behaviors of the thermal diffusion layers and the NAB
alloy were investigated by conducting salt spray test according to
the ASTM-B117-73 Standard with the following conditions: 1) the
concentration of NaCl solution was 5 wt.% with the pH between 6.5
and 7; 2) the rate was 1 2 mL/h80 cm2; 3) the temperature was
set at 35 C; 4) the spray pattern was continuous. The corroded sam-
ples were observed with a Canon Camera and a scanning electron
microscope (SEM) (JEM-2100F, Japan).
107
2.5. The electrochemical impedance tests
The EIS tests were carried out with the traditional three-electrode
system. Before the tests, the samples were immersed in the 3.5 wt.%
NaCl solution for120 min to obtain the stable open circuit potential.
The data were recorded at the open circuit potential with the AC ampli-
tude of 10 mV and the frequency range between 20 kHz and 0.01 Hz.
Every test was repeated three times.
2.6. The chemical analysis of the protective lm with XPS
In order to understand the protective lm formed on the Ni-Cu layer
during the salt spray test, the XPS measurements were conducted on a
Kratos Axis UltraDLD spectrometer (Krato Analytica-A Shimadzu Group
Company), using a monochromatic Al K X-ray source with in vacuum
of 5 109 mBar or better. All the survey scans and the high-resolution
spectra were recorded at the randomly chosen sites on the surface. The
data reduction was performed by deconvoluting the Ni2p 3/2 peak and
Cu2p 3/2 peak with the CasaXPS 2.3.16 software.
3. Results and discussion
3.1. Microstructure
The cross-sectional microstructure morphologies of the speci-
mens are shown in Fig. 1. Annealed for 0.5 h (Fig. 1a), only a thin
Ni-Cu layer is observed with the thickness of 2.65 m, which was
demonstrated by the EDS line scan results. When annealing time in-
creased to 6 h (Fig. 1b), a double layer containing the Ni-Cu solid so-
lution and the Ni-Al-Cu layer could be seen with the thickness of
8.98 m and 5.71 m, respectively. Further increasing the annealing
time to 12 h, the thickness of the double layers both increased to
13.75 m and 14.25 m, respectively, as shown in Fig. 1c. The chem-
ical composition of the outer solid solution layer was gradient
change, while the inner layer was uniform with the chemical compo-
sition (wt.%): Ni 67.3, Cu 23.6, and Al 9.1, according to the EDS re-
sults. It is believed that the triple diffusion system (Ni, Cu and Al)
could be simplied as two binary diffusion processes consisting of
Ni/Cu and Ni/Al. The double layers generated during the annealing
process were attributed to the different diffusion process between
Ni/Cu and Ni/Al. The sketch of the atomic diffusion process upon an-
nealing time is shown in Fig. 1(d, e and f). The priority of Ni/Cu diffu-
sion couple is assumed to be the innite solid solubility. According to
previous research, the inter-diffusion coefcient of Ni-Al is
10 14 m2/s at 1100 C, while Cu-Ni is 10 14 m2/s at 300 C [21,22].
Besides, it is well accepted that the diffusion process is also related
to the driving force, which is induced from the different content be-
tween the diffusion couple. Thus, it is considered that Cu atom dif-
fused faster than Al atom within Ni coating with the much higher
Cu drop between Ni coating and NAB substrate. Therefore, the Ni-
Cu solid solution layer was the outer layer and the Ni-Al-Cu interme-
tallic layer was the inner layer. As annealing time increased (Fig. 1e),
Al atoms continuously accumulated in the diffusion region, which
resulted in the formation of the inner layer. Moreover, both layers
grew with annealing time as described in Fig. 1f.
In order to conrm the formation mechanism of the double
layers, more annealing times were selected for detailed analysis.
The growth rate of the Ni-Cu solid solution layer and the Ni-Al-Cu in-
termetallic layer was determined by measuring the thickness of the
layers at selected time intervals annealed at 675 C, which were
0.5 h, 1 h, 2 h, 6 h, 12 h, 18 h and 24 h, respectively. The relationship
between the diffusion thickness d and the annealing time t can be
expressed as follows:
d Dt=t 0 n 1
108 Q. Luo et al. / Surface & Coatings Technology 309 (2017) 106113

Fig. 1. Cross-section line scan and the sketch of the atomic diffusion process of the Ni-coated NAB specimens annealed with different times: (a, d) 0.5 h; (b, e) 6 h; (c, f) 12 h. layers.

where t0 is unit time, 1 s, adopted to make the ratio t/t0 dimension-
less [23]; D is the growth rate constant; n is the time exponent. Gen-
erally, the growth behavior of the diffused layer against time could
follow the linear or parabolic relationship. The linear relationship
suggests that the growth behavior is controlled by the reaction rate
at the growth site, while the parabolic relationship implies the vol-
ume diffusion controlled model during annealing process [24]. In
this study, the growth behaviors of the layers were mainly controlled
by the atomic diffusion of Cu, Ni and Al, thus the annealing process
was volume diffusion controlled and n took the value of 0.5 [25]. It
can be seen that the growth thickness of two layers follows the par-
abolic law as shown in Fig. 2, which conrms the volume diffusion
controlled model. The growth rate constant D could be calculated
from the tting linear slope of d versus t1/2, which was 1.3539E 7
and 7.284E 8 for the Ni-Cu solid solution layer and the Ni-Al-Cu
layer, respectively. It was similar to the previous studies in Ni/Cu-
Ni diffusion couples with D = 1.0E 7.71 0.12 and n = 0.564
0.025 [23]. The growth rate of the Ni-Cu solid solution layer is
much larger than that of the Ni-Al-Cu intermetallic layer according
to Fig. 2.
Fig. 3 shows the GAXRD patterns of different Ni-Cu layers and the
Ni-Al-Cu layer. The reections of (1 1 1) and (2 0 0) planes of NiCu
and Ni could be found from all the layers while the AlNi3 peaks
only appeared in the Ni-Al-Cu layer. According to the patterns of
Ni-Cu layers, it can be seen that the peaks of NiCu and Ni are difcult
to distinguish from each other. It is probably due to the fact that the
Cu atoms diffused into Ni substrate and formed the -Ni(Cu) solid
solution layer during the heat treatment process [26]. Besides, the
2 angle of (1 1 1) plane expresses a progressive shift towards the
smaller angles as the Cu content increased. It is mainly attributed
to the expanding of the lattice parameter of Ni/Cu solid solution
with the increase of Cu content, as the lattice parameter of Cu
(Cu = 3.6148 ) is higher than that of Ni (Ni = 3.5232 ) [26]. Fur-
thermore, the different width of the (1 1 1) and (2 0 0) peaks is also
observed, suggesting the existence of the stacking faults. The inten-
sity ratio of the (1 1 1) peak and the (2 0 0) peak of the Ni-Cu layer

Fig. 2. Diffusion layer thickness with various times annealed at 675 C: (a) Cu/Ni solid solution; (b) Ni-Al-Cu intermetallic layer.
 Q. Luo et al. / Surface & Coatings Technology 309 (2017) 106113
Fig. 3. GAXRD patterns of Ni, Ni-40.7Cu, Ni-20.3Cu, Ni-3.4Cu and the intermetallic.
is much bigger than that of the polycrystalline Ni coating, indicating
that all the diffused coatings are textured in the Ni (1 1 1) plane. For
the GAXRD pattern of the intermetallic layer, the peaks of the AlNi3
are observed by the formation of the intermetallic phase in the diffu-
sion process, during which the Al atoms preferred to afne Ni atoms
rather than Cu atoms. It is attributed to the thermodynamic stability
that the formation enthalpy ( H) of the Ni-Al compounds is lower
than that of the Cu-Al compounds [27,28].
3.2. SKPFM analysis
The cross-sectional Volta potential distribution of the modied
NAB alloy is shown in the SKPFM image (Fig. 4a). The NAB substrate
is distinguished by the structural feature of phases, while the
middle layer is related to the Ni-Al-Cu intermetallic layer and the
outer layer for the Ni-Cu solid solution. The Volta potentials
showed the values of the united work functions of the elements.
The relatively lower potential implies the lower work function,
which means the active sites for corrosion [20,29]. The work func-
tion values are attributed to their chemical composition, described
Fig. 4. (a) Volta potential map of the thermal diffusion layers and (b) the line scan proles.
109
Fig. 5. Topography image of the thermal diffusion layers immersed in the neutral 3.5 wt.%
NaCl solution for 20 h.
as follows [20]:
X X
W i
wi  i = i i 2
where W is the work function; W i is the work function of the ele-
ment i; and i is the atomic percent. For the NAB substrate, the
bright areas exhibited higher Volta potentials compared with the
dark ones, which were corresponding to phases. In other words,
there was a difference in the Volta potential between and
phases, dened as E and expressed by prole 2 in Fig. 4b, which
was the mean factor to assess the driving force for the selective
phase corrosion of the NAB alloys [20]. It is noted that the Ni-Cu
layer expressed the gradual change in the Volta potential, which
indicated that the driving force for the selective phase corrosion
was effectively relieved, thus appearing homogenous shallow at-
tack in the corrosive media.
According to Fig. 4b (prole 1), it can be found that the Ni-Al-Cu
intermetallic layer with relatively higher Al content exhibited
lower Volta potential than that of the NAB substrate, due to the
110 Q. Luo et al. / Surface & Coatings Technology 309 (2017) 106113

Fig. 6. Macroscopic morphologies of the corroded surface of the Ni-Cu layer, intermetallic layer and NAB alloy after salt spray test in 5 wt.% NaCl solution for 0, 1, 4 and 12 days.

much lower work function of Al compared with that of Cu and Ni
[20]. The gradual increase in the Volta potential of the Ni-Cu solid so-
lution was consistent with the gradual distribution of Cu and Ni, as
shown in Fig. 1. Both of the Ni-Cu solid solution layer and the Ni-
Al-Cu intermetallic layer showed lower Volta potentials compared
with the NAB alloy, indicating the preferential corrosion attack.
However, immersed in the neutral 3.5 wt.% NaCl solution for 20 h,
the Ni-Cu solid solution layer and the intermetallic layer both exhib-
ited cathodic behavior compared to the NAB substrate, as shown in
Fig. 5. It can be seen that the NAB alloy expressed severe corrosion
attack with phases preferentially dissolved, indicating the obvious
selective phase corrosion and consistent with the potential differ-
ence of different phases in Fig. 4. However, there was no obvious cor-
rosion attack in the Ni-Cu and Ni-Al-Cu layers. Those ndings were
contrary with the results of SKPFM measurements. It is acknowl-
edged that the present Volta potential values are measured in air,
which is related to the corrosion tendency of microstructural constit-
uents. When immersed in NaCl solution, the passive lm formed on
phases [29] and the modied layers, resulting in the change in the
corrosion behavior.

Fig. 7. SEM images of different layers after salt sprayed for 12 days: (a, d) NAB alloy; (b, e) Ni-Cu solid solution; (c, f) Ni-Al-Cu intermetallic layer.
 Q. Luo et al. / Surface & Coatings Technology 309 (2017) 106113
Fig. 8. Impedance spectra of the Ni-Cu layers, the intermetallic layer and the NAB substrate in 3.5 wt.% NaCl solution: (a) Nyquist spectra; (b) Bode-impedance; (c) Bode spectra- phase.
3.3. Salt spray test
The macroscopic surface morphologies of the Ni-Cu layer, the Ni-
Al-Cu intermetallic layer and the NAB alloy during the salt spray test
for 12 days are shown in Fig. 6. It can be seen that the NAB alloy was
covered with red rust after 1 day in the salt spray chamber, while the
Ni-Cu layer exhibited uniform dark appearance with partial mirror
surface, suggesting improved corrosion resistance of the Ni-Cu
layer. The intermetallic layer showed pitting corrosion behavior
with corrosion products piling up on the pitting sites. With salt
spray time increasing, the NAB alloy suffered severe corrosion attack
with the accumulation of red rust and green corrosion products. For
the Ni-Cu layer, the mirror surface gradually became dark, and the
corrosion products were uniformly distributed on the surface. The
Ni-Al-Cu intermetallic layer suffered serious pitting corrosion with
red rust and green corrosion products piling up, implying the pitting
sites penetrating into the NAB substrate.
Fig. 7 shows the SEM images of the Ni-Cu layer (Ni 55.4 wt.% and
Cu 44.6 wt.%), the Ni-Al-Cu intermetallic layer and the NAB substrate
for 12 days in the salt spray chamber. Before observation, the speci-
mens were immersed in 50% HCl solution for 1 3 min to remove the
corrosion products according to the International Standard. Accord-
ing to Fig. 7(a, d), it can be found that the NAB alloy exhibited severe
selective phase corrosion with phase as well as phase in + III
eutectoid structure. Fig. 7b shows that the outer layer of the Ni-Cu
solid solution presented homogenous attack. It was probably due to
the formation of the protective lm, which mainly consisted of
Ni(OH)2 and Cu2O incorporated with Ni ions according to the previ-
ous research [13]. The incorporated Ni ions occupied the mobile cat-
ion vacancies in Cu2O structure, which increased the resistivity of the
protective lm. It could not only inhibit the transfer of the ions and
electrons between the surface and the chloride solution, but also
act as a sacricial anode to protect the surface from being attacked
[13]. With the magnication in Fig. 7e, the uniform attack of the Ni-
Cu layer experienced preferential corrosion at the grain boundaries,
which are some kind of defects and provide a short-cut path for the
transportation of electrons and ions between grains. As is known to
all, the protective lm of Cu oxidations is porous and loose. The Ni
ions dissolved and incorporated into the porous and loose lm as
the ionic state through the grain boundaries. The denickelication
occurred, resulting relatively lower Ni content on the grain bound-
aries [13]. Therefore, it built up corrosion microcells and resulted in
shallow attack along the grain boundaries. As a comparison, Fig.
7(c, f) shows the pitting corrosion in the Ni-Al-Cu intermetallic
layer rather than uniform corrosion in the Ni-Cu layer. With the at-
tack of aggressive Cl ions, the pits were caused by the local galvanic
reaction because of the dealumination [30]. Besides, the galvanic
corrosion between the corrosion productions and the bare substrate
111
accelerated vertical pit growth. Thus, the Cl penetrated though the
pitting and attacked the NAB substrate, which led to the breakdown
of the coating and promoted the corrosion of the NAB substrate, as
shown in Fig. 6.
3.4. The electrochemical impedance tests
The impedance measurements were carried out to characterize the
corrosion properties of the Ni-Cu layer, the Ni-Al-Cu intermetallic
layer and the NAB substrate in the 3.5 wt.% NaCl solution. As shown in
Fig. 8(a), the diameters of semicircles for the Ni-Cu layer and the inter-
metallic layer increase remarkably compared with that of the NAB sub-
strate, which indicates improved corrosion resistance of the Ni-Cu layer
and the intermetallic layer. The impedance Bode plots in Fig. 8(b) show
that the impedance magnitudes of the Ni-Cu layer and the Ni-Al-Cu in-
termetallic layer are ~ 4.7 and ~ 4.6, much larger than that of the NAB
alloy with ~3.4. It could be concluded that the enhanced corrosion resis-
tance of the Ni-Cu layer and the intermetallic layer was attributed to the
growth of the protective lm. The phase maximum angles shown in Fig.
8(c) are derived from the formation of the multi-layer protective lm
[31,32], with the values of 80, 75and 60 for the Ni-Cu layer, the inter-
metallic layer and the NAB alloy, respectively. It is indicated that the Ni-
Cu layer and the intermetallic layer exhibited decreasing corrosion rate
compared with that of the NAB alloy. The data was tted by the corre-
sponding equivalent circuit as shown in Fig. 9. The Rs presents the solu-
tion resistance; CPE contains two parameters of a pseudocapacitance
and an exponent; Rp = Rp1 + Rp2 accounts for the corrosion resistance;
W is the Warburg impedance for the diffusion process. The tting re-
sults are described in Table A.1. It can be found that the corrosion resis-
tance (Rp = Rp1 + Rp2) of the Ni-Cu layer and the intermetallic layer is
much larger than that of the NAB alloy, conrming the improved corro-
sion resistance of the modied layers. Besides, the parameter n1
Fig. 9. The corresponding equivalent circuit used to t the impedance data after immersed
in 3.5 wt.% NaCl solution.
112 Q. Luo et al. / Surface & Coatings Technology 309 (2017) 106113

2CuCl2 H2 OCu2 O 4Cl 2H 7

Cu2O is the main composition of the protective lm of the Cu-based

alloys [34,35]. With a prolonged corrosion time in the salt spray cham-
ber, further oxidation occurred through the reactions as follows [36]:

1
Cu2 O O2 2CuO 8
2

Cu2 O 3H2 O2CuOH2 2H 2e 9

It can be seen that the major content of the protective lm was

Ni(OH)2, Cu/Cu2O and CuO, and only a small content of NiCl2 and
Cu(OH)2 was recorded. It is conrmed that the protective lm on the
Ni-Cu surface protected the Ni-Cu surface from further corrosion and
improved the corrosion resistance as discussed above.

4. Conclusions

This work has developed a surface modication of the NAB alloy

Fig. 10. XPS spectra of the corrosion product layer on the surface of the Ni-Cu layer after
salt spray test for 12 days: (a) core-level Ni2p 3/2 spectrum; (b) core-level Cu2p 3/2
spectrum.
increases with the modied layers, indicating the formation of the com-
pact protective lm.
3.5. XPS analysis of the Ni-Cu layer
In order to analyze the protective lm formed on the Ni-Cu layer,
the XPS spectra of the Ni-Cu layer after salt spray test for 12 days
were recorded as shown in Fig. 10. It shows the Ni2p 3/2 peak and
the Cu2p 3/2 peak, which were deconvoluted by the CasaXPS soft-
ware. From Fig. 10(a), the deconvolution of the core-level Ni2p 3/2
spectrum appeared two peaks at 855.6 eV and 856.9 eV, correspond-
ing to Ni(OH)2 and NiCl2, respectively [32,33]. The relative quantities
of Ni(OH)2 and NiCl2 are 86.1% and 13.9%, indicating that only a small
amount of Ni(OH)2 was further oxidized to NiCl2 and the main con-
tent of the Ni oxidations was Ni(OH)2. The Ni oxidations were possi-
bly described as the following equations [33]:
by thermal diffusion process, which was designed as the outer gradi-
ent layer of the Ni-Cu solid solution and the inner layer of the Ni-Al-
Cu intermetallic layer by means of intrinsic properties of the triple
diffusion system of Cu, Ni and Al. Cu atoms diffused faster than Al
atoms within Ni matrix, which resulted in the continuous accumula-
tion of Al atoms in the inner layer to generate the Ni-Al-Cu interme-
tallic layer, and the Ni-Cu solid solution acted as the outer layer. The
Volta potential changed gradually in the Ni-Cu solid solution,
resulting in the relief of driving force for selective phase corrosion.
According to the salt spray test, it can be found that the outer layer
of the Ni-Cu solid solution presented less serious corrosion behavior
compared to the NAB alloy and exhibited homogeneous corrosion.
Therefore, the selective phase corrosion of the NAB alloy could be ef-
fectively improved by the thermal diffusion modied coating. The
EIS test showed that the modied Ni-Cu layer improved the corro-
sion resistance of the NAB substrate due to the growth of the protec-
tive lm, which mainly consisted of Ni(OH)2 and Cu2O according to
the XPS results.
Acknowledgements
This work was nancially supported by the National Basic Research
Program of China (973 program) under Grant No. 2014CB046701 and
the National Natural Science Foundation of China under Grant No.
51601114.

Ni 2OH NiOH2 2e 3 Appendix A

NiOH2 NiOOH H e 4

Ni2 2Cl NiCl2 5 Table A.1
Fitting parameters for the Ni-Cu layer, the intermetallic layer and the NAB substrate in 3.5
wt.% NaCl solution.
The deconvolution of the core-level Cu2p 3/2 spectrum yielded
three peaks at the B.E. of 932.6 eV, 934.5 eV and 936.1 eV, corre- Parameters NAB Intermetallic layer NiCu layer
sponding to Cu/Cu 2O, CuO and Cu(OH)2 , as shown in Fig. 10(b). Rs/ cm2 6.362 7.951 7.236
The relative quantities are 50.64%, 42.16% and 7.2%, respectively, Y1Q/F cm2 1.551E4 1.492E5 2.358E5
suggesting that the corrosion process on the surface was restrained n1 0.768 0.912 0.972
RP1/k cm2 1.378 4.991 1.073
with little content of Cu(OH)2. The Cu oxidations occurred during
RP2/k cm2 0.227 12.18 18.02
the corrosion process through the reactions [34]: Y2Q/F cm2 0.0062 6.385E6 1.472E5
n2 0.8 0.776 0.824

Cu 2Cl CuCl2 e 6 W 103/ cm2 4.067 0.5108 0.5718
 Q. Luo et al. / Surface & Coatings Technology 309 (2017) 106113
Appendix B
d Dt=t 0 n B:1 [15] M. Ishikawa, H. Enomoto, N. Mikamoto, T. Nakamura, M. Matsuoka, C. Iwakura,
X X
W i
wi  i = i
i B:2
Ni 2OH NiOH2 2e B:3
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1
Cu2 O O2 2CuO B:8
2 micro-multilayer system, Mater. Lett. 89 (2012) 223225.
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