Corrosion Science xxx (xxxx) xxx–xxx

Contents lists available at ScienceDirect

Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

The role of nickel in mechanical performance and corrosion behaviour of

nickel-aluminium bronze in 3.5 wt.% NaCl solution
⁎
Fenfen Yang, Huijun Kang, Enyu Guo, Rengeng Li, Zongning Chen , Yanhua Zeng,
⁎
Tongmin Wang
Key Laboratory of Solidification Control and Digital Preparation Technology (Liaoning Province), School of Materials Science and Engineering, Dalian University of
Technology, Dalian 116024, China

A R T I C LE I N FO A B S T R A C T

Keywords: The mechanical properties and corrosion behaviour in 3.5 wt.% NaCl solution of as-cast nickel-aluminium
A. Nickel-aluminium bronze bronze (NAB) alloys with four Ni contents were investigated. The increase in Ni content leads to more pre-
A. Nickel cipitated κ phases, therefore improving the yield strength and hardness of the NAB alloys. Ni addition was found
B. TEM to significantly suppress the formation of corrodible β' phase and increase the Ni concentration in α solid so-
B. EIS
lution. The electrochemical impedance spectroscopic and static immersion tests showed that the increase in Ni
B. Mass loss
C. Selective phase corrosion
content (4.5–10 wt.%) improved the corrosion resistance of the NAB alloys in 3.5 wt.% NaCl solution.

1. Introduction
Nickel-aluminium bronze (NAB) containing specified amounts of Ni,
Al and Fe in copper matrix has a desired combination of mechanical
properties and corrosion resistance. Therefore, NAB alloys have found
many applications in seawater systems such as pumps, valves and ship
propellers [1]. Generally, the microstructure of as-cast NAB alloy con-
sists of α Cu-rich matrix, retained martensitic β or β' phase and several
intermetallic phases collectively known as κ phases [2]. The aluminium
element mainly acts as a strengthening agent, enhancing the mechan-
ical properties of the NAB alloy by solid-solution strengthening [3]. The
nickel and iron additions suppress the formation of brittle phase γ2, i.e.
Al4Cu9, which is attacked preferentially in seawater and thus, is usually
undesirable [4].
Recently, attempts have been made to improve the corrosion re-
sistance and mechanical properties of the NAB alloys through compo-
sition design [5,6], heat treatment [7,8], plastic deformation techni-
ques [9–12] and surface modifying methods [13–15]. Wu et al. [7]
reported that the strength and hardness, as well as the erosion-corrosion
resistance of the NAB alloy, can be effectively improved by the gen-
eration of many hard phases such as β' and κ phase through normalizing
and quenching treatment. Hot working and equal channel angular
pressing are also effective in enhancing the mechanical properties of the
NAB alloy [10–12]. It is reported that friction-stir processing (FSP) can
refine the coarse microstructure of the NAB alloy and eliminate the
porosity defects, thereby significantly increasing the corrosion
resistance of the alloy in 3.5 wt.% NaCl solution [13]. Other surface
modifying methods including nickel ion implantation [14], thermal
diffusion of Ni coating [15], laser surface melting [16] and laser surface
alloying [17] are also adopted to improve the anti-corrosion property of
the NAB alloy. However, heat treatment and plastic deformation tech-
niques fail to process the heavy castings such as propeller. Surface
modifying treatments can only improve the mechanical properties and
corrosion resistance of the surface layer rather than the bulk material.
Alloy composition plays a critical role in the microstructural evolution
of metallic materials, especially the NAB alloys, and thus it is able to
effectively modify the mechanical and corrosion properties of the NAB
alloys through composition optimization. Cheng et al. [18] found that
rust layers formed on weathering steels tend to be more compact and
more adherent to the substrate with the increasing alloyed Ni content in
weathering steels, thus improved the corrosion resistance in acidic at-
mospheres. Badawy et al. systematically investigated the corrosion
behaviour of Cu-xNi (x = 5, 10, 30, 65 wt.%) alloys in a series of dif-
ferent solutions, including neutral sodium sulphate solution [19],
neutral sodium chloride solution [20], acidic chloride solution [21] and
acidic sulphate solution [22], and they found that the increase in Ni
content increases the corrosion resistance of the alloy and improves its
stability due to the formation of a more stable passive film on the
surface. However, in the case of Cu-Al-Ni ternary alloys, the effect of Ni
content on the corrosion rate shows entirely different trends in sul-
phate-chloride solution and chloride free neutral solutions [23,24]. The
Cu-Ni binary alloy is a basic single phase material in which copper and

⁎
Corresponding authors.
E-mail addresses: znchen@dlut.edu.cn (Z. Chen), tmwang@dlut.edu.cn (T. Wang).

https://doi.org/10.1016/j.corsci.2018.05.012
Received 17 January 2018; Received in revised form 10 May 2018; Accepted 11 May 2018
0010-938X/ © 2018 Elsevier Ltd. All rights reserved.

Please cite this article as: Yang, F., Corrosion Science (2018), https://doi.org/10.1016/j.corsci.2018.05.012
F. Yang et al.
nickel can form complete solid solution in both liquid and solid states,
while the microstructures of Cu-Al-Ni system consist of α phase (Cu-rich
solid solution), β2' (NiAl), γ2 (Cu9Al4) and μ phase [25]. The existence
form of Ni element (solid solution or intermetallic compounds) is clo-
sely correlated to the effect of Ni content on the corrosion behaviour of
multi-phase copper alloys. However, little attention is focused on the
relationship between the various phases and the comprehensive prop-
erties, both corrosion properties and mechanical properties, of the
multi-phase copper alloys.
This study aims to explore the role of Ni in affecting the mechanical
properties and corrosion resistance of NAB alloy. Microstructural ob-
servation was carried out to link the change in the microstructure to the
mechanical performance and corrosion behaviour of NAB alloys, at four
compositions with varying Ni content. Both electrochemical impedance
spectroscopy (EIS) measurements and mass loss measurements were
conducted to evaluate the corrosion property of NAB alloys in this
work.
2. Material and methods
2.1. Material and microstructure characterization
The alloys studied in this work were melted using pure Cu (99.97%
purity, weight percentage, all in the same unit unless otherwise speci-
fied), Al (99.99%), Ni (99.995%), Fe (99.95%) and Mn (99.8%) in a
vacuum induction melting furnace under argon atmosphere. After fully
mixing, the melt was cast into an iron mould with a size of
40 × 50 × 150 mm3. Samples taken from the as-cast ingots were di-
rectly used for microstructural observation, mechanical tests and cor-
rosion tests. The nominal compositions of four as-cast ingots are Cu-
9Al-xNi-4Fe-1.2Mn (denoted as NAB-xNi in the text), where x = 4.5, 6,
8, and 10, respectively. The real compositions of four alloys, as mea-
sured by X-ray fluorescence spectrometry method, are listed in Table 1.
The microstructures of the samples were examined using optical
microscope (Olympus GX51, Olympus Corp., Japan) and scanning
electron microscope (SEM, Zeiss supra 55, Zeiss Corp., Germany) fitted
with an energy dispersive spectroscopy (EDS). The samples were me-
chanically ground, polished and then etched with a solution having 3 g
FeCl3, 2 ml HCl (36–38 wt.%, AR) and 95 ml C2H5OH (AR). The samples
for transmission electron microscope (TEM) investigation were ground
to 50 μm and then ion-beam milled using a Gatan Precision Ion
Polishing System (Gatan model 695, Gatan Inc., America). The TEM
foils were characterized using a Talos field emission transmission
electron microscope (Talos F200x, FEI Corp., America) operating at an
accelerating voltage of 300 kV. Phase fraction of various phases in NAB
alloys were analysed at three representative positions on the samples
using Image-Pro Plus V6.0 software package.
2.2. Mechanical tests
Vickers micro-hardness (HV) measurements were conducted using
an applied load of 200 g for 10 s on a micro-hardness tester (MH-50,
Shanghai Everone Precision Instruments Corp., China). For each
sample, the measurements were repeated 10 times at an interval of
150 μm to obtain an arithmetic mean value. Each flat tensile sample
(2 mm in thickness), as shown in Fig. 1a, was tested on a universal
Table 1
Chemical compositions of materials used in the present study (in wt.%).
Al Ni Fe Mn
NAB-4.5Ni 9.26 4.40 3.92 1.15
NAB-6Ni 9.38 5.91 4.07 1.19
NAB-8Ni 9.65 7.93 4.04 1.19
NAB-10Ni 9.53 9.85 4.06 1.20
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tensile machine (Instron 5569, Instron Corp., America) with a strain
rate of 2 mm/min at room temperature. At least three tensile tests were
carried out for each NAB alloy. The fracture morphology of each sample
after tensile test was observed by SEM.
2.3. Electrochemical impedance tests
The samples for EIS tests were ground consecutively with SiC
abrasive paper starting from 240 to 2000 grit size, washed thoroughly
with distilled water, dried by cold air and then transferred quickly to
the 3.5 wt.% NaCl solution. The solution was replaced by a freshly
prepared one after each measurement. The dimension of the active
section of the electrochemical test samples was 0.6 cm in diameter and
0.2827 cm2 in area.
All electrochemical measurements were conducted at room tem-
perature (25 ± 1 °C) using a Gamry electrochemical workstation
(Reference 600, Gamry Instruments Inc., America). A conventional
three-electrode system with studied alloy as the working electrode, a
large platinum foil of 20 mm × 20 mm as the counter electrode and a
Ag/AgCl electrode (saturated KCl with electrode potential of 0.1981 V
vs. Standard Hydrogen Electrode) as reference electrode was used in the
measurements. After immersion in the test solution, reaching a steady
open circuit potential (OCP), the EIS measurement was performed at
OCP in the frequency range from 105 Hz to 10−2 Hz with an alternate
current signal of 5 mV rms (root mean square). For each condition, at
least three samples were tested to ensure the reproducibility. According
to the general variation trend of EIS experimental results, the most
representative data were selected for plotting. Then these EIS data were
fitted and analysed carefully using Zsimpwin 3.10 software package.
2.4. Static immersion tests
The test samples for the mass loss measurement (Fig. 1b) had a
mounting hole with diameter of 3 mm and thickness of 2 mm. Each
sample was ground with 240 grit SiC paper, ultrasonically cleaned in
ethanol for 3 min, rinsed with distilled water, dried by cold air and then
weighed carefully on an analytical balance (ME204E, Mettler Toledo
Corp., Switzerland) with an accuracy of ± 0.1 mg. The exposed area of
each sample was calculated independently. Each sample was suspended
by fine coated metallic wire and immersed in a container with 300 ml
naturally aerated 3.5 wt.% NaCl solution which well satisfies the re-
quirement of the minimum solution volume to sample area ratio
(0.20 ml/mm2) according to the ASTM Standard G31-72 [26]. The NaCl
solution was prepared using distilled water and analytical grade che-
micals. The temperature of solution was maintained at 25 ± 1 °C
throughout the whole experimental procedure in a thermostatic water
bath. To compensate for the evaporation losses, appropriate distilled
water was added to the solution every day to maintain the original
volume. The solution was replaced with a fresh one every week. At the
end of the immersion test (1, 3, 5, 7, 14, and 28 days), the corroded
samples were immersed in a solution of 500 ml HCl (36–38 wt.%,
AR) + 500 ml distilled water for 3 min to remove the corrosion pro-
ducts, rinsed with distilled water, dried in a thermostatic drier box at
80 °C for 2 h, and finally weighed. For each condition, three samples
were tested and an average value was reported.
Another group of corrosion samples for surface morphology analysis
and phase identification were prepared in a dimension of 10 × 10 × 7
mm3. These samples were successively ground with SiC abrasive papers
to 2000 grit and polished with 1 μm diamond paste. After immersion in
Cu naturally aerated 3.5 wt.% NaCl solution for 60 days, the phases in the
corrosion product film were identified using an X-ray diffractometer
Bal. (XRD, PANalytical Empyrean, Netherlands) with Co Kα radiation at a
Bal.
scanning speed of 0.13926°/s. The surface morphologies and cross-
Bal.
Bal. section morphologies of the corroded samples were also observed by
SEM.
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Fig. 1. The dimensions of the sample for (a) tensile test and (b) static immersion test (unit: mm).

Fig. 2. Optical micrographs of the NAB samples with different Ni contents: (a) NAB-4.5Ni; (b) NAB-6Ni; (c) NAB-8Ni; (d) NAB-10Ni.

3. Results and discussion Table 2

The average chemical composition of α phase in the NAB alloys.
3.1. Microstructures Material Chemical composition (in wt. %)

The optical micrographs of the as-cast NAB alloys are presented in Al Ni Fe Mn Cu

Fig. 2. The microstructure of the NAB-4.5Ni alloy (Fig. 2a) consists of α
NAB-4.5Ni 7.55 3.04 3.22 0.90 85.30
phase (light etched area), retained β or β' phase (dark etched area), and NAB-6Ni 7.36 3.99 3.43 1.03 84.18
several intermetallic κ phases. With increasing Ni content, an evident NAB-8Ni 7.33 5.33 3.22 0.96 83.17
change in the morphology of α phase is noticed. The NAB-4.5Ni alloy NAB-10Ni 7.36 6.57 3.27 1.16 81.62
and NAB-6Ni alloy were associated with the Widmanstätten α phase.
Whilst increasing the Ni to 8%, α phase became continuously wheatear-
shaped (Fig. 2c), nevertheless, the α phase appeared to be coarse and and the intergranular β' phase is martensite which contains a high
irregular block in the NAB-10Ni alloy (Fig. 2d). density of NiAl precipitates [27]. The globular κII precipitates, which
The average chemical composition of α phase in different NAB al- mainly distribute at the grain boundaries, can be more clearly observed
loys, as measured by EDS analysis, is listed in Table 2. The Ni content in at high magnification, as shown in Fig. 3b. The eutectoid transforma-
α phase increases from 3.04% to 6.57% with the increase of Ni addition tion product κIII phase appears as lamellar or globular (degenerate la-
from 4.5% to 10%, whilst little change is observed with respect to other mellar) structure. The EDS results in Fig. 3c and d show that κII particles
alloying elements. The variation of Ni content in α phase is in ac- are iron-rich and the κIII precipitates are rich in nickel and aluminium.
cordance with the nominal composition, indicating that part of the For detailed examination, the microstructure was further observed
added Ni element has dissolved into the α phase. using TEM and the results are shown in Fig. 4. It is seen that the
Fig. 3 shows the SEM image of the as-cast microstructure of the morphology of the κII precipitates is a bit globular, and those pre-
NAB-4.5Ni alloy. The microstructure of NAB-4.5Ni consists of α phase, cipitates have a size of around 1 μm. The κII precipitates can be iden-
β' phase, κII and κIII precipitates, as marked by the black arrows in tified as Fe3Al phase [2] according to the selected area diffraction
Fig. 3a. The α phase is face-centered cubic (fcc) Cu-rich solid solution, pattern (SADP) (see the inset in Fig. 4a). The high resolution

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Fig. 3. SEM images of microstructure of NAB-4.5Ni sample: (a) secondary electron image; (b) the magnified image of area A in square frame in (a) ; (c) and (d) are the
EDS results at selected point B and C, respectively.

transmission electron microscope (HRTEM) image in Fig. 4b shows the The area fraction of various phases in NAB alloys is shown in Fig. 6.
κII/α interface, which exhibits a large number of well-defined alternate For the ease of measurement and the fact that the various precipitates
bright and dark parallel Moiré patterns with a mean spacing D between play a similar role in mechanical property, the κII particles (mainly
1.02 and 1.42 nm. This observation suggests a good bonding interface located in the eutectoid region), lamellar κIII phase and the coarse NiAl
[28] between the κII precipitates and α matrix. Fig. 4c shows the bright strips are all counted as “κ phase” in this work. According to the
field TEM image of the lamellar α + κIII eutectoid and β' phase. Mar- quantitative data, the amount of κ phase increases monotonously as the
tensitic twins with an average thickness of about 40 nm can be clearly Ni content increases. The area fraction of both α and β' phases show a
distinguished within the β' phase. The eutectoid κIII precipitates with trend of decrease. Note that when the nominal content of Ni reaches
thickness between 10 nm and 70 nm are identified as NiAl phase, which 8%, β' phase disappears completely.
can be further confirmed by the (110)NiAl lattice fringes in the HRTEM
image (Fig. 4d).
3.2. Mechanical properties
Fig. 5a is the SEM image showing the microstructure of NAB-6Ni.
Strips of continuous and coarse intermetallic compound (IMC), instead
The tensile mechanical properties and micro-hardness of each NAB
of κII phase, are formed both at the grain boundary of α phase and at the
alloy are summarized in Table 3 for comparison. The addition of Ni
periphery of the lamellar eutectoid regions. Furthermore, only a small
element improves the yield strength (σ0.2) and hardness of the NAB
amount of β' phase is observed in the microstructure of NAB-6Ni
alloys. However, the ultimate tensile strength (σb) and elongation ex-
compared with that of NAB-4.5Ni. Further increasing the Ni content
hibit an inverse trend, which is in consistent with the regression cal-
results in the disappearance of the martensitic β' phase (Fig. 5b and c),
culations reported by Łabanowski et al. [6].
which has not been reported (to our knowledge). Likewise, more and
It is well known that the variations of mechanical properties are
more coarse IMC strips are present in the microstructure of the NAB
closely connected with the chemical composition and microstructures
alloys with the increasing Ni content. The EDS analysis (Fig. 5d) reveals
of alloys. Among the phases in the as-cast NAB alloys, the α phase
that the coarse IMC phase is enriched in nickel and aluminium. It is
matrix is a soft Cu-rich solid solution with the highest ductility, while
conceived that the coarse IMC strips should have the same composition
martensitic β' phase is much stronger and harder [7]. The precipitates,
as the eutectoid κIII phase, i.e. NiAl phase. In order to further confirm
including the globular κII, fine lamellar κIII and coarse NiAl strips, are all
the crystal structure of the coarse IMC phase, detailed TEM observa-
hard phases, but less ductile, which can be considered as brittle phases.
tions of the NAB-10Ni alloy were conducted. Fig. 5e shows the bright
The soft α phase mainly contributes to the excellent ductility of the NAB
field TEM image of the coarse IMC strip. From the SADP (the inset in
alloys, but has a negative effect on the yield strength and hardness.
Fig. 5e), the coarse IMC phase has been ascertained to be NiAl phase,
In general, the three NAB samples with increased Ni addition ex-
which is further confirmed by the HRTEM in Fig. 5f. The thickness of
hibit apparently improved yield strength and hardness. The yield
coarse IMC strips in NAB-10Ni (Fig. 5e) was measured to be 180 nm ∼
strength of the NAB-8Ni sample reaches 322 MPa, 34 MPa higher than
500 nm, much larger than that of the lamellar eutectoid κIII phase in
that of the NAB-4.5Ni sample. This improvement is ascribed to the
NAB-4.5 Ni alloy (Fig. 4a and c).
change in fraction ratio of various phases and the strengthening of α

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F. Yang et al.
Fig. 4. TEM images of microstructure of NAB-4.5Ni sample: (a) the bright-field TEM image with SADP inset from κII precipitates; (b) the HRTEM image showing the
κII/α interface; (c) the bright field TEM image with SADP inset from κIII precipitates; (d) the HRTEM image showing the κIII/α interface.
matrix. As the Ni content increases, the microstructures of the NAB
alloys contain fewer soft α phase and more hard precipitates (Fig. 6),
resulting in a significant increase in yield strength and hardness. The
increased amount of Ni solute in α phase (Table 2) can also strengthen
the α matrix and improve the yield strength of the NAB alloys via the
solid-solution strengthening. Among the four NAB samples, the NAB-
6Ni sample shows the highest hardness (208.5 H V, 23 H V higher than
that of NAB-4.5Ni sample), which is associated with the homogeneous
and fine microstructure (Fig. 2b).
With respect to the ultimate strength and elongation, the descend
trend with the increasing Ni content is closely related to the size of α
matrix and the morphology of the precipitates. Compared with the
wheatear-shaped and coarse block α phase in NAB-8Ni and NAB-10Ni
alloy, the α phase in NAB-4.5Ni and NAB-6Ni alloy is apparently
smaller in size and the overall microstructure is more homogeneous
(Fig. 2). With the increasing Ni content in NAB alloys, the fine globular
κII precipitates disappear, while the amount of coarse and continuous
NiAl strips is increased (Fig. 5), which results in the decrease of ulti-
mate strength and elongation. The mechanical property of the multi-
phase materials is the result of the comprehensive effect of a number of
critical factors, such as the concentration of solute atoms in the matrix,
the grain size, the morphology and distribution of the reinforcement
phases, and the volume fraction of various composed phases [29–32].
Fig. 7 shows the fracture morphologies of the NAB alloys after
tensile tests. The SEM micrograph of fracture surface (Fig. 7a) shows a
great number of conical equiaxed dimples, suggesting a good ductile
fracture nature of the NAB-4.5Ni sample. Besides, a few small flat facets
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as marked with the black arrow are also observed. As shown in Fig. 7b,
the fracture morphology of NAB-6Ni sample is similar to that of the
NAB-4.5Ni, except that the dimples are less in quantity. As expected,
the elongation of the NAB-6Ni sample decreases to 20.7%, 10% lower
than that of the NAB-4.5Ni alloy. Both the NAB-8Ni and NAB-10Ni
samples (Fig. 7c and d) exhibit a brittle fracture with a large quantity of
small flat facets. According to these fracture morphologies, it seems that
the addition of Ni in the NAB alloys tends to induce the ductile to brittle
transition, which is in accordance with the elongation results.
3.3. Electrochemical impedance tests
To study the influence of Ni content on the electrochemical beha-
viour of NAB alloys, the EIS measurements for the NAB alloys in stag-
nant neutral 3.5 wt.% NaCl solution were carried out. The corre-
sponding Nyquist plots and Bode plots are presented in Figs. 8 and 9,
respectively.
As shown in Fig. 8a, the Nyquist plots of the four alloys after 0.5 h
immersion in 3.5 wt.% NaCl solution exhibit the similar shape, with a
depressed capacitive reactance arc in higher frequency (HF) range and
a straight Warburg line in lower frequency (LF) range. The HF capa-
citive arc represents a combination of the charge transfer resistance on
bare electrode and that contributed by the surface film [33]. The LF
Warburg impedance is related to the diffusion process of oxygen from
the solution to electrode surface [34] or of the cuprous chloride ion
complex (CuCl2−) from the electrode surface across a diffusion layer
[35]. This indicates that the corrosion mechanism of NAB alloys in
F. Yang et al. Corrosion Science xxx (xxxx) xxx–xxx

Fig. 5. (a, b, c) Secondary electron images of microstructures of NAB-6Ni, NAB-8Ni, and NAB-10Ni sample, respectively; (d) the EDS result at selected point A; (e) the
bright-field TEM image with SADP inset from coarse IMC strips in NAB-10Ni; (f) the HRTEM image showing the interface between coarse IMC strips and α phase.

Table 3
Mechanical properties of the NAB alloys with different Ni contents.
Material σ0.2 (MPa) σb (MPa) Elongation (%) Hardness (HV)

NAB-4.5 Ni 288 ± 8 696 ± 14 31.2 ± 1.5 185.3 ± 11.5

NAB-6 Ni 320 ± 2 656 ± 25 20.7 ± 2.5 208.5 ± 18.8
NAB-8 Ni 322 ± 6 590 ± 10 11.6 ± 0.4 192.4 ± 10.5
NAB-10 Ni 312 ± 8 589 ± 6 14.0 ± 1.6 192.5 ± 27.6

Fig. 6. Phase fraction in NAB alloys with different Ni contents.
3.5 wt.% NaCl solution is controlled not only by a charge transfer step
but also by a diffusion process [20,36,37]. The increase in the diameter
of capacitive arcs with the increasing Ni content (Fig. 8a–d), regardless
of the immersion time, reveals an enhancement of the corrosion re-
sistance through Ni addition. With the prolonged immersion time, the
LF straight line or Warburg impedance is difficult to identify gradually.
At the onset of immersion test, the interfacial charge transfer process is
fast, the diffusion behaviour of redox reactants plays a prominent role
in the corrosion process and the Warburg impedance can be observed
clearly in the Nyquist plots [38]. On the contrast, the interfacial charge
transfer resistance increases with the formation of the protective film

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F. Yang et al.
Fig. 7. Fracture morphologies of NAB samples with different Ni contents: (a) NAB-4.5Ni; (b) NAB-6Ni; (c) NAB-8Ni; (d) NAB-10Ni.
on the electrode surface and becomes the major factor affecting the
corrosion process, the impedance spectrum presents a large semicircle
(Fig. 8c and d) and Warburg impedance cannot be identified [33]. As a
result, the LF straight line disappears first (Fig. 8b) for NAB-10Ni
sample with the prolonged immersion time due to the formation of
more stable oxide film.
Fig. 9 shows the corresponding Bode plots of the impedance spec-
trum present in Fig. 8. Initially, the LF magnitude |Z| plots are close to
each other (Fig. 9a), meaning that there is only a small difference be-
tween the corrosion resistances of the four alloys. Along with the in-
crease in test duration, the LF magnitude |Z| plots are shift upwards and
far apart from each other, indicating that the corrosion resistance in-
creases with both the immersion time and the Ni content. Besides, the
recorded gradual increase of the phase maximum and the broadening
phase angle with the increasing Ni content also suggests an improve-
ment in anti-corrosion quality [39].
Different equivalent electrical circuit models have been performed
to interpret the corrosion behaviour of NAB alloys in chloride solutions.
The most commonly used circuits [14,36,37,40–42] are shown in
Fig. 10, where Rs represents the solution resistance, Rf the film re-
sistance, Rct the charge transfer resistance, Rp the polarization re-
sistance and Wd the Warburg diffusion impedance. In order to evaluate
the overall corrosion resistance, Rp can be expressed as Rp = Rf + Rct
for the equivalent circuit shown in Fig. 10a. Take into account the ca-
pacitance dispersion originated from the surface roughness and het-
erogeneities, CPE is introduced to feature the non-ideal capacitor [43]
and realize an optimum fitting. Therefore, CPE1 and CPE2 in Fig. 10a
correspond to the non-ideal capacitance of the passive film and the
double-charge layer, respectively. The impedance of CPE can be defined
by ZCPE = [Q(jω)n]−1, where Q is the magnitude of the CPE, j the
imaginary number (j = −1 ), ω the angular frequency (ω = 2πf, f is
the frequency), and n the CPE exponent [44,45]. If n = 1, the CPE is
identical to an ideal capacitor, while for n = 0.5, the CPE represents a
Warburg impedance with a diffusional character. The circuit with two
time constants in parallel (Fig. 10a) has been used to explain both
passivity behaviour (CPEf, Rf) and corrosion activity (CPEdl, Rct)
[14,20,40–42], while Fig. 10b shows a simple circuit with one time
constants which represents (CPEf + dl, Rp) for the overall surface, where
the subscript (f + dl) denotes surface films and the double-charge layer
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Corrosion Science xxx (xxxx) xxx–xxx
at the interface [36,37,46]. These two different equivalent electrical
circuits are both used to fit the impedance data in present study, the
former (Fig. 10a) is used to fit the EIS data corresponding to the short
immersion time (0.5 h and 1 day), and the latter (Fig. 10b) is for the
cases of 3 and 7 days immersion. This choice is a compromise between a
reasonable description of the variations of electrochemical system and a
good fitting quality. In fact, trials fitting the EIS data of long immersion
time using the circuit with two time constants were done, but the fitting
errors were high.
The fitted impedance parameters obtained for the NAB alloys after
different immersion time are listed in Tables 4 and 5. The chi-square
value, which is used to evaluate the goodness of fit, is in the order of
10−3 to 10−4 in all cases. Both the small chi-square values and the good
agreement between the experimental points and the fitting curves
suggest a good fitting quality. As compared in Table 4, a sharp increase
of the polarization resistance Rp i.e. the overall corrosion resistance of
NAB alloy with the increasing Ni content is observed. In the initial
immersion stage (0.5 h), both the film resistance (Rf) and the charge
transfer resistance (Rct) of NAB alloys increase with the Ni content.
With the prolonged immersion time, all of the four alloys show an in-
crease in Rf value, reflecting the growth of the surface film and an
improvement in its protective property [47]. Moreover, the Ni addition
also gives rise to an increase in the n1 values. This is probably related to
the more compact oxide film formed on the surface [14]. In the case of
1 day immersion, Rct values of NAB-6Ni and NAB-8Ni alloys are lower
than that of NAB-4.5 Ni alloy whereas the overall corrosion resistance
are still improved due to their higher Rf values. Consequently, the im-
proved protective property of the surface film is believed to be the main
course for the enhanced corrosion resistance of NAB alloys by Ni ad-
dition. Based on the fitted electrochemical parameters summarised in
Table 5, it can be seen that the Ni addition and the immersion time
continuously increase the polarization resistance i.e. the corrosion re-
sistance. For example, the Rp value increases significantly to
12,770 Ω cm2 with the increasing Ni content, almost 7 times that of the
NAB-4.5Ni sample (1854 Ω cm2).
The variation of the polarization resistance is plotted against the
immersion time for all of the alloys in Fig. 11, making the EIS results
more intuitive and clear. For NAB-4.5Ni and NAB-6Ni samples, the
polarization resistance value continues to increase slowly in the
F. Yang et al.
Fig. 8. Nyquist plots for different NAB alloys after various periods of immersion in 3.5 wt.% NaCl solution: (a) 0.5 h; (b) 1 d; (c) 3 d; (d) 7 d. The solid curves are the
fitted results. The insert in (a) shows the details of the curves.
duration of 7 days immersion test. In comparison, the polarization re-
sistance curves of NAB-8Ni and NAB-10Ni samples show a rapid in-
crease in the first 3 days of immersion and then tend to reach a steady
state. The polarization resistance value of NAB-10Ni is always the
highest throughout the whole test period. It can be concluded that a
significant enhancement of anticorrosion property of NAB alloys is
achieved by Ni addition.
It has been generally accepted that for the corrosion behaviour of
copper and its alloys in naturally aerated neutral chloride solution
[48–51], the cathodic process is dominated by the oxygen reduction
reaction:
O2 + 2H2 O + 4e− → 4OH−
The major anodic reaction of the NAB alloys is the copper dissolu-
tion to form dichlorocuprous anion complex which can be simplified as
following [52–55]:
Cu + 2Cl− → CuCl 2− + e−
It was reported that the hydrolysis reaction of cuprous dichloride
anion in neutral solutions results in the formation of cuprous oxide
(Cu2O) [39,56]:
Corrosion Science xxx (xxxx) xxx–xxx
2CuCl 2− + H2 O → Cu2 O + 4Cl− + 2H+ (3)
With longer exposure time to seawater, Cu2O is further oxidised to
cupric hydroxide Cu(OH)2, or copper hydroxychlorides including
Cu2(OH)3Cl and Cu(OH)Cl [3,49]. Cu2(OH)3Cl is formed according to
the following reaction [41,57]:
Cu2 O + Cl− + 2H2 O → Cu2 (OH )3 Cl + H+ + 2e− (4)
Different from the Cu2O formed by dry oxidation, Cu2O formed in
chloride solution is a highly defective p-type semiconductor, in which
some Cu+ are missing from the cation lattice and a significant number
of cation vacancies are created [58]. The Ni (or Fe) ions enter into the
(1)
degraded Cu2O films by two means [58,59]: (i) Each Ni2+ fills a cation
vacancy site, leading to the annihilation of two positive holes thereby
increasing the ionic resistivity as well as the electronic resistivity of the
Cu2O film. (ii) Each Ni2+ replaces a Cu+ ions in Cu2O lattice, resulting
in the annihilation of one positive hole, which increases the electronic
(2) resistivity of the protective film. Efficiency of the Ni addition on the
corrosion performance improvement is closely related to its existence
form in the alloy such as solid solution and precipitates. It is reported
that only alloy additions dispersed uniformly in solid solution substrate
can be incorporated into the oxide film and improve its corrosion
8
F. Yang et al. Corrosion Science xxx (xxxx) xxx–xxx

Fig. 9. Bode plots of the measured impedance present in Fig. 8: (a) 0.5 h; (b) 1 d; (c) 3 d; (d) 7 d. The solid curves are the fitted results.

3.4. Static immersion tests

The variations of cumulative mass loss and corrosion rate of the

Fig. 10. The equivalent circuits used in the fitting of the impedance data of
different NAB alloys after various periods of immersion in 3.5 wt.% NaCl so-
lution.
resistance [60]. Since part of the added Ni is dissolved into the α solid
solution (as shown in Table 2), undoubtedly the incorporation of more
Ni into the Cu2O film increases the resistivity of the protective film. As a
result, the corrosion performance of the NAB alloy increases sig-
nificantly with the Ni addition.
NAB alloys as a function of immersion time are plotted in Fig. 12.
Corrosion rate is calculated according to ASTM Standard G31-72(2004)
[26]:
K×W
Corrosion rate =
A×T×D (5)
4
where K is a constant (8.76 × 10 ), W mass loss in g, A the exposed area
of the sample in cm2, T the exposure time in hour, and D the density in
g/cm3. The variation curves in Fig. 12 show the gradual increase in the
mass loss of the four alloys with the increase of immersion time. The
mass loss of the NAB-10Ni alloy corresponding to each immersion time
is lower than that of the other three alloys. Zheng et al. [13] reported
that, after 14 days immersion, the mass loss of the C95800 NAB alloy
(the same as NAB-4.5Ni alloy in this work) decreased from ∼ 7 g/m2 to
5 g/m2 through FSP treatment. In the present study, the corresponding

Table 4
Equivalent circuit parameters for different NAB alloys after 0.5 h and 1 d immersion in 3.5 wt.% NaCl solution.
Immersion Material Rs Q1 n1 Rf Q2 n2 Rct Rp Wd χ2
time (Ω cm2) (μF cm−2 sn-1) (Ω cm2) (μF cm−2 sn-1) (Ω cm2) (Ω cm2) (×10−3 S cm-2 s1/2) (×10−3)

0.5 h NAB-4.5 Ni 6.4 237 0.79 124 169 0.84 382 506 2.1 2.34
NAB-6 Ni 5.1 193 0.82 140 215 0.79 495 635 2.0 2.42
NAB-8 Ni 4.4 234 0.84 145 340 0.68 819 964 2.0 1.93
NAB-10 Ni 5.0 207 0.84 163 260 0.66 1245 1408 2.0 3.89

1d NAB-4.5 Ni 25.0 177 0.80 179 136 0.69 921 1100 8.4 0.53
NAB-6 Ni 3.9 225 0.82 753 327 0.81 918 1671 3.0 1.08
NAB-8 Ni 11.4 224 0.84 1568 288 0.84 635 2203 2.2 0.83
NAB-10 Ni 6.0 151 0.84 2603 101 0.76 4987 7590 4.6 2.20

9
F. Yang et al. Corrosion Science xxx (xxxx) xxx–xxx

Table 5
Equivalent circuit parameters for different NAB alloys after 3 d and 7 d immersion in 3.5 wt.% NaCl solution.
Immersion Material Rs Q n Rp Wd χ2
time (Ω cm2) (μF cm−2 sn-1) (Ω cm2) (×10−3 S cm-2 s1/2) (×10−3)

3d NAB-4.5 Ni 4.6 324 0.78 1854 2.7 1.76

NAB-6 Ni 4.5 352 0.83 4336 3.0 1.50
NAB-8 Ni 8.0 278 0.78 10290 4.6 2.99
NAB-10 Ni 5.9 210 0.82 12,770 4.0 5.59

7d NAB-4.5 Ni 4.6 184 0.87 4057 9.0 3.11

NAB-6 Ni 5.6 349 0.81 5464 4.7 4.93
NAB-8 Ni 6.2 266 0.81 10350 2.8 5.46
NAB-10 Ni 4.1 269 0.83 12960 1.6 1.51

corrosion rate in all cases. In electrochemical impedance tests, the po-

Fig. 11. Variation of the polarization resistance of the NAB alloys in 3.5 wt.%
NaCl solution as a function of the immersion time.
larization resistance curves tend to reach a steady state after 3 days, and
for the corrosion rate curves in the immersion tests, it needs 14 days to
reach a quasi-steady stage. This difference is due to that the EIS results
are related to the transient behaviour of an electrochemical interface,
while the mass loss and corrosion rate in immersion test reflect the
average cumulative mass loss. The great change in corrosion rate in the
first 3 days in immersion tests still affects the overall corrosion rate in
the following 11 days. After 14 days immersion, the immersion time is
long enough to weaken the dramatic decrease in the corrosion rate in
the first 3 days and the corrosion rate curve advanced into the quasi-
steady stage.
Fig. 13 shows the XRD patterns of the four NAB alloys after im-
mersion in 3.5 wt.% NaCl solution for 60 days. Due to the limited
amount of corrosion product, the peak intensity partially comes from
the substrate. The similarity of α phase and β' in composition and
structure results in the overlapping of their peaks [61]. Therefore, only
the Cu-rich α matrix, NiAl phase and Fe3Al phase in the substrate are
identified in the XRD patterns. This partially supports the micro-
structure analysis of the NAB alloys in section 3.1. For NAB-4.5Ni and
NAB-6Ni alloys, both copper chloride hydroxides (probably
Cu2(OH)3Cl) and Cu2O, are identified on the corroded surface. How-
ever, for NAB-8Ni and NAB-10Ni alloys, the intensity of the copper
chloride hydroxides decreases, indicating a decrease in its volume
fraction. Besides, the absence of Cu2O peak in the XRD patterns of the
NAB-8Ni and NAB-10Ni is probably due to the small amount. Based on
the XRD analysis, it is concluded that the amount of corrosion product
decreases with the increasing Ni content, which is in good agreement
with the mass loss results.
Fig. 14 shows SEM micrographs of the freshly polished surface and

Fig. 12. Mass loss (ML) and corrosion rate (CR) of different NAB alloys as
functions of immersion time in 3.5 wt.% NaCl solution.

mass loss decreased from 7.5 g/m2 to 3.2 g/m2 as the Ni content in-
creased from 4.5% to 10%, indicating that the improvement in corro-
sion resistance of NAB alloy through alloying seemed to be more ef-
fective than the FSP treatment. Further, the corrosion rate goes through
three characteristic processes during four weeks of exposure. In the first
5 days, the corrosion rate experiences a dramatic decrease (specified as
stage I, sharp-down stage); over the next 9 days, the corrosion rate
tends to decrease at a slower rate (specified as stage II, slow-down
stage); the corrosion rate begins to decrease with a more modest slope
in the following 14 days (specified as stage III, quasi-steady stage). Fig. 13. XRD patterns of different NAB alloys after 60 days of immersion in
Besides, the increase of immersion time causes a significant decrease in 3.5 wt.% NaCl solution.

10
F. Yang et al.
Fig. 14. Surface morphology evolution of the NAB alloys after different periods of immersion in 3.5 wt.% NaCl solution: (a) NAB-4.5Ni; (b) NAB-6Ni; (c) NAB-8Ni;
(d) NAB-10Ni; (e–g) the EDS results at selected point A, B and area C, respectively.
the corroded surface of the NAB alloys after immersion in 3.5 wt.%
NaCl solution for 1 day, 3 days and 60 days, respectively. For the NAB-
4.5Ni alloy, β' phase is corroded severely after 1 day immersion as
presented in Fig. 14a, leaving behind a lot of undissolved NiAl particles
[2]. The eutectoid α phase is also dissolved, while the globular κII and
lamellar κIII are not corroded. All of other three alloys have similar
surface morphologies after 1 day of immersion. The eutectoid α phase
and the α matrix adjacent to coarse NiAl strips are only slightly cor-
roded, whereas the lamellar κIII and coarse NiAl strips are retained.
Besides, some flocculent aggregate is observed after 1 day of immersion
in 3.5 wt.% NaCl solution in all cases. The EDS result (Fig. 14g) shows
that the flocculent aggregate is enriched in copper and oxygen, in-
dicating that the flocculent aggregate might be copper oxide.
As the immersion time increases to 3 days, there is a large amount of
corrosion product on the surface of the NAB-4.5Ni sample, making it
difficult to distinguish β' phase from the eutectoid region. At a higher
magnification, it can be observed that the α matrix is covered by thick
fluffy corrosion product, suggesting that the α matrix also suffers a
certain degree of uniform corrosion damage. For the other three alloys,
11
Corrosion Science xxx (xxxx) xxx–xxx
the microstructures are still clearly distinguishable, although a small
amount of fluffy corrosion product is also observed on their surfaces. In
addition, urchin-like corrosion products (Fig. 14b) appear on the cor-
roded surfaces of all of the four alloys after 3 days of immersion. As
shown in Fig. 14f, the urchin-like corrosion product is probably the
copper chloride hydroxide [34], since it is abundant in copper, oxygen
and chlorine. This is also supported by the XRD results in Fig. 13.
When the immersion time reaches 60 days, the severely damaged
surfaces of the NAB-4.5Ni and NAB-6Ni samples are covered by thick
corrosion product film and a large amount of loose urchin-like corro-
sion products. The EDS results (Fig. 14e) suggest that the underlying
corrosion product film mainly consists of cuprous oxide Cu2O with
minor incorporation of Fe and Ni [57]. The presence of cuprous oxide
on the corrosion product film is supported by the XRD analysis in
Fig. 13. This is clearly in accordance with the earlier study by Blundy
and Pryor [59]; they reported that the corrosion products formed on the
Cu-Ni alloys in chloride solution are duplex structures carrying a
compact oxide film below an outer layer of copper chloride hydroxide
Cu2(OH)3Cl. As shown in Fig. 14a and b, some cracks appear in the
F. Yang et al.
Fig. 15. Cross section BSE images of the NAB alloys after 30 days immersion in 3.5 wt.% NaCl solution: (a) NAB-4.5Ni; (b) NAB-6Ni; (c) NAB-8Ni; (d) NAB-10Ni.
corrosion product film, as indicated by the blue arrow. These cracks
may be induced by the stresses generated in the film during its growth
[62]. In contrast, for the NAB-8Ni and NAB-10Ni samples (Fig. 14c and
d), the corroded surface almost remains the same as that after 1 day of
immersion, except that the flocculent aggregate gradually evolved into
the blocky corrosion products. Considering that Cu2O is the main
constituent of corrosion products for NAB alloys in chloride solution
[41,55], it is likely that the Cu2O film also exists on the surface of NAB-
8Ni and NAB-10Ni samples. However, they are not identified in the two
samples, probably because of the small amount [57,63]. These SEM
observations agree quite well with the XRD results. During the corro-
sion process of NAB alloys with low Ni contents, the corrosive medium
may penetrate into the cracks in the thick product film and this severely
reduces the corrosion performance of the alloy. On the contrary, the
thin but complete oxide films formed on the surfaces of NAB samples
with higher Ni content have better protection for the substrate and thus
improve the corrosion resistance remarkably.
Fig. 15 shows the back-scattered electron (BSE) images of various
NAB alloys in cross section after 30 days immersion in 3.5 wt.% NaCl
solution. For NAB-4.5Ni alloy, corrosion product film with different
thickness is observed on various phases (Fig. 15a). The κ phases are not
corroded and retain in the film [57], while α matrix is slightly attacked.
Moreover, the β' phase is most seriously corroded and the maximum
local corrosion depth is 6.4 μm as indicated in Fig. 15a. For NAB-6Ni
alloy, its corrosion behaviour is similar to that of NAB-4.5Ni alloy, but
the maximum local corrosion depth on β' phase decreases by 2 μm as
shown in Fig. 15b. With increasing alloyed Ni content in NAB alloy, the
corrodible β' phase disappears completely (Fig.15 c and d). The α phase
adjacent to the coarse NiAl phase is preferentially corroded and the
maximum local corrosion depth decreases to 3.1 and 2.9 μm, respec-
tively. Therefore, local corrosion of NAB alloy is also alleviated through
Ni addition.
The potential difference between various phases can be regarded as
the driving force for micro-galvanic in the localized corrosion of NAB
alloys [64]. The aluminium rich κ phases exhibit relatively higher no-
bility due to the formation of an aluminium-oxide protective film in
neutral solution [65]. Thus, the copper rich β' phase and α phase be-
come anodic to the κ phases and are preferentially corroded as shown in
Figs. 14 and 15. With the increase of Ni content in α phase, the driving
force for the selective phase corrosion is effectively relieved due to the
increased potential of α phase. Furthermore, the martensitic β' phase,
which is deleterious to the corrosion resistance of NAB alloys, is di-
minished by the Ni addition (Fig. 6). Consequently, the increase in the
potential of α phase and the decrease in the amount of β' phase lead to
the excellent corrosion resistance of NAB alloys with higher Ni content.
12
Corrosion Science xxx (xxxx) xxx–xxx
4. Conclusions
The microstructural evolution, mechanical properties and corrosion
behaviour of the as-cast NAB alloys with different Ni contents, namely
4.5, 6, 8 and 10% Ni, in 3.5 wt.% NaCl solution were investigated. The
significant findings are drawn as follows:
1 With the increase in Ni addition level, more Ni was dissolved into
the α solid solution and the amount of κ phase was increased. The
yield strength and hardness of the NAB alloys were improved via the
solid-solution strengthening and second phase strengthening.
However, the ultimate tensile strength and elongation were de-
creased, owing to the formation of the coarse NiAl strips.
2 The NAB alloys with higher Ni content exhibited higher corrosion
resistance both in the EIS measurements and the static immersion
tests. The improvement is due to the following mechanisms: (i) the
amount of corrodible β' phase decreased with the increase of Ni
content; (ii) a more stable protective oxide layer incorporated with
Ni ions formed on the surface of NAB alloys at higher Ni con-
centrations; (iii) the dissolved Ni in the α solid solution increased
the potential of α phase and thus relieved the driving force for the
microgalvanic corrosion of NAB alloys.
Acknowledgements
This work was supported by the National Key Research and
Development Program of China [grant No. 2017YFA0403803]; the
National Natural Science Foundation of China [grant Nos. 51525401,
51601028, 51774065 and 51690163] and Dalian Support Plan for
Innovation of High-level Talents [Top and leading Talents, 2015R013].
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