SSRN Id4241652

Corrosion behavior and antibacterial properties of nickel-aluminum bronze/steel
composite structures fabricated through wire‐arc additive manufacturing
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(WAAM)
Xiang Caia; Mengmeng Yanga; Shuo Wanga; Zan Wanga; Jian Zhoua,*; Feng Xuea
aJiangsu Key Laboratory for Advanced Metallic Materials, School of Materials Science and Engineering, Southeast
University, Nanjing 211189, China
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Abstract
This paper discusses the differences in corrosion resistance and antimicrobial
properties between nickel aluminum bronze (NAB)/steel composite structures
fabricated by WAAM and cast NAB. Compared with castings, the grain size of
WAAM-NAB was smaller, and the precipitation of the κ phase was limited. The
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corrosion of WAAM-NAB occurred in the residual β phase, selective phase corrosion
was suppressed and corrosion resistance was improved. The Cu ions of the composite
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structure were released more rapidly and were more effective in sterilization. The
microbial corrosion resistance of WAAM-NAB was better than that of cast alloys.
Keywords: Nickel-aluminum bronze; Microstructure; Corrosion behavior;
Antibacterial property; Microbial corrosion
Introduction
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As a type of copper alloy, nickel-aluminum bronze is a multiphase alloy formed
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by adding Al as the main element, supplemented by small amounts of Fe, Mn, and Ni
elements [1]. Due to an excellent combination of low density, high strength, and
corrosion resistance, NAB alloys have been widely used in landing gear bearings and
bushings for commercial aircraft, seawater valves and pumps, propellers for naval and
commercial shipping, and non-sparking tools for the oil and gas industry [2,3]. During
the melting process, as the cooling temperature decreases, Fe and Ni absorb Al from
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the matrix, and various κ-phase organizations (Fe3Al or NiAl) are formed in the matrix
(at 930°C: β → α + κⅠ / κⅡ, at 860°C: α → α + κⅣ, at 800°C: β → α + κⅢ). Many scholars
have reported that the large size of the κ phase is extremely detrimental to corrosion
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resistance, especially when used in seawater, where severe selective phase corrosion
occurs in the substrate near the κ phase. Selective phase corrosion leads to localized
damage penetrating the matrix, producing porous surface structures, reducing
mechanical strength, posing safety hazards to marine equipment, and leading to a
significant reduction in the service life of alloy components [4].
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Recently, scholars have tried to improve the corrosion resistance of NAB alloys
by heat treatment [5], plastic deformation techniques [6], composition design [7], and
surface modification methods [8]. Yang has reported that increasing the Ni content
significantly inhibited the formation of the corrodable residual β (β') phase and
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increased the concentration of Ni in the α-solid solution, thus improving the corrosion
resistance of the NAB alloy [4]. The friction surfaced extruded NAB alloy has reduced
grain size compared to cast NAB alloy, the casting porosity of the alloy was eliminated
during the friction process, and the corrosion rate of the alloy is reduced [9]. Lv
shot−peened the surface of NAB alloys, and the dislocation density in the α-Cu and β'
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martensitic phases in the matrix increased and the grains were refined. The refined and
homogenized microstructure facilitates the rapid formation of protective passive films
and promotes the occurrence of uniform corrosion on the surface of shot−blasted NAB
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* Corresponding author.
E-mail address: [email protected] (J. Zhou).
This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4241652
alloys, thus significantly improving their corrosion resistance [10]. Cr is introduced into
the surface of cast NAB [11] using ion implantation, and the protective film formed by
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chromium oxide and hydroxide can effectively inhibit the inherent selective phase
corrosion. Wu [5] obtained a homogeneous single-phase organization by quenching at
a temperature close to the solid phase, eliminating the defects of the cast alloy
composition bias and improving corrosion resistance. However, large components such
as propellers, heat treatment, and plastic deformation techniques cannot handle
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strengthening. Moreover, the overall hardening of the workpiece reduces its plasticity
and triggers brittle fracture. Surface modification treatments can only improve the
mechanical properties and corrosion resistance of the surface layer, but not the overall
properties of the material [4]. Alloying treatments usually involve adding more
elements to the metal or adjusting the ratio of each element. The NAB system already
contains enough elements and by adding more elements, new compounds may be
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formed that increase the tendency of the matrix to galvanic coupling corrosion.
Additive manufacturing (AM) is evolving into a revolutionary tool and disruptive
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technology for the 21st century. In addition to the aerospace and medical industries,
AM can offer unique benefits to the shipbuilding, marine, and offshore sectors [12-14].
Traditional additive manufacturing techniques are mainly classified into three
categories: laser additive manufacturing (LAM), electron beam selective melting
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(EBSM), and wire-arc additive manufacturing (WAAM) [15,16]. LAM is mostly
suitable for printing parts with complex structures, small sizes, and high surface
accuracy. And Cu has a high reflectivity to laser, and the molding rate using laser
additive manufacturing is low [17]. EBSM needs to be performed in a vacuum
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environment, which requires high site requirements and low molding efficiency and is
not suitable for preparing large parts such as propellers and air pumps [18]. In contrast,
WAAM enables the hybrid manufacturing of multiple materials, low-cost, high-
efficiency, and rapid near-net forming of large-size complex parts, and does not require
the protection of sealed silos during the forming process (except for some metals), with
high material utilization and cost savings [19]. Based on this, a concept was proposed
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to deposit nickel-aluminum bronze on all surfaces of steel using an arc additive to form
a fully clad copper-steel composite structure to replace the conventional cast NAB parts.
In recent studies [3, 20], researchers deposited 60 layers of NAB with a total height of
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160 mm on steel plates using an arc addition technique. These samples had significantly
finer matrix dendrites and did not have any rosette-like κI intermetallic compound
particles. Spherical κⅡ and lamellar κⅢ, as well as fine κⅣ phases (5−10 nm), are present
in the dendritic region and their sizes are smaller than those of the κ phase in the cast
alloy [20]. During tempering of the composite structure at 450°C, κⅡ and κⅢ phases
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precipitated in the grains and grain boundaries of the alloy matrix. When the
temperature reaches 650°C, a large number of needle-like κⅣ phases began to
precipitate in the α-Cu grains [21]. In addition to the above-mentioned studies, most of
the existing literature reports have focused on the formation of composite structures
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and the microstructure of the prepared NAB. The corrosion behavior of the composite
structures has not been reported systematically.
In the study of the corrosion behavior of NAB alloy, researchers found that the Al-
rich κ phase surface will rapidly generate Al2O3-based passivation film so that the κ
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phase is effectively protected, the α-Cu phase region in contact with the κ phase in
neutral corrosion solutions is a corrosion-sensitive region [22]. Especially the Cu-rich
α-Cu phase in the α+κⅢ co-precipitation tissue, which undergoes significant selective
anodic dissolution [23,24]. In the NAB alloy matrix prepared by WAAM, the
precipitation of the κ phase is suppressed, but the content of residual β-phase in the
matrix increases due to faster cooling, and the β-phase undergoes a martensitic
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transformation during cooling and becomes chemically active and preferentially
corroded in the corrosive medium [21,25]. Whether this microstructural difference
leads to a change in the corrosion mechanism of the alloy and whether the corrosion
resistance of the composite structure is better than that of the cast alloy to meet the
service requirements has not been reported in detail in the relevant literature. In addition,
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during marine service, copper alloys form a relatively dense protective film that hinders
the erosion of the substrate by seawater, but operating equipment such as pumps and
propellers will inevitably be damaged by sand and gravel in seawater during operation,
even exposing the substrate. What happens to the corrosion behavior of the alloy during
the subsequent immersion? In addition to strength and corrosion resistance, the superior
resistance of copper alloys to microbial corrosion is an important reason for their use
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as irreplaceable marine service components. However, with the intensification of ocean
eutrophication, especially in near-shore waters, the N and P elements in seawater are
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severely exceeded and the number of microorganisms in seawater has increased
dramatically. In this environment, do composite structures have superior antibacterial
as well as microbial corrosion resistance than cast alloys? To address the above
questions, this paper will systematically analyze and discuss, and lay the theoretical
foundation for whether the composite structure can replace the cast NAB alloy.
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2. Materials and methods
2.1. Materials preparation
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As shown in Fig. 1(a), a six-axis robotic WAAM system developed by Fronius
was used to build a cube sample of the NAB/steel composite structure. The WAAM
system consisted of: a computer interface to program the experimental process; a robot
controller to coordinate the robot movements of the welding power source and NAB
alloy deposition; a gas metal arc welding (GMAW) torch in cold metal transfer (CMT)
mode to deposit nickel-aluminum bronze onto 316L stainless steel (316LSS) according
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to the experimental requirements. In the WAAM process, NAB filler wires

corresponding to AWS A5.7 ERCuNiAl with a diameter of 1.2 mm were deposited on
a 3 mm thick 316LSS. To suppress the development of penetration cracks on the steel
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side during deposition, a low heat input was used on all surfaces of the steel. The
specific deposition route and deposition parameters are shown in Fig. 1(b) and Table 1.
Ar was used as the protective gas throughout the process. The composition of the NAB
wire and 316LSS and the cast NAB alloy(CNAB) used as a comparison sample are
shown in Table 2. Under these conditions, the thickness of each deposited layer was
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controlled to 1.5 mm, forming a 1:2:1 thickness ratio with the steel base material. Fig
1(c) shows the WAAM-NAB after forming.
2.2 Microstructure characterization
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The samples were ground with SiC paper gradually up to 5000 grit finish, finely
polished to 2.0 and 1.0 μm finish with diamond suspension and etched with corrosive
solution (5 g FeCl3 + 2 ml HCl + 95 ml C2H5OH). The microstructures of the samples
were examined using an optical microscope (OM; VHX-900F) and scanning electron
microscope (SEM, FEI Sirion 200) fitted with an energy dispersive spectroscopy (EDS).
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Grain size and orientation in the alloy were tested by electron backscatter diffraction
(EBSD, INCA Crystal EBSD) and analyzed by Channel 5 software. The phase
composition of the CNAB and WAAM‐NAB corrosion products was determined by X-
ray diffraction (XRD, Bruker D8-Discover), which was performed at 30 kV and Cu Κα
radiation (wavelength 0.154 nm) with diffraction angles from 5° to 90° at a rate of 0.15
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steps/s. The X-ray photoelectron spectroscopy (XPS, ESCALAB 250Xi T) analysis was
performed by using an AlKα (1486.6 eV) radiation source to characterize the valence
state of the ions on the surface of the alloy. The obtained XPS data were analyzed by
Avantage software. The samples for transmission electron microscope (TEM)
investigation was ground to 80 μm and then ion-beam milled using an ion thinning
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instrument (Gatan 691) with an ion energy of 0.1 KeV − 6 KeV and an incident angle
of 10°, thinning to 10 μm. The TEM foils were characterized using a high-resolution
transmission electron microscope (HRTEM, TalosF200X), the working voltage was
200 kV. High‐angle annular dark-field (HAADF) detectors were used in combination
with EDS to obtain elemental distribution maps.
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2.3 Corrosion behavior in artificial seawater
2.3.1 Mass loss
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Specimens with dimensions of 10 × 10 × 5 mm were ground with SiC papers to
3000 grit, washed ultrasonically in ethanol for 3 min, rinsed with distilled water, and
dried with cold air. The samples were then carefully weighed on an analytical balance
(ME204E, Mettler-Toledo, Switzerland) with an accuracy of ± 0.1 mg and the exposed
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area of each sample was calculated separately. Each sample was immersed in a
container containing 600 ml of artificial seawater solution that met the ratio of
minimum solution volume to sample area (0.20 ml·mm-2). The proportions of the
artificial seawater configuration are shown in Table 3. The solution temperature was
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maintained at RT (25 ± 1°C) throughout the experiment. To compensate for evaporation
losses, a new solution was replenished every 3 days to maintain the original volume.
Samples immersed for 30, 60, 90, and 180 days were soaked in a mixture of 200 ml
hydrochloric acid and 200 ml distilled water for 5 min to remove corrosion products,
rinsed with distilled water, and dried in a vacuum drying oven at 80°C for 30 min. The
samples were finally weighed. For each case, 5 samples were tested and the average
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value was taken.

2.3.2 Static immersion tests
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The samples used for surface corrosion morphology analysis and corrosion
product identification were sequentially ground with SiC papers to 3000 grit and
polished with a 1 µm diamond suspension. After immersion in artificial seawater
solution for different times, the corrosion products of the samples and the morphology
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of the samples after removal of the products were observed by SEM. The composition
of the surface corrosion products was calibrated mainly by XRD and XPS.
2.3.3 Electrochemical tests
All electrochemical measurements were performed at RT using a Gamry
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electrochemical workstation (Gamry Instruments, Ref. 600, USA). A conventional

three-electrode system was used in the measurements, with the studied alloy as the
working electrode, a 10 mm × 10 mm platinum sheet as a counter electrode, and an
Ag/AgCl electrode (with an electrode potential of 0.1981 V for saturated potassium
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chloride compared to a standard hydrogen electrode) as a reference electrode. The

exposed area of the electrochemical test sample was 1 cm2. After the test system
reached a stable open circuit potential (OCP), the samples were Tafel tested at a scan
rate of 1 mV/S at potentials ranging from -0.6 V to 1.6 V (relative to the OCP) for fresh
samples and samples after 30 days of immersion. Electrochemical impedance
spectroscopy (EIS) was performed at a fixed time each day for 30 days, with EIS
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measurements in the frequency range of 105 Hz to 10-1 Hz. To avoid serendipity, at
least three samples were tested. Based on the overall trend of the EIS results, the most
representative data were selected for plotting. These EIS data were then fitted and
analyzed by the Zsimpwin 3.10 software.
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The evolution of the local corrosion behavior of the sample surface was monitored
by the scanning vibrating electrode technique (SVET) in a scanning electrochemical
workstation (Ametek VersaSCAN, USA). The SVET probe (Pt-Ir electrode probe, 10
µm) was scanned over the sample surface (3 × 3 mm2) at a measurement rate of 100
µm/s. The measurements were collected and analyzed according to Eq (1) [26]：
i = -k(ΔV)/(Δr)
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Where i is current density, and the solution conductivity k is 30000 mS⋅cm-1 in
simulated seawater. The reaction potential difference (ΔV) was measured in the
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amplitude of Δr (Δr = 30 µm).
2.3.4 Self-repairing for corrosion resistance
A scalpel was used to scratch the surface of the 15 days immersed sample with a
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width of 40 μm to expose the substrate. The samples were then immersed in artificial
seawater and the morphology of the surface was observed periodically by SEM. The
EIS was tested at specific times each day, and the most representative data were selected
for plotting based on the overall trend of the experimental results. These EIS data were
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then fitted and analyzed by Zsimpwin 3.10 software.
2.4 Antibacterial properties and microbial corrosion
2.4.1 Antibacterial properties
1 ml of Gram-negative Escherichia coli (E.coli) was added to 10 ml of Luria-
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Bertani (LB) liquid medium autoclaved at 121°C for 20 min, and then shaken at 180
rpm for 24 h at 37°C to activate E.coli. The concentration of the activated bacteria
solution was determined by a UV spectrophotometer. And then a new immersing
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solution was configured in the ratio of 6 g yeast powder: 3 g beef paste: 600 mL
artificial seawater, and 2 mL of 109 colony-forming unit/mL (CFU/mL) was added to
some of the culture flasks, and the other part was used as immersing solution for
comparison blank experiments. The samples polished to 0.5 μm were then sterilized
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under UV light for 30 min, placed in a culture medium, and incubated in a biochemical
incubator at a constant temperature of 37°C for 3,7,15 days. To obtain bacteria adhering
to the metal surface, the immersed metal was sonicated in 10 mL of sterile water for 5
min to separate the bacteria from the metal surface. The isolated bacteria were diluted
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to 10-4 and 100 μL of the dilution was incubated on Luria Bertani agar plates at 37°C
for 24 h for colony counting.
2.4.2 Live and dead bacteria staining
Calcein M (CM) and propidium iodide (PI) were mixed at RT in the dark to
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visualize live (green) and dead (red) bacteria. Samples cultured in E.coli suspension for
15 days were removed and washed with sterile PBS to remove non-adherent bacteria.
Live and dead bacteria adhering to the sample surface were stained using the Live and
Dead Bacteria Staining Kit (Beyotime, Shanghai, China). Green fluorescent CM was
used to stain live bacteria with intact cell membranes, and red fluorescent PI was used
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to stain dead bacteria with damaged cell membranes. A mixture of CM and PI was
prepared in a 1:1 volume ratio, and then 50 μL of the mixture was added to sample
surface and kept in the dark for 15 minutes. Finally, live and dead bacteria were
identified using a fluorescence microscope (OLYMPUS IX71).
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2.4.2 Ion release
The release of copper ions from two alloys by immersion for 1, 3, 7, 10, and 15
days was determined by inductively coupled plasma mass spectrometry (ICP-MS,
Thermo, USA) in solutions containing bacteria at 37.5°C and a solution/sample surface
area ratio of 1.25 cm2/ml according to the ISO 10993-12 standard [22].
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2.4.3 Morphology observation
The immersion samples were fixed in 4% paraformaldehyde solution for 4 h to
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activate the biofilm, and then the metals were dehydrated in batches of 4×15 min with
graded concentrations of ethanol solutions (25%, 50%, 75%, and 100%). The
morphology of the biofilm formed on the sample was observed by SEM and Atomic
force microscopy (AFM, ARC2). The chemical morphology and functional groups on
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the sample surface were analyzed by XPS and attenuated total reflectance Fourier
transform infrared spectrometer (FTIR, Thermo Scientific Nicolet iS10), respectively.
2.4.4 Electrochemical impedance spectroscopy test
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EIS tests were performed on samples immersed in artificial seawater containing
bacteria and a culture medium in the manner in 2.3.2, and comparative tests were
performed in solutions without bacteria, but with a culture medium. Representative data
were selected for plotting based on experimental trends, and these EIS data were fitted
and analyzed using the Zsimpwin 3.10 software package. To avoid experimental chance,
each experiment was repeated three times.
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3. Result
3.1 Microstructure characterization
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The microstructures of the CNAB and WAAM-NAB alloy are shown in Fig. 2.
The microstructure of the CNAB alloy (Fig. 2(a)) consists of α-Cu phase (light area),
β' phase (dark area), and intermetallic κ phases. κ phase is mainly composed of Fe (Fig.
2(d)), when the Fe element is enriched with more than 5 % in the region, κⅠ phases with
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rosette‐like or spherical shapes can be formed. κⅠ is usually Fe3Al with DO3 structure
and FeAl with B2 structure. The spherical κⅡ phase is smaller than the κⅠ phase, and the
crystal structure is based on the DO3 structure of Fe3Al. κⅢ is a NiAl intermetallic
compound with a B2 crystal structure, and can form a layered eutectic organization with
the matrix α-Cu phase, or degrades forming phase particles distributed along a straight
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line. The κⅣ has the smallest size and consists of Fe3Al with DO3 structure and is
dispersed in the matrix [27]. The β' phase is the residual phase that has not undergone
a eutectic transformation to produce α-Cu and κ phases, so EDS-mapping shows that
Al and Ni elements are enriched in and around the β' phase (Fig. 2(d)). The size of the
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dendritic α-Cu and β' phases in WAAM-NAB is significantly smaller than that of the
CNAB, while the β' phase content per unit area in the matrix (37.7%) is calculated by
Photoshop to exceed that of the CNAB alloy (20.5%) (Fig. 2(b)). As in the case of the
CNAB, the content of Al, and Ni in the α-Cu phase is less than that of the β' phase.
However, the precipitation of the κI phase in the matrix of WAAM‐NAB was
suppressed, the size of the κⅡ phase was significantly reduced, and all κⅢ phases are
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lamellar (Fig. 2(f)). Brezina [28] has reported that the precipitation of the κ phase is
limited, especially the precipitation of the κⅣ phase is completely suppressed after Ni-
Al bronze is subjected to rapid cooling and rapid heat treatment. In recent years, it has
been found that the κⅣ phase was not completely suppressed, but was only small in size
and difficult to detect. Therefore, whether the κⅣ phase was completely suppressed in
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this experiment needs further observation.
The microstructure of the alloy matrix was further observed by TEM and the
results are shown in Fig. 3. As mentioned above, the size of κⅠ is the largest in the
CNAB, followed by κⅡ with a size of about 1 μm. The layered κⅢ (NiAl) phase, which
exists at the boundary between α-Cu and β′ phases, has a thickness of about 50 nm. κⅣ
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phase has a very small size of about 100 nm and is distributed in the α-Cu phase. In the
WAAM‐NAB, the κⅡ phase is only 400 nm; the thickness of the layered κⅢ phase is 10
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nm; the κⅣ phase is present in the matrix by EDS-mapping, with a very small size of
only 20 nm. In binary Cu-Al, the addition of Ni induces an ordered-disordered structural
transition in the β phase during cooling, resulting in a different martensitic product [25].
These martensitic structures are usually classified as FCC-β' (9R), ordered
orthorhombic/monoclinic β1' (18R), and ordered orthorhombic γ1' (2H) [29-31].
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According to available reports on this rapid hot and cold process, the transformation
forms mostly martensitic structures of β1' (18R in the orthorhombic lattice [32]) or γ1'
(P2mm space group [33,34]). Swann and Warlimot [30] found that the γ1' structure of
martensite in the Cu-Al system is associated with twinning, while the β1' structure
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usually contains stacking fault (SF) defects. The observation of the residual β phase
revealed a large number of fine streaks in the slatted martensite, which is similar to the
β phase organization formed by quenching and rapid cooling of the Cu-Al alloy at high
temperatures by Zhang and Swann. The diffraction pattern shows distinct streaks along
the (-2,-1,-1) direction. For this phenomenon, Xiang explained that the presence of
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multiple SFs in the matrix leads to diffraction streaks along the direction perpendicular
to the SF plane [35]. The fine streaks of martensite in Fig. 3(f) are the result of the
extension of high-density SFs through the martensitic plate. Combined with the
characteristics of β1' and γ1' mentioned earlier, it is determined that the residual β phase
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at this point is the β1' structure.

Fig. 4 shows the EBSD microstructure and crystallographic characterization of the
CNAB and WAAM-NAB. The inverse pole figure (IPF) of both samples is shown in
Fig. 4(a) and (e), which reveals that the crystal orientation of the grains in WAAM-
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NAB is homogeneous as in the CNAB. This is in contrast to the directional growth

characteristic of the conventional AM process along the build direction. The grain
boundary misorientation plots (Fig. 4(b) and (f)) show that large-angle grain boundaries
(greater than 15°, blue line segment) dominate in the alloys with a percentage of 90.7%
and 82.0% (Fig. 4(d) and (h)), respectively, which may be related to the presence of
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low local stress and low dislocation density in both alloys. Grain size disparity in CNAB
is significant, ranging from 18−89 µm (the κ phase of small particles is not involved in
the statistics), with an average size of 49.6 µm. The grain size of WAAM-NAB is
smaller and more homogeneous than that of the CNAB, ranging from 6−15 µm with an
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average size of 8.7 µm.
3.2 Electrochemical testing
To investigate the differences in the electrochemical behavior of CNAB and
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WAAM‐NAB, potentiodynamic polarization and EIS measurements were carried out
at different times for the two alloys immersed in artificial seawater. Fig. 5 shows the
potentiodynamic polarization curves of the CNAB and WAAM-NAB before and after
30 days of immersion. Before immersion (red and black curve), the two specimens have
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similar polarization behavior: the reduction of oxygen occurred in both alloys in the
cathodic polarization region [4]: O 2 +H 2 O+4e - →4OH - . Then entering the anodic zone,
with the increase in corrosion potential, the current density increased rapidly, the
corrosion potential to about 0.027 and 0.077 V, respectively, and the anodic current
density then decreased, and a passivation film was formed on the surface of the alloy.
The film inhibited the charge transfer process, indicating that the alloy entered the
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passivation interval, which ranged from 0.027 to 1.149 V for CNAB and from 0.077 to
1.343 V for WAAM-NAB. At this stage, the curve was divided into several regions. In
region 1, Al in the matrix was complexed with chloride, and then hydrolysis produces
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Al(OH)3 and Al2O3 passivation film [36-38]: Al+4Cl - →AlCl 4 - +3e - ; AlCl 4 - +3H 2 O
→Al(OH) 3 +3H + +4Cl - ; 2AlCl 4 - + 3H 2 O → Al 2 O 3 + 6H + + 8Cl - . The corrosion
current does not increase with the voltage, and the alloy passivation is
obvious. In region 2, with the increase of polarization voltage, the corrosion current
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increased slowly, which should be the active dissolution zone of Cu. The polarization
potential of this region was relatively low, and the Cu in the alloy was dissolved in the
form of Cu+, then Cu+ complexes with Cl- in seawater, the specific reaction equation is
[4,38]: Cu+e - →Cu + , Cu + +Cl - →CuCl; CuCl+Cl - →CuCl 2 - . Region 3 is the
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obvious passivation zone, CuCl is insoluble in water, it is deposited on the surface of
the alloy and hydrolyzed to form a more stable Cu2O, the reaction formula is
[39]:2CuCl+2OH - →Cu 2 O+ H 2 O+2Cl - . Cu2O is the main component of the NAB
surface passivation film, which has a symmetrical cubic structure with each Cu atom
surrounded by two O atoms. Cu2O is insoluble in water and can form a layer of oxide
film on the surface of the alloy, which can prevent the diffusion of Cl- to the electrode
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surface and CuCl2- from the alloy to the reaction solution, so that the corrosion current
was reduced. The appearance of white corrosion products can be observed on the
sample surface. Region 4 is the limit current zone, with the continuous increase of
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polarization potential, the products of Cu+ will be oxidized to form the products of Cu2+:
CuO and Cu(OH)2. The formed CuCl2- can be used as seed crystals to form Cu2Cl(OH)3
through subsequent dissolution, ion pairing and redeposition [4,40], the reaction
formula is: Cu + +1/2O 2 +e - →CuO; CuO+H 2 O→Cu(OH) 2 ; 2CuCl 2 - +3OH + +2e -
→Cu 2 Cl(OH) 3 +3Cl - . The sample reaction produced a large amount of green alkaline
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copper chloride precipitate diffused into the solution, the passivation film broke, and
the corrosion current density increased rapidly with voltage. Fitting the polarization
curve, the corresponding parameters are shown in Table 4. The corrosion potential of
the two alloys is similar to about -0.160 V, and the corrosion current density is obtained
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by the trilinear method: WAAM-NAB (7.35×10-5 A·cm-2) < CNAB (1.24×10-4 A·cm-
2). After 30 days of immersion, a product film formed on the surface of the alloys, and
the polarization curves (brown and pink curves) were significantly different from those
of the fresh samples. The corrosion potentials of the two alloys were positively shifted
to 0.023 V. The corrosion current densities decreased significantly, the WAAM-NAB
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(2.68×10-9 A·cm-2) was still smaller than that of the CNAB (6.54×10-9 A·cm-2), and
passivation intervals of 0.464 to 1.194 V and 0.477 to 1.146 V, respectively. Comparing
the corrosion potentials, corrosion current densities, and passivation potential intervals
of the two alloys before and after immersion, it can be tentatively concluded that the
corrosion resistance of the WAAM-NAB is higher than that of the CNAB. Fig. 6 shows
the Nyquist curves of two alloys immersed in artificial seawater at different times. The
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curves of the two alloys exhibit two shapes. In the pre-immersing period, the capacitive
reactance arc in the high frequency (HF) range and a straight Warburg line in the low
frequency (LF) range; in the late stage, only the capacitive reactance arc consists. HF
capacitive arc represents the combination of charge transfer resistance on the bare
electrode and the charge transfer resistance generated by the surface film [41]. The LF-
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Warburg impedance is related to the diffusion process of oxygen from the solution to
the electrode surface [42] or to the diffusion process of the cuprous chloride ion
complex (CuCl2) (from the electrode surface through the diffusion layer) [43]. This
suggests that the corrosion mechanism of NAB alloys is controlled not only by the
charge transfer step but also by the diffusion process [44-46]. At this stage, the diffusion
behavior of redox reactants plays an important role in the corrosion process due to the
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rapid transfer of interfacial charges. After 1 day of immersion, as shown in Fig. 6(a),
the WAAM-NAB substrate was covered by a thick film layer, and the Warburg straight
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line segment disappeared. Multiple corrosion pits were produced on the exposed
surface of CNAB, and the Warburg line still existed; as the corrosion products produced
on the surface gradually increased, the straight section of Warburg disappeared after 2
days of immersion.
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The equivalent circuit model is shown in Fig. 6(b) and (c) was used to simulate
Nyquist curves. The circuit includes two-time constants for the HF charge transfer
reaction and the LF film resistance. Where Rs represents the solution impedance, Rf
represents the corrosion product film resistance, Rct represents the charge transfer
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resistance at the two-electron layer, and W is the Warburg impedance. Considering the
capacitive dispersion caused by surface roughness and inhomogeneity, the CPE is
introduced to characterize the non-ideal capacitor [47], and achieve the best fit.
Therefore, CPEf and CPEct in Fig. 6 ((b) and (c)) correspond to the non-ideal
capacitance of the product film and the double-charge layer, respectively. The
impedance of CPE can be calculated by Eq. 2:
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ZCPE = [Q(jω)n]-1
where Q is the size of the CPE, j is an imaginary number (j = ( - 1)), ω is the angular
frequency (ω = 2πf, f is the frequency), and n is the CPE index [48,49]. If n = 1, the
tn
CPE is the ideal capacitor, while for n = 0.5, the CPE represents a Warburg impedance
with a diffusional character. The EIS data were fitted to the samples using Zsimpwin
3.10 software, and the results are shown in Table 5. The Rf and Rct of samples gradually
increased during the immersion, indicating the accumulation of product films and a
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steady increase in the corrosion resistance of the alloys. The nf of CNAB continued to
increase in the first stage (7 days) and started to decrease when the immersion time
reached 15 days, indicating that the product film density on the surface becomes smaller.
A specific analysis of the sample product film morphology will be presented below.
For WAAM-NAB, the specific values of Rf and Rct are greater than those of the CNAB,
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especially after 30 days of immersion, the Rct value is an order of magnitude greater
than that of the CNAB. The nf gradually increased and remained at a consistently high
value, indicating that the film is becoming denser and can provide effective protection
against long-term corrosion. Fig. 7 shows the local current density distribution on the
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sample surfaces during the immersion process using the SVET technique. In the early
stage, the κ phase potential present in the CNAB differs from the α-Cu phase [22],
forming corrosion cells, resulting in a decrease in corrosion resistance and high
corrosion current density in this region. Thus causing a large difference in corrosion
current density on the surface of the alloy, reaching 5 mA·mm-2 (the highest value
reaches 2.1 mA·mm-2 and the lowest value is -2.9 mA·mm-2). With the extension of the
ed
immersing time, the corrosion product film with Cu2+ mainly formed on the surface of
the alloy gradually, the overall corrosion resistance of the alloy improved, and the
surface corrosion current density gradually decreased. After 15 days, the corrosion
current density difference on the surface of the substrate decreased to 0.0434 mA·mm-
2. As mentioned before, the precipitation of the second phase in WAAM-NAB is limited,
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then the area of potential difference that can be formed by the matrix is reduced and the
current density difference on the alloy surface becomes smaller, 1.7 mA·mm-2 (the
highest value is 1.1 mA·mm-2 and the lowest value is -0.6 mA·mm-2). After 15 days of
immersion, the current density difference on the surface of the alloy has been reduced
to 0.0115 mA·mm-2.
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3.3 Mass loss
Fig. 8 shows the variation of the cumulative mass loss with immersing time for
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the CNAB and WAAM‐NAB. The curves show that the mass loss corresponding to
each immersing time for the WAAM-NAB is lower than that of the CNAB. During the
180 days of exposure, the alloy corrosion underwent three characteristic processes. The
corrosion rate is faster (high slope of the curve, acceleration stage) in the first 30 days.
The sample has just been immersed in artificial seawater, the exposed fresh metal
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surface is in direct contact with the seawater. Due to the small radius and high
permeability of Cl-, it can easily interact with the exposed metal and form soluble
compounds. Although an oxide film was produced on the surface of the specimen, the
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initial oxide film was not dense enough and had limited protection for the metal surface,
so the corrosion rate was faster. In the next 60 days, the corrosion rate slowed down
(slope of the curve decreases, moderate stage), the oxide film at this stage became dense,
the thickness increased, and the Cl- blocking effect of artificial seawater was enhanced,
thus the corrosion rate of the specimens in the second and third months decreased. In
the next 90 days, the corrosion rate was the lowest (stabilization stage).
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3.4 Corrosion product film

To determine the composition of alloy corrosion products, XRD and XPS were
performed on two alloys immersed for 30 days. Due to the limited amount of corrosion
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products, the XRD diffraction high−intensity peaks were partially from the matrix.
Corrosion products such as Cu2(OH)3Cl, Cu(OH)Cl, CuO, and Al2O3 were produced
on the surface of the immersed alloys compared to the fresh alloys. To understand
specifically the structure of the corrosion product films on the alloy surface, the product
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films of different layers were calibrated for elemental valence using XPS. The peak
intensities of Cl and O were higher in the surface layer of the alloy than in the inner
layer; the spectra of the inner layer show enhanced signals of Cu, Mn, Fe, and Al, and
weakened signals of O and Cl. During the corrosion process, Cu ions are present in
different valence states. The chemical valence state of Cu present in the film and its
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proportion can be determined by splitting the peaks after a fine sweep of the
characteristic peak positions of Cu by XPS. The peaks of Cu+ compounds appear near
932 eV, while the peaks of Cu2+ appear near 935 eV. The concentration ratios of Cu2+
and Cu+ in the surface films of surface CNAB and WAAM-NAB were determined to
Pr
be 92.27% and 7.73%, and 95.21% and 4.79%, respectively. After etching 50 nm with
SiO2, the percentages of Cu2+ and Cu+ became 5.36% and 94.64%, and 24.0% and
76.0%, respectively. Etching 150 nm, the Cu ions in WAAM-NAB have been all Cu+,
with percentages of 10.2% and 89.8% in CNAB. Etching 200 nm on the CNAB surface,
10
the Cu was all in the form of Cu+. According to the available literature, NAB alloys
form two product film structures during corrosion, the inner layer is an oxide composed
ed
of Al/Ni and the outer layer is a Cu compound [50,51]. However, in combination with
the XPS results, the outer Cu compound is divided into two layers of Cu2+ and Cu+, the
specifics of which will be analyzed in the following with the product film structure of
the samples by SEM.
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3.5 Corrosion morphologies
Fig. 10 shows the morphology of the alloy after 30 days of immersion in artificial
seawater. It can be seen that after 4 h, there were obvious corrosion pits on the surface
of the CNAB, and the number and size of the corrosion pits increased significantly with
the extension of time. By 5 days, the surface of the alloy had already appeared larger
size corrosion pits and the whole surface became extremely rough. The WAAM-NAB
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did not show obvious corrosion pits during the whole immersion process. After 24 h,
the surface corrosion out of the arc deposition path, but no obvious corrosion pits. By
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5 days, the surface formed a more uniform distribution of blue-green corrosion product
film. By 30 days, the surface of the alloy was completely covered by the corrosion
products, and after removing the corrosion products, the substrate still had no obvious
corrosion traces.
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Fig. 11 shows the corrosion morphology of the sample after 7 days of immersion.
The corrosion products on the surface of CNAB and WAAM-NAB in Fig. 11(b) and
(g) have a three-layer film structure: the corrosion products near the substrate are
honeycomb (film A), followed by flakes (film B), and the outermost layer is flocculent
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(film C). The elemental distribution shows that the content of O, C, and Cl decreases
gradually from the outer layer to the inner layer, and the content of Cu, Al, Mn, Ni, and
Fe increases gradually. In seawater, the electrode potential of Al and Ni is less than that
of Cu, which preferentially forms honeycomb dense Al oxides (Al2O3) on the surface
of the alloy, which can effectively protect the substrate. The anodic dissolution of Cu
in the medium is not related to the pH of the solution, but only to the concentration of
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Cl- [52]. When the concentration of Cl- is less than 1 mol/L, Cu undergoes an anodic
reaction to form CuCl and CuCl2-, while CuCl32- and CuCl43- are formed when the
concentration of Cl- is greater than 1 mol/L. The concentration of Cl- in this study was
tn
less than 1 mol/L. The generated CuCl was not dissolved in solution but deposited on
the surface of the specimen, after which CuCl was further hydrolyzed to form a more
stable Cu2O. Cu2O is the main component of the passivation film on the surface of the
specimen and is insoluble in water; therefore, film B is a Cu+-based film layer. These
products of the Cu+ are gradually oxidized to form the products of the Cu2+: CuO and
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Cu(OH)2, and the formed CuCl2- can act as seed crystals that form Cu2Cl(OH)3 through
subsequent dissolution, ion pairing, and redeposition. Therefore, film C is a Cu2+-
dominated film layer, which is also consistent with the above XPS results. In addition
to the above corrosion products, in the CNAB, κⅠ, κⅡ, and κⅣ phase in addition to the
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formation of dense Al2O3 product film, also generated the corresponding product Fe2O3.
The Fe2O3 film is loose and can adhere to the κ phase surface without flaking due to its
small initial generation size, thus forming a discontinuous film layer on the alloy
surface. In general, at the phase boundaries of different phases, the growth rate of the
corrosion product film at these locations is slower than at the in-phase locations due to
Pr
the change in composition. And the stress of the product film at the phase boundary
exceeds the strength of the film, and cracks will appear on the film surface, which will
reduce the protective effect of the film on the substrate. The cracks between the film
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layers of the α-Cu phase and large size κ phase in Fig. 11(d) explain why the nf of
CNAB (Table 4) decreased. κ phase precipitation of WAAM-NAB alloy was limited
ed
(κⅠ precipitation is inhibited) and both were small in size, which made the product film
on the surface of the alloy more continuous and homogeneous, and therefore more
protective to the substrate.
Removing the corrosion products, Fig. 12 shows that the corrosion of the CNAB
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alloy occurred in the β' phase and the α-Cu phase near the κ phase, which is typical of
phase-selective corrosion. With the extension of the immersing time, the depth and area
of the corrosion pits in the β' phase became larger and larger, the corrosion of the α-Cu
phase near the κ phase increased significantly, and part of the κ phase had fallen off.
The corrosion of the WAAM-NAB occurred in the β′ phase, while the α-Cu phase was
not corroded and the surface was relatively intact. With the extension of immersing
v
time, small corrosion pits began to appear on the surface of the α-Cu phase, but the
corrosion still occurred mainly in the β' phase. After 30 days, the corrosion pits depth
formed on the surface of CNAB was 31 μm and that of WAAM-NAB was 9 μm, and
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the corrosion crater area of CNAB was much larger than that of WAAM-NAB.
3.6 Self-repair
Fig.13 shows the change in corrosion morphology of both alloys within 10 days
er
after the surface was scratched. Fig. 14 shows the Nyquist curves of the samples for the
corresponding immersing times. The corrosion resistance of the samples was drastically
reduced due to the destruction of the surface film layer. The Rct of CNAB and WAAM-
NAB decreased from 5.116 × 104 and 1.263 × 105 to 1.963 × 104 and 4.055 × 104 Ω·cm2
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(Table 4) for CNAB and WAAM-NAB, respectively, when the impedance spectra were
fitted with the equivalent circuit of Fig. 6(c). Due to the potential difference between
the exposed substrate and the surrounding corrosion products, the substrate was
preferentially corroded, the generated corrosion products accumulated in the scratches,
as shown in Fig. 13 (b) and (d), and the corrosion resistance of the alloy steadily
improved (Table 4). Due to the high corrosion resistance of the WAAM-NAB, the rate
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of corrosion product generation in scratches during this period is significantly less than
that of the CNAB. The morphology can be seen that after 6 days of immersion, the
scratches on the surface of CNAB have been filled with corrosion products and the Rct
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value (5.108×104 Ω·cm2) was similar to that before the scratch. While the WAAM-
NAB scratches were still clear, Rct value was lower than before the scratch; after 10
days, the scratches were filled with corrosion products and the Rct value (1.338×105
Ω·cm2) was similar to that before the scratch.
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3.7 Microbial corrosion morphology

Fig. 15 shows the surface morphology of the alloy after immersing it in the
solution containing E.coli. After immersing for 3 days, some rod-shaped bacteria were
attached to the metal surface, and colonies had formed on the surface of CNAB; the
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number and size of colonies formed on the surface of WAAM-NAB were significantly
smaller than those of CNAB. AFM showed that the area and height of colonies on the
surface of the CNAB exceeded those of the WAAM-NAB. These bacteria deposited on
the surface of the alloy secreted extracellular polysaccharides (Exopolysaccharides)
[53,54] containing organic macromolecules such as polysaccharides, proteins, fatty
Pr
acids, and nucleic acids. Organic and inorganic substances adhering to the metal surface,
or even reacting directly with the metal matrix, further form extracellular polymeric
substances (EPS) that regulate biofilm surface adhesion and mechanical stability, and
12
finally form organic 3D network structures with adhesive properties that become sites
for bacterial metabolism and reproductive accumulation [53]. The size and the number
ed
of colonies on the alloy increased significantly with the increase of immersing time (Fig.
15(e) and (f)). After 15 days, the surface of CNAB was completely covered with
bacteria, and after shaking off the bacteria from the alloy surface, corrosion pits of 1−3
µm in size were present on the CNAB surface, which were almost all formed on the κ
phase surface by EDS-mapping calibration (Fig. 15(j)). In contrast, some areas of the
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WAAM-NAB surface remain uncovered and the corrosion pits on the surface are much
smaller in number and size (0.2−0.5 µm) than those on CNAB.
As comparison experiments, Fig. 16 shows the surface morphology of the CNAB
and WAAM-NAB after 3, 7, and 15 days of immersion in artificial seawater containing
culture medium. After 3 days, corrosion pits appeared on the surface of the CNAB,
v
which were calibrated to be in the κ phase of the alloy, compared to the WAAM-NAB
where the surface corrosion pits appeared in the matrix α-Cu and β phases and were
smaller in size. After immersion for up to 7 and 15 days, the corrosion pits on the
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surface of the samples increased in size and number, but the corrosion levels were much
lower than those in artificial seawater (Fig. 12). This is mainly due to the chelation
reaction of the alloy in the solution containing high levels of proteins [55]. When
proteins bind to heavy metal ions, leading to changes in their structure and loss of
er
activity, they collect and settle on the surface of the sample, forming a complete film
layer that greatly inhibits the cathodic and anodic reactions during corrosion. Thus, in
addition to the alloying elements, the sample surface is enriched with C, O, and N (Fig.
16).
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3.8 Ion release
Fig. 17 shows a comparison of the Cu ion release results for the CNAB and
WAAM-NAB in the bacteria-containing solution. The release of Cu ions from WAAM-
NAB was faster than that from CNAB alloy in all periods. At the early stage of
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immersion (1−7 days), Cu ion release was faster for both alloys; after that, the release
of Cu ions slowed down significantly, indicating that a colony biofilm was formed on
the alloy surface (Fig. 15), which could effectively slow down the corrosion of the alloy
tn
and thus inhibit the release of Cu ions. The bactericidal behavior of the alloy is related
to the concentration of Cu ions, which implies that the WAAM-NAB has superior
bactericidal ability.
3.9 In vitro antibacterial properties
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The staining results of live/dead bacteria on the surfaces of the alloys immersed
for 15 days are shown in Fig. 18. Most of the bacteria present on the surface were dead
(red fluorescence), and the number of bacteria (both live and dead) on the CNAB
surface was significantly higher compared to WAAM-NAB. The bacteria shaken from
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the samples soaked for 15 days were diluted to 10-4 and then applied on a solid medium
and incubated for 24 h. Counting statistics showed that the number of colonies formed
after incubation of bacteria shaken from WAAM-NAB was significantly less than that
of CNAB (Fig. 18(d)). Combined with the bacterial staining results and the number of
Pr
colonies on the agar plate, it can be determined that WAAM-NAB has a better
bactericidal effect and antibacterial adhesion.
13
3.10 Electrochemical testing
To visualize the corrosion trend of both alloys during immersion, EIS was tested
ed
for samples at different times, and the results are shown in Fig.19. The Nyquist curve
consists of two capacitive-resistance arcs at low and high frequencies, which were fitted
with the equivalent circuit of Fig. 6(c), and the parameters obtained are shown in Tables
7 and 8. The Rct of the alloys was significantly higher compared with those in artificial
iew
seawater. For the CNAB, the Rct of the fresh sample in the bacteria-containing solution
was slightly smaller than that of the non-bacteria solution, and after 1 day, the Rct value,
as well as the Rf value of the alloy in the bacteria-containing solution, increased sharply,
exceeding that of the sample immersed in the non-bacteria-containing solution. The Rct
values continued to increase with immersing time until they stabilized at 4.169 × 105
and 7.03 × 105 Ω·cm2 after 9 days. Similar to CNAB, the Rct values of WAAM-NAB
v
also increased substantially during the immersing period and then gradually stabilized
after 9 days. However, when WAAM-NAB was immersed in a solution containing
bacteria, its Rct value was always smaller than that of the samples immersed in a solution
re
without bacteria.
3.11 Surface composition
Fig. 20 depicts the FTIR spectra of the functional groups on the surface of the alloy
er
after 15 days in the bacteria-containing solution. In the figure, a strong and broad
absorption band at 3300 cm-1, which according to Abdoli's study could be hydroxyl
O-H stretching or N-H stretching vibration of bacterial nucleic acid component
(adenine, guanine, and/or cytosine). The peak intensity and width at 3300 cm-1 of the
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CNABE.coli and WAAM-NABE.coli were larger than those of the sample immersed in the
solution without bacteria. Therefore, it was determined that the CNABE.coli and
WAAM-NABE.coli surfaces were N-H and hydroxyl O-H groups, and the blank CNB
and WAAM-NAB samples were hydroxyl O‐H groups [56]. Many spectral peaks
appear in the typical C-H stretching region between 2960 and 2850 cm-1. This is
attributed to the fact that some cell wall components of Gram-negative bacteria, such
ot
as lipids, lipoproteins, and polysaccharides are usually absorbed [57,58], and the IR
absorption of cellular proteins then shows multiple amide-related bands. The IR band
at 1660 cm-1 indicates C=O and C-N (amide I) stretching, while a peak at 1540 cm-1
tn
reflects a combination of N-H bending and C-N (amide II) stretching (amide I and
amide II correspond to the functional groups in the protein) [59]. In some aliphatic
compounds (fatty acids), stretching vibrations of -CH2 and -CH3 functional groups can
be detected at 1454 cm-1 and 1393 cm-1. Carbonyl groups in cell wall-associated
glycopeptides as well as P=O stretching and P-O-C (P-O-P) bonds in phospholipids and
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esters are thought to be responsible for the strong absorption at 1080 cm-1. The IR
region between 900 and 600 cm-1 shows some rather broad but weak spectral features
that may belong to aromatic ring vibrations [60]. By comparison, the peak intensity of
the organic matter on the surface of WAAM-NAB was significantly higher than that of
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CNAB in the solution without bacteria, while the peak intensity of CNAB was high in
the solution containing bacteria.
Fig. 21 shows the XPS spectra of the samples after 15 days of immersion in the
solution containing bacteria. By calculating the percentage of each element on the
Pr
surface, it was found that the percentage of Cu on the surface of WAAM-NAB was
much higher than the other elements, reaching 44.15%, while the surface of CNAB was
mainly dominated by C and O, and the percentage of Cu was only 17.63%. A fine sweep
of the locations of the characteristic peaks for Cu was performed, and unlike the surface
14
layer of the samples after simulated seawater immersion in the previous paper, which
was dominated by Cu2+, Cu ions were present as Cu+ at this time. Shimabukuro has
ed
reported that the presence of E.coli inhibited the production of Cu2+ in copper alloys
and led to the elution of Cu ions, promoting the production of Cu+ [61].
4. Discussion
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4.1 Corrosion behavior
During the WAAM process, due to the extremely fast cooling rate, the NAB alloy
solidifies with a large degree of undercooling, resulting in a small matrix grain size
(Fig. 4) and an increase in grain boundaries. The higher distortion energy and a large
number of irregularly arranged atoms at the grain boundaries make corrosion easy to
occur. As a result, fine-grained materials have more initially active atoms compared to
v
large-grained materials, which makes the free transport of corrosion ions easier, the
passivation ability of the alloy is reduced, and the corrosion rate is accelerated.
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However, in this experiment, the corrosion resistance of the coarse-grained CNAB alloy
was significantly weaker than that of the WAAM-NAB alloy (combined with the
corrosion morphology and electrochemical test results). This is mainly due to two
reasons. First, according to the electrochemical theory, during metal corrosion, the
corrosion rate is directly related to the corrosion current. The corrosion current is
er
generally determined by the relative area of the anode and cathode, the electrode
potential difference between the positive and negative reactions, the reaction kinetics,
and the oxidant (O2 and H+) [62]. In alloys, grain boundaries have high free energy
forming a low electrode potential, while the internal free energy of grains is low
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forming a high electrode potential. Therefore, there is a spatial distribution of potential
differences on the surface of the alloy, leading to non-uniform corrosion, and the degree
of local corrosion is related to both the potential and the oxidation capacity of the
solution (equilibrium potential of the reduction reaction). When the oxidation force is
between the grain boundary and the intra-grain electrode potential, the anodic position
ot
is confined to the grain boundary, resulting in localized corrosion of the grain boundary.
In this case, the relative surface area from the anode to the cathode position affects the
degree of penetration caused by the local anodic reaction [63]. A large cathode area
favors the reduction reaction, so the anodic dissolution current must be increased to
tn
comply with the requirement of local electrical neutrality. Therefore, when the area
inside the grain is several orders of magnitude larger than the area of the grain boundary,
the penetration of the grain boundary is enhanced and the corrosion of the grain
boundary is more severe. Conversely, when the differential polarization concentration
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of the cathodic reaction overpotential is high, the cathodic area is reduced by the
reduction of the grain, resulting in a reduction of the cathodic current and thus the
reduction of the anodic current (slowing down the grain boundary corrosion). Cu+/Cu2+
ions dissolved at the grain boundaries easily flow near the inner surface of the grain,
and these Cu ions near the surface interrupt the O2 supply and reduction reaction,
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leading to a reduction in cathodic current. In addition, the dilution of biased impurities

at grain boundaries can also be considered a beneficial effect of grain size reduction on
corrosion resistance [64].
Second, NAB is a multiphase alloy consisting of α-Cu phase, β′ phase, and several
Pr
κ phases with different morphologies (Fig. 2). Due to the differences in chemical
composition and crystal structure, the relative potentials of the phases are inevitably
inconsistent when NAB is immersed in seawater. Nakhaie found that when immersed
15
in a solution containing Cl-, there is a significant potential difference between these κ
phases and the matrix phase, specifically Eβ ≈ Eα > EκⅢ > EκⅣ > EκⅡ > EκⅠ, where the
ed
potential difference between the α and κⅠ phases is up to 70 mV [22]. According to the
electrochemical corrosion theory, the material phase with high potential will act as the
cathode in the galvanic corrosion and be protected. The sensitive area for phase
selection corrosion of NAB alloy should be the κ phase, but this is contrary to the
experimental phenomenon (Fig. 12). As shown in Fig. 22, in the corrosion process Al-
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rich κ phase surface in the corrosion medium will quickly generate Al2O3-based
passivation film so that the κ phase was effectively protected. The Cu2O-based product
film formed on the surface of the substrate is semi-conductive and has defects such as
holes inside, so it is less effective in protecting the substrate. The α-Cu and β' phase
regions in contact with the κ phase in neutral solution became sensitive to corrosion
and were preferentially corroded. Since the precipitation of the κ phase was limited, the
v
selected phase corrosion of WAAM-NAB disappeared and the matrix α-Cu phase was
hardly corroded during the corrosion process. The β′ phase, which underwent a
re
martensitic transformation in the rapid cooling mode, is similar to the anode of the α-
Cu phase in the corrosion medium due to its high chemical activity, and corrosion was
concentrated within the β′ phase (Fig. 22(b)). As the β′ phase and α-Cu phase are similar
in composition, the corrosion product film formed on the surface of the substrate is
more uniform in composition, which effectively protects the substrate, and the surface
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corrosion is weaker than that of CNAB alloy.
4.2 Antibacterial and microbial corrosion
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When the sample was immersed in a solution containing a culture medium, the
interaction of metal ions with proteins (amino acids) can form protein adsorption, which
forms metal-protein complexes (chelates) on the surface, slowing down the ion
exchange between the alloy surface and the corrosion medium [65], reducing the release
of metal ions, blocking electrochemical dissolution, and slowing down corrosion
[66,67]. The proteins also fill the voids in the product film on the alloy surface, making
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the layer denser. By EDS calibration, the immersed CNAB and WAAM-NAB surfaces
have the presence of C, N, O, and P in addition to the matrix elements. This indicates
that the proteins have been adsorbed on the samples, isolating the attack of the matrix
by Cl- in solution, and therefore the alloy is more resistant to corrosion than the samples
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immersed in simulated seawater. Since the size of WAAM-NAB is much smaller than
that of the CNAB alloy (Fig. 4), grain refinement promotes the formation of charged
spots on the surface, which facilitates the adsorption of proteins and increases the
number of hydroxyl groups (O-H). Therefore, in the infrared spectrum (Fig. 20), the
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peak of WAAM-NAB at 3300 nm was significantly higher than that of CNAB.

Generally, heavy metal ions can form stable complexation ability with N, O, and S and
bind to proteins. κ phase is mainly composed of Fe and Al elements, which are weakly
bound to proteins, and the corrosion of CNAB alloy was transferred to the κ phase (Fig.
19). On the contrary, the surface layer of WAAM-NAB alloy that inhibited the
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precipitation of κ phase was almost completely covered by the protein layer, and only
a very small number of corrosion pits were found on the surface after 15 days of
immersion, and the corrosion resistance of the alloy was still stronger than that of
CNAB.
Pr
In Fig. 15, the corrosion of the CNAB alloy occurred in the κ phase consisting of
Fe/ Al and Ni, and there is no significant corrosion of the matrix, and the antibacterial
properties of Fe, Al, and Ni were not sufficient to inactivate the bacteria. Although the
16
corrosion of WAAM-NAB was much lower than that of CNAB, it almost occurred in
the matrix, resulting in the continuous release of Cu ions into the solution, and Fig. 17
ed
demonstrates that the release rate of Cu ions from the WAAM-NAB matrix was faster
than that of the CNAB. And according to the "small size effect", the smaller the particle
size of the antimicrobial material, the better the antimicrobial effect. Therefore, the
bactericidal effect of WAAM-NAB alloy is better than that of CNAB, and the number
of colonies (live and dead bacteria) deposited on the surface of the WAAM-NAB is
iew
much smaller than that of CNAB alloy.
Although Cu ions have a good bactericidal effect, but not instant extermination,
bacteria can survive on the surface of Cu for some time[68]. During this process,
bacteria secrete EPS for self-protection and mutual adhesion [69]. One of the most
essential functions of EPS is to act as a binding material for bacterial cells, allowing
v
them to adhere to the biofilm substrate and eventually form biofilms with bacteria on
the metal surface, etc. The presence of functional groups such as -COOH, -NH2, and
phosphate groups in EPS makes them negatively charged themselves [70,71], allowing
re
EPS to give or receive electrons and chelate with metal cations such as Cd2+, Cu2+, Cr2+,
and Pb2+ through electrostatic or covalent bonding to form complexes. Eventually, EPS
adsorbs on the metal surface, forming a denser film to protect the metal from corrosion
[72]. Some functional groups in the extracellular polysaccharides secreted by EPS also
er
affect the density of the passivation layer and enhance the protective properties of the
biofilm. In addition to biofilm, some functional groups in EPS replace the anode to
react with cathode electrons, thus protecting the anode metal from dissolution. For
example, Juntao Jin [72,73] studied the changes of functional groups in EPS before and
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after immersion in cast iron and showed that the number of C=O and C-(O, N)
decreased and the number of C-(C, H) increased. It is presumed that C=O and C-(O, N)
replace the anode as electron donors and react with the cathode electrons, converting to
C-(C, H), and the corrosion of cast iron is significantly reduced. In this experiment, the
EPS secreted by bacteria provided landing sites for subsequent colony attachment, and
a protein-colony biofilm gradually formed on the surface of the alloy (as shown in Fig.
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22), which further enhanced the corrosion resistance of the CNAB relative to the sterile
environment. WAAM-NAB alloy has less colonies attached to the surface due to the
better sterilization effect (Fig.23). After 24 hours of incubation, E.coli can utilize sugar,
tn
which decomposed to produce acids and gases, causing the pH of the surrounding
environment to drop and the metal to corrode. As a result, corrosion pits remained on
the surface of the alloy after removal of the colonies. This explains the lower impedance
value of WAAM-NAB alloy in the solution containing bacteria than in the solution
without bacteria. As mentioned earlier, copper is more capable of chelating with
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substances such as proteins compared to Fe, Al and Ni, therefore, the protein layer
formed by CNAB will be depressed and inhomogeneous (Fig. 23). Therefore, the
location of the κ phase was easily penetrated by the acid and corrosion occurred on the
κ phase.
ep
Conclusion
In this study, wire arc additive manufacturing technology was used to fabricate
composite structures of NAB and 316L stainless steel. By comparing the microstructure,
corrosion behavior, and antimicrobial properties with those of the as-cast NAB alloy,
Pr
the significant findings are drawn as follows:

1. Compared with the CNAB, the WAAM-NAB matrix has a higher proportion of
residual β phase per unit area, the grain size is smaller and no significant grain
17
orientation. The precipitation of the κ phase was limited, where the precipitation of the
rossite-like κI phase was suppressed, and the number of κⅡ, κⅢ, κⅣ phases was reduced
ed
and the size was decreased.
2. The corrosion product film formed by NAB alloy can be divided into three layers:
the inner layer is mainly Al2O3 honeycomb organization, the second inner layer is
mainly Cu2O and CuCl to form a sheet-like organization, and the outer layer is mainly
iew
CuO and Cu2Cl(OH)3 formed flocculent organization. However, Fe2O3-based product
film was formed on the κ phase, which was discontinuous with the product film of the
substrate and created cracks, which reduced the protection of the substrate. In WAAM-
NAB, because the precipitation of the κ phase was restricted, the selected phase
corrosion was suppressed, the corrosion occurred in the β' phase, the corrosion
resistance was much higher than that of CNAB and the difference in current density
v
distribution on the surface was small. After scratching the substrate, the corrosion
products of the cast alloy can pile up the scratches in a short time (6 days) and the Rct
value returned to the pre-scratch value due to its poor corrosion resistance, while
re
WAAM-NAB took a longer time (10 days) to return to the pre-scratch Rct value.
3. In the solution containing culture medium, metal ions chelate with proteins, etc., and
the corrosion resistance of the alloy increases substantially; the heavy metal Cu ions
and proteins are more tightly bound than Fe, Ni, and Al, and the corrosion of the cast
er
alloy is transferred to the κ phase. The corrosion resistance of WAAM-NAB alloy is
still higher than that of the cast alloy, and corrosion pits of smaller size appear in the α-
Cu phase, in addition to the β phase. In solutions containing bacteria, the Cu ions of the
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WAAM-NAB were released more rapidly and are more effective in sterilization. After
15 days of immersion, the surface of the cast alloy was completely covered by bacteria
(live and dead bacteria), forming a dense biofilm layer, and the corrosion resistance of
the alloy was higher than that in the solution without bacteria. The WAAM-NAB was
not completely covered by bacterial colonies and the corrosion resistance was reduced
compared to immersion in a solution without bacteria.
ot
Acknowledgments
This work was supported by the National Key Research and Development Program of
China (grant number 2016YFC1102402).
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Data availability
The raw/processed data required to reproduce these findings cannot be shared at this
time as the data also forms part of an ongoing study.
rin
Reference
[1] F. Yang, H. Kang, Z. Chen, E. Guo, Y. Zeng, W. Wang, T. Wang, Electrochemical corrosion
ep
mechanisms of nickel-aluminium bronze with different nickel contents using the rotating disc electrode,
Corros. Sci. 157 (2019) 438-449. https://doi.org/10.1016/j.corsci.2019.06.018.
[2] E.A. Culpan, A.G. Foley, The detection of selective phase corrosion in cast nickel aluminum bronze
by acoustic-emission techniques, J. Mater. Sci. 17(4) (1982) 953-964.
https://doi.org/10.1007/BF00543513.
[3] C. Dharmendra, S. Shakerin, G.D.J. Ram, M. Mohammadi, Wire-arc additive manufacturing of nickel
Pr
aluminum bronze/stainless steel hybrid parts - Interfacial characterization, prospects, and problems,
Materialia 13 (2020). https://doi.org/10.1016/j.mtla.2020.100834.
[4] F.F. Yang, H.J. Kang, E.Y. Guo, R.G. Li, Z.N. Chen, Y.H. Zeng, T.M. Wang, The role of nickel in
mechanical performance and corrosion behaviour of nickel-aluminium bronze in 3.5 wt.% NaCl solution,
18
Corros. Sci. 139 (2018) 333-345. https://doi.org/10.1016/j.corsci.2018.05.012.
[5] Z. Wu, Y.F. Cheng, L. Liu, W.J. Lv, W.B. Hu, Effect of heat treatment on microstructure evolution
and erosion–corrosion behavior of a nickel–aluminum bronze alloy in chloride solution, Corros. Sci. 98
ed
(2015) 260-270. https://doi.org/10.1016/j.corsci.2015.05.037.
[6] Y.T. Lv, L.Q. Wang, Y.F. Han, X.Y. Xu, W.J. Lu, Investigation of microstructure and mechanical
properties of hot worked NiAl bronze alloy with different deformation degree, Mater. Sci. Eng. A-Struct.
Mater. Prop. Microstruct. Process. 643 (2015) 17-24. https://doi.org/10.1016/j.msea.2015.06.078.
[7] M. Wysiecki, L. Labuc, Optimization of chemical composition of five-component aluminium bronze
iew
for the production of ship's propellers. II. Multicriterion optimization, Int. J. Mater. Product. Technol.
1990 5 (4) 339–348. https://doi.org/10.1504/IJMPT.1990.036653.
[8] D.R. Ni, B.L. Xiao, Z.Y. Ma, Y.X. Qiao, Y.G. Zheng, Corrosion properties of friction-stir processed
cast NiAl bronze, Corros. Sci. 52(5) (2010) 1610-1617. https://doi.org/10.1016/j.corsci.2010.02.026.
[9] S. Rajakumar, V. Balasubramanian, Corrosion performance of friction surfaced nickel aluminium
bronze (NAB) alloy under erosion corrosion and salt fog environment, Corros. Eng. Sci. Technol. 53
(2018) 21-26. https://doi.org/10.1080/1478422X.2018.1425178.
v
[10] Y.T. Lv, B.J. Zhao, H.B. Zhang, C.J. Su, B. Nie, R. Wang, L.M. Cao, F.Y. Lyu, Improving corrosion
resistance properties of nickel-aluminum bronze (NAB) alloys via shot peening treatment, Mater. Trans.
60 (2019) 1629-1637. https://doi.org/10.2320/matertrans.M2019031.
re
[11] V. Dutta, L. Thakur, B. Singh, H. Vasudev, A Study of erosion-corrosion behaviour of friction stir-
processed chromium-reinforced NiAl bronze composite, Materials 15(15) (2022).
https://doi.org/10.3390/ma15155401.
[12] T. DebRoy, H.L. Wei, J.S. Zuback, T. Mukherjee, J.W. Elmer, J.O. Milewski, A.M. Beese, A.
Wilson-Heid, A. De, W. Zhang, Additive manufacturing of metallic components - Process, structure and
properties, Prog. Mater. Sci. 92 (2018) 112-224. https://doi.org/10.1016/j.pmatsci.2017.10.001.
er
[13] A. Shahriari, L. Khaksar, A. Nasiri, A. Hadadzadeh, B.S. Amirkhiz, M. Mohammadi, Microstructure
and corrosion behavior of a novel additively manufactured maraging stainless steel, Electrochim. Acta
339 (2020). https://doi.org/10.1016/j.electacta.2020.135925.
[14] A. Cd, B. Bsaa, C. Al, D. Gdjra, M.A.J.A. Manufacturing, Wire-arc additive manufactured nickel
pe
aluminum bronze with enhanced mechanical properties using heat treatments cycles, Addit. Manuf.
36(2020). https://doi.org/10.1016/j.addma.2020.101510.
[15] S.Y. Tang, L. Yang, Z.T. Fan, W.M. Jiang, X.W. Liu, A review of additive manufacturing
technology and its application to foundry in China, China Foundry 18(4) (2021) 249-264.
https://doi.org/10.1007/s41230-021-1003-0.
[16] L. Chen, Y. He, Y. Yang, S. Niu, H. Ren, The research status and development trend of additive
manufacturing technology, Int. J. Adv. Manuf. Technol. 89(9-12) (2017) 3651-3660.
ot
https://doi.org/10.1007/s00170-016-9335-4.
[17] H. Lee, C.H.J. Lim, M.J. Low, N. Tham, V.M. Murukeshan, Y.J. Kim, Lasers in additive
manufacturing: A Review, Int. J. Precis Eng Manuf-Green Technol. 4(3) (2017) 307-322.
https://doi.org/10.1007/s40684-017-0037-7.
tn
[18] C. Zhou, L. Luo, Y. Liu, J. Wu, Research status of additive manufacturing technology for metal, hot
working technology 47(6) (2018) 9-14. https://doi.org/10.14158/j.cnki.1001-3814.2018.06.003.
[19] D. Liu, B. Lee, A. Babkin, Y. Chang, Research progress of arc additive manufacture technology,
Materials 14(6) (2021). https://doi.org/10.3390/ma14061415.
[20] C. Dharmendra, A. Hadadzadeh, B.S. Amirkhiz, G.D.J. Ram, M. Mohammadi, Microstructural
rin
evolution and mechanical behavior of nickel aluminum bronze Cu-9Al-4Fe-4Ni-1Mn fabricated through
wire-arc additive manufacturing, Addit. Manuf. 30 (2019).
https://doi.org/10.1016/j.addma.2019.100872.
[21] C. Shen, Z. Pan, D. Ding, L. Yuan, N. Nie, Y. Wang, D. Luo, D. Cuiuri, S. van Duin, H. Li, The
influence of post-production heat treatment on the multi-directional properties of nickel-aluminum
bronze alloy fabricated using wire-arc additive manufacturing process, Addit. Manuf. 23 (2018) 411-
ep
421. https://doi.org/10.1016/j.addma.2018.08.008.
[22] X. Cai, Z. Wang, L. Dong, M. Yang, J. Zhou, F. Xue, Advanced mechanical properties of
nickel‐aluminum bronze/steel composite structure prepared by wire‐arc additive manufacturing, Mater.
Des. 221 (2022). https://doi.org/10.1016/j.matdes.2022.110969.
[23] D. Nakhaie, A. Davoodi, A.J.C.S. Imani, The role of constituent phases on corrosion initiation of
Pr
NiAl bronze in acidic media studied by SEM–EDS, AFM and SKPFM, Corros. Sci. 80 (2014) 104-
https://doi.org/110. 10.1016/j.corsci.2013.11.017.
[24] S. Neodo, D. Carugo, J.A.Wharton, K.R. Stokes, Electrochemical behaviour of nickel-aluminium
bronze in chloride media: Influence of pH and benzotriazole, J. Electroanal. Chem. 695 (2013) 38-46.
https://doi.org/10.1016/j.jelechem.2013.02.007.
19
[25] E.A. Culpan, G. Rose, Corrosion Behaviour of cast nickel aluminium bronze in seawater, Br. Corros.
J. 14 (2014) 160-166. https://doi.org/10.1179/bcj.1979.14.3.160.
[26] T. Murray, S. Thomas, Y. Wu, W. Neil, C. Hutchinson, Selective laser melting of nickel aluminium
ed
bronze, Addit. Manuf. 33 (2020). https://doi.org/10.1016/j.addma.2020.101122.
[27] Q.S. Dong, J.W. Dai, K. Qian, H. Liu, X.X. Zhou, Q.Q. Yao, M.M. Lu, C.L. Chu, F. Xue, J. Bai,
Dual self-healing inorganic-organic hybrid coating on biomedical Mg, Corros. Sci. 200 (2022).
https://doi.org/10.1016/j.corsci.2022.110230.
[28] Q. Luo, Z. Wu, Z. Qin, L. Liu, W. Hu, Surface modification of nickel-aluminum bronze alloy with
iew
gradient Ni-Cu solid solution coating via thermal diffusion, Surf. Coat. Technol. 309 (2017) 106-113.
https://doi.org/10.1016/j.surfcoat.2016.11.013.
[29] P . Brezina, Heat treatment of complex aluminium bronzes, Int. Mater. Rev. 27 (1982) 77-120.
https://doi.org/10.1179/imr.1982.27.1.77.
[30] F. Hasan, G.W. Lorimer, N. Ridley, Crystallography of marensite in a Cu-10Al-5Ni-5Fe alloy. J.
Phys. Colloques 43 (1982) 653-658. https://doi.org/10.1051/jphyscol:19824105.
[31] P.R. Swann, H. Warlimont, Electron-metallography and crystallography of copper aluminum
v
martensites, Acta. Metall. Mater. 11 (1963) 511-516. https://doi.org/10.1016/0001-6160(63)90086-5.
[32] L.M. Schetky, Shape-memory alloys, Sci. Am. 241(5) (1979) 74-82.
https://doi.org/10.1038/scientificamerican1179-74.
re
[33] Z. Nishiyam, J. Kakinoki, S. Kajiwara, Stacking faults in martensite of Cu-Al alloy, J. Phys. Soc.
Jpn. 20 (1965) 1192-1196. https://doi.org/10.1143/JPSJ.20.1192.
[34] M.J. Duggin, Futher studies of martensitic transformations in gold-copper-zinc and copper-
aluminium-nickel alloys, Acta. Metall. Mater. 14 (1966) 123-128. https://doi.org/10.1016/0001-
6160(66)90293-8.
[35] M.J. Duggin, W.A. Rachinger, Nature of martensite transformation in copper-aluminium-nickel
er
alloy, ACTA METALL MATER 12 (1964) 529-534. https://doi.org/10.1016/0001-6160(64)90025-2.
[36] C. Xiang, C. Liu, X. Wen, H. Nie, C. Hu, Z. Luo, Y. Li, J. Luo, Z. Yu, Formation of stacking faults
in tungsten carbide during sintering, Ceram. Int. 46 (2020) 15851-15857.
https://doi.org/10.1016/j.ceramint.2020.03.132.
pe
[37] H. Nady, N.H. Helal, M.M. El-Rabiee, W.A. Badawy, The role of Ni content on the stability of Cu-
Al-Ni ternary alloy in neutral chloride solutions, Mater. Chem. Phys. 134 (2012) 945-950.
https://doi.org/10.1016/j.matchemphys.2012.03.096.
[38] Z.B. Qin, Z. Wu, X.S. Zen, Q. Luo, L. Liu, W.J. Lu, W.B. Hu, Improving corrosion resistance of a
nickel-aluminum bronze alloy via nickel ion implantation, Corrosion 72 (2016) 1269-1280.
https://doi.org/10.5006/2097.
[39] Y. Ding, Y. Lv, K. Chen, B. Zhao, Y. Han, L. Wang, W. Lu, Effects of microstructure on the stress
ot
corrosion cracking behavior of nickel-aluminum bronze alloy in 3.5% NaCl solution, Mater. Sci. Eng.
A-Struct. Mater. Prop. Microstruct. Process. 733 (2018) 361-373.
https://doi.org/10.1016/j.msea.2018.07.066.
[40] W.A. Badawy, M.M. El-Rabiei, H. Nady, Synergistic effects of alloying elements in Cu-ternary
tn
alloys in chloride solutions, Electrochim. Acta 120 (2014) 39-45.

https://doi.org/10.1016/j.electacta.2013.12.043.
[41] B. Sabbaghzadeh, R. Parvizi, A. Davoodi, M.H. Moayed, Corrosion evaluation of multi-pass welded
nickel-aluminum bronze alloy in 3.5% sodium chloride solution: A restorative application of gas tungsten
arc welding process, Mater. Des. 58 (2014) 346-356. https://doi.org/10.1016/j.matdes.2014.02.019.
[42] I.O. K'Owino, O.A. Sadik, Impedance spectroscopy: A powerful tool for rapid biomolecular
rin
screening and cell culture monitoring, Electroanalysis 17(23) (2005) 2101-2113.

https://doi.org/10.1002/elan.200503371.
[43] Z.B. Qin, Q. Zhang, Q. Luo, Z. Wu, B. Shen, L. Liu, W.B. Hu, Microstructure design to improve
the corrosion and cavitation corrosion resistance of a nickel-aluminum, Corros. Sci. 139 (2018) 255-266.
https://doi.org/10.1016/j.corsci.2018.04.043.
ep
[44] A.M. Alfantazi, T.M. Ahmed, D. Tromans, Corrosion behavior of copper alloys in chloride media,
Mater. Des. 30 (2009) 2425-2430. https://doi.org/10.1016/j.matdes.2008.10.015.
[45] B. Zhang, J. Wang, F. Yan, Load-dependent tribocorrosion behaviour of nickel-aluminium bronze
in artificial seawater, Corros. Sci. 131 (2018) 252-263. https://doi.org/10.1016/j.corsci.2017.11.028.
[46] W.A. Badawy, K.M. Ismail, A.M. Fathi, Effect of Ni content on the corrosion behavior of Cu–Ni
alloys in neutral chloride solutions, Electrochim. Acta 50 (2005) 3603-3608.
Pr
[47] M.M. Sadawy, M. Ghanem, Grain refinement of bronze alloy by equal-channel angular pressing
(ECAP) and its effect on corrosion behaviour, Def. Technol. 12 (2016) 316-323.
https://doi.org/10.1016/j.dt.2016.01.013 .
20
[48] J.B. Jorcin, M.E. Orazem, N. Pebere, B. Tribollet, CPE analysis by local electrochemical impedance
spectroscopy, Electrochim. Acta 51(8-9) (2006) 1473-1479.
ed
[49] F. Rosalbino, R. Carlini, F. Soggia, G. Zanicchi, G.J.C.e. Scavino, Influence of rare earth metals
addition on the corrosion behaviour of copper in alkaline environment, Corros. Sci. 58 (2012) 139–144.
[50] Y. Qiang, S. Zhang, S. Yan, X. Zou, S.J.C.S. Chen, Three indazole derivatives as corrosion
inhibitors of copper in a neutral chloride solution, Corros. Sci. 126 (2017) 295-304.
iew
[51] A. Schüssler, H.E.J.C.S. Exner, The corrosion of nickel-aluminium bronzes in seawater—I.
Protective layer formation and the passivation mechanism, Corros. Sci. 34 (1993) 1793-1802.
https://doi.org/10.1016/0010-938X(93)90017-B.
[52] A.A. El-Meligi, Corrosion behaviours of copper alloy in solutions containing Na2SO4 and NaCl with
different concentrations, J. Mater. Sci. Technol. 18(6) (2002) 549-551.
https://doi.org/10.3321/j.issn:1005-0302.2002.06.019.
[53] G. Kear, B.D. Barker, F.C. Walsh, Electrochemical corrosion of unalloyed copper in chloride media
v
- a critical review, Corros. Sci. 46(1) (2004) 109-135. https://doi.org/10.1016/S0010-938X(02)00257-3.
[54] H. Zhao, Y. Sun, L. Yin, Z. Yuan, Y. Lan, D. Xu, C. Yang, K. Yang, Improved corrosion resistance
re
and biofilm inhibition ability of copper-bearing 304 stainless steel against oral microaerobic
Streptococcus mutans, J. Mater. Sci. Technol. 66 (2021) 112-120.
https://doi.org/10.1016/j.jmst.2020.06.027.
[55] B.E.T. Bautista, A.J. Wikiel, I. Datsenko, M. Vera, W. Sand, A. Seyeux, S. Zanna, I. Frateur, P.
Marcus, Influence of extracellular polymeric substances (EPS) from Pseudomonas NCIMB 2021 on the
corrosion behaviour of 70Cu-30Ni alloy in seawater, J. Electroanal. Chem. 737 (2015) 184-197.
er
https://doi.org/10.1016/j.jelechem.2014.09.024.
[56] Y. Li, C. Shi, L. Guan, Y. You, W. Tan, Correlation between protein adsorption and electrochemical
corrosion behavior of niobium for bio-implant application, J. Solid State Electrochem. 24 (2020) 1325-
1336. https://doi.org/10.1007/s10008-020-04634-x.
pe
[57] L. Abdoli, J. Huang, H. Li, Electrochemical corrosion behaviors of aluminum-based marine coatings
in the presence of Escherichia coli bacterial biofilm, Mater. Chem. Phys. 173 (2016) 62-69.
https://doi.org/10.1016/j.matchemphys.2016.01.038.
[58] S.R.R. Rajasree, M. Gobalakrishnan, L. Aranganathan, M.G. Karthih, Fabrication and
characterization of chitosan based collagen/gelatin composite scaffolds from big eye snapper Priacanthus
harmrur skin for antimicrobial and anti oxidant applications, Mater. Sci. Eng. C-Mater. Biol. Appl. 107
(2020). https://doi.org/10.1016/j.msec.2019.110270.
ot
[59] M. Liu, T. Liu, X. Chen, J. Yang, J. Deng, W. He, X. Zhang, Q. Lei, X. Hu, G. Luo, J. Wu, Nano-
silver-incorporated biomimetic polydopamine coating on a thermoplastic polyurethane porous
nanocomposite as an efficient antibacterial wound dressing, J. Nanobiotechnol. 16 (2018).
https://doi.org/10.1186/s12951-018-0416-4.
tn
[60] D. Naumann, Infrared Spectroscopy in Microbiology, Encyclopedia of Analytical Chemistry, Berlin,

Germany, 2006.
[61] Z. Filip, S. Hermann, K. Demnerova, FT-IR Spectroscopic Characteristics of Differently Cultivated
Escherichia coli, Czech. J. Food Sci. 26 (2008) 458-463. https://doi.org/10.17221/14/2008-CJFS.
[62] M. Shimabukuro, T. Manaka, Y. Tsutsumi, K. Nozaki, P. Chen, M. Ashida, A. Nagai, T. Hanawa,
Corrosion Behavior and Bacterial Viability on Different Surface States of Copper, Mater. Trans. 61(6)
rin
(2020) 1143-1148. https://doi.org/10.2320/matertrans.MT-M2020008.

[63] L. Beaunier, Corrosion of grain-boundaries-initiation processes and testing, J. Phys. I 43 (1982)
271-282. https://doi.org/10.1051/jphyscol:1982624.
[64] H. Miyamoto, K. Harada, T. Mimaki, A. Vinogradov, S. Hashimoto, Corrosion of ultra-fine grained
copper fabricated by equal-channel angular pressing, Corros. Sci. 50 (2008) 1215-1220.
ep
[65] G. Palumbo, U. Erb, Enhancing the operating life and performance of lead-acid batteries via grain-
boundary engineering, MRS Bull. 24 (1999) 27-32. https://doi.org/10.1557/S0883769400053422.
[66] C.L. Liu, Y.J. Wang, R.C. Zeng, X.M. Zhang, W.J. Huang, P.K. Chu, In vitro corrosion degradation
behaviour of Mg-Ca alloy in the presence of albumin, Corros. Sci. 52 (2010) 3341-3347.
Pr
[67] Y. Hedberg, X. Wang, J. Hedberg, M. Lundin, E. Blomberg, I.O. Wallinder, Surface-protein

interactions on different stainless steel grades: effects of protein adsorption, surface changes and metal
release, J. Mater. Sci.-Mater. Med. 24 (2013) 1015-1033. https://doi.org/10.1007/s10856-013-4859-8.
[68] J.L. Smith, N. Tran, T. Song, D. Liang, M. Qian, Robust bulk micro-nano hierarchical copper
21
structures possessing exceptional bactericidal efficacy, Biomaterials, 280 (2022).
https://doi.org/10.1016/j.biomaterials.2021.121271.
[69] F. Ye, Y. Ye, Y. Li, Effect of C/N ratio on extracellular polymeric substances (EPS) and
ed
physicochemical properties of activated sludge flocs, J. Hazard. Mater. 188 (2011) 37-43.
https://doi.org/10.1016/j.jhazmat.2011.01.043.
[70] Z.Q. Hu, J. Jin, H.D. Abruna, P.L. Houston, A.G. Hay, W.C. Ghiorse, M.L. Shuler, G. Hidalgo,
L.W. Lion, Spatial distributions of copper in microbial biofilms by scanning electrochemical microscopy,
Environ. Sci. Technol. 41 (2007) 936-941. https://doi.org/10.1021/es061293k.
iew
[71] S. Comte, G. Guibaud, M. Baudu, Biosorption properties of extracellular polymeric substances (EPS)
towards Cd, Cu and Pb for different pH values, J. Hazard. Mater. 151 (2008) 185-193.
https://doi.org/10.1016/j.jhazmat.2007.05.070.
[72] J.T. Jin, G.X. Wu, Z.H. Zhang, Y.T. Guan, Effect of extracellular polymeric substances on corrosion
of cast iron in the reclaimed wastewater, Bioresour. Technol. 165 (2014) 162-165.
https://doi.org/10.1016/j.biortech.2014.01.117.
[73] J.T. Jin, Y.T. Guan, The mutual co-regulation of extracellular polymeric substances and iron ions
in biocorrosion of cast iron pipes, Bioresour. Technol. 169 (2014) 387-394.
v
https://doi.org/10.1016/j.biortech.2014.06.059.
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(b) (c)
(a)
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Fig. 1. Schematic diagram of WAAM‐NAB preparation: (a) wire arc additive manufacturing components, (b)
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deposition tracks, (c) WAAM-NAB.
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(a) (b)
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(c) (d)
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22
(e) (f)
ed
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(g)
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Fig. 2. Microscopic morphology of two samples: (a) and (b) optical maps of CNAB and WAAM-NAB, respectively;
(c) and (e) SEM of CNAB and WAAM-NAB; (f) is the enlarged part of (e), (d) and (g) are elemental distributions
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of (c) and (f).
(a) (b) (c) (d)

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(e) (f) (g)

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Fig. 3. HRTEM image of samples: (a), (b) matrix image of CNAB; (c), (d), (e), (f) matrix of WAAM-NAB; (g) the
elemental distribution of (e).
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25 14
(a) (b) 20
(c) 12 (d)
10
Proportion /%)
Proportion /%
15
8
10 6
4
5
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0 0
0 15 30 45 60 75 90 0 10 20 30 40 50 60
Grain Size /µm Angle /°
(e) (f) 10
(g)
18
(h)
15
8
Proportion /%
12
Proportion /%
Pr
6
9
4
6
2 3
0 0
0 5 10 15 20 25 0 10 20 30 40 50 60
Grain Size /µm Angle /°
23
Fig. 4 EBSD results from CNAB and WAAM-NAB: (a) and (e) inverse pole figure (IPF) map; (b) and (f) grain
boundary misorientation map; (c) and (g) grain size distribution plot; (d) crystal boundary angle statistics chart.
ed
2.0
CNAB
WAAM-NAB region 4
1.5 CNAB immersion 30d
WAAM-NAB immersion 30d 1.343
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1.149 1.194
1.146
1.0
ESCE /V
region 3
0.5 0.477
region 2 0.464
0.077
0.0 region 1 0.027
-0.5
v
-7 -6 -5 -4 -3 -2 -1 0
Log i /Acm-2
Fig. 5 Potentiodynamic polarisation curves of CNAB and WAAM-NAB immersed in artificial seawater.
re
40000
WAAM-NAB-0d (b)
35000
(a) WAAM-NAB-1d
WAAM-NAB-7d
WAAM-NAB-15d
30000 er WAAM-NAB-30d
CNAB-0d
CNAB-1d
25000
2
|Z"| /cm
CNAB-2d
CNAB-7d
20000 CNAB-15d
CNAB-30d
15000 (c)
pe
10000 WAAAM-NAB
5000
CNAB
0
0 5000 10000 15000 20000 25000 30000 35000 40000
Z' /cm
2
Fig. 6 (a) Nyquist plots for CNAB and WAAM-NAB alloys after various periods of immersion in artificial seawater;
(b) and (c) equivalent circuits used for the fitting.
ot
(a)
tn
rin
(b)
ep
Pr
Fig. 7 SVET 3D mapping of (a) CNAB and (b) WAAM-NAB in artificial seawater.
24
ed
12 CNAB
stable
WAAM-NAB stage
10
mitigation
Mass loss /g·m-2

stage
8
acceleration
6 stage
iew
2
0 20 40 60 80 100 120 140 160 180 200

Time /d
Fig. 8 Mass loss (ML) of different NAB alloys as functions of immersion time in artificial seawater.
v
 Al2O3 CNAB surface surfce
(c)
etching-50nm
(a)  Cu2(OH)3Cl
 Cu(OH)Cl
 WAAM-NAB (b) Cu 2p3
O 1s
etching 50 nm
re
CNAB Product etching 150 nm
Intensity (a.u.)
Intensity (a.u.)
 CuO WAAM-NAB Product etching 200 nm
Cu2+ Cu+
 α-Cu Cu 2p1
Intensity (a.u.)

Intensity /a.u.
O KL1
 Cu+
Cu2+
 Fe 2p1 Cu LM2
Fe 2p3 Mn 2p1
 940 938 936 934 932 930 928
940 938 936 934 932 930 928
C 1s Binding Energy (ev) Binding Energy (ev)
Na KL1
Cl 2p etching-150nm etching-200nm
Cl 2s Mn 3s
Al 2p

   
Intensity (a.u.)
Intensity (a.u.)
Cu+
Cu+
20 30 40 50
2 /deg.
60 70 80 90
er 1000 800 600
Binding Energy (ev)
400 200 0
940 938
Cu2+
936 934
Binding Energy (ev)
932 930 928 940 938 936 934 932
Binding Energy (ev)
930 928
surface
(d)
surface etching-50nm
Cu 2p3 etching 50 nm
etching 150 nm
(e)
Intensity (a.u.)
Intensity (a.u.) Cu+

pe
Cu2+
Cu 2p1
Intensity (a.u.)
O 1s
Cu+ Cu2+
O KL1
Cu LM2
Fe 2p1 940 938 936 934 932 930 928 940 938 936 934 932 930 928
Fe 2p3 Mn 2p1
Binding Energy (ev) Binding Energy (ev)
etching-150nm
Na KL1 C 1s
Cl 2s Cl 2p Al 2p 3s
Mn 3s
Intensity (a.u.)
Cu+
1000 800 600 400 200 0

Binding Energy (ev) 940 938 936 934 932
Binding Energy (ev)
930 928
ot
Fig. 9 Corrosion products of CNAB and WAAM-NAB alloys: (a) XRD physical phase analysis, XPS spectra of
CNAB (b) and WAAM-NAB (d), respectively; (c) and (e) for the detailed Cu 2p3/2 XPS spectra in (b) and (d).
(a)
tn
rin
(b)
ep
Pr
Fig. 10 Morphology of CNAB (a) and WAAM-NAB (b) alloys immersed in artificial seawater.
25
(a) (b) (c)
ed
iew
(d) (e)
v
(f) (g) (h)
re
er
Fig. 11 Corrosion morphology of samples immersed for 7 days: (a) CNAB; (b) and (d) for the area in (a); (c) and
(e) for (b) elemental EDS; (f) WAAM-NAB alloy; (g) and (h) for the area in (f).
(a)
pe
(b)
ot
(c) (d)
tn
rin
Fig. 12 Morphology of samples immersed for different times: (a) CNAB; (b) WAAM-NAB; (c) and (d) cross
sections of CNAB and WAAMNAB immersed for 30 days.
ep
(a)
Pr
26
(b)
ed
iew
(c)
v
(d)
re
(e)
er
pe
Fig. 13 Evolution of sample surface scratches during immersion: (a) and (b) for CNAB; (c) (d) (e) for WAAM-NAB.
ot
45000 45000
(a) 15D (b) 15d
40000 scratched 40000 scratched
scratched-3d scratched-3d
35000 35000 scratched-6d
scratched-6d
tn
scratched-10d scratched-10d
30000 30000
2
2
Z" /cm
Z" /cm
25000 25000
20000 20000
15000 15000
10000 10000
rin
5000 5000
0 0
0 5000 10000 15000 20000 25000 30000 35000 40000 0 5000 10000 15000 20000 25000 30000 35000 40000
Z' /cm Z' /cm
2 2
Fig. 14 Nyquist curves of samples with scratches on the surface: (a) CNAB; (b) WAAM-NAB.
ep
(a) (b)
Pr
27
(c) (d)
ed
(e) (f)
iew
(g) (h)
v
re
(i) (j)
er
(l)
pe
(k)
Fig. 15 Morphology of samples immersed in bacteria-containing solutions: (a)(c) and (b)(d) for CNAB and WAAM-
ot
NAB immersed for 3 days; (e) and (f) for 7 days; (g) and (h) for 15 days; (i) and (j) CNAB alloys to remove colonies,
(k) and (l) are WAAM-NAB.
(a)
tn
rin
(b)
ep
(c) (d)
Pr
28
(e) (f)
ed
Fig. 16 Micromorphology of samples immersed in solutions without bacteria: (a) and (b) for CNAB and WAAM-
iew
NAB for 3 days, respectively; (c) and (d) for 7 days; (e) and (f) for 15 days.
1000 CNAB
WAAM-NAB
Cu ions release profile /μg·L-1

800
600
v
400
200
re
0
0 2 4 6 8 10 12 14 16
Time /d
Fig. 17 Comparison of Cu ion release from samples immersed for different times.
(a)
er (b)
pe
✱✱✱
(c) (d)
200
Colony count
150
ot
100
50
0
tn
B
B
A
A
-N
N
C
M
A
A
W
Fig. 18 Antimicrobial properties of alloys: (a) CLSM images of live/dead cell staining tests on the surface of samples
immersed in CNAB and (b) WAAM-NAB for 15 days; (c) the images of the bacterial colony growth after co-culture
with alloys, (d) statistical Chart (⁎⁎⁎: P < 0.001).
rin
120000
(a) 0d (b) 120000 0d
1d 1d
100000 3d 100000
3d
9d 9d
80000 12d 80000 12d
ep
15d
2
15d
Z" /cm
2
Z" /cm
60000 60000
40000 40000
20000 20000
Pr
0 0
0 10000 20000 30000 40000 50000 60000 0 10000 20000 30000 40000 50000 60000
Z' /cm Z' /cm
2 2
29
120000 120000
(c) 0d
(d) 0d
1d 1d
ed
100000 3d 100000 3d
9d 9d
12d 12d
80000 80000
15d 15d
Z" /cm2
2
Z" /cm
60000 60000
40000 40000
iew
20000 20000
0
0
0 10000 20000 30000 40000 50000 60000
0 10000 20000 30000 40000 50000 60000
Z' /cm Z' /cm2
2
Fig. 19 Nyquist plots of different samples in solutions: with E.coli (a)CNAB; (b)WAAM-NAB; without E.coli:
v
(c)CNAB; (d)WAAM-NAB.
re
C=O; C‒N
‒CH2
C=O; P=O; P‒O‒C (P‒O‒P)

C‒H
N-H; C‒N
‒CH3
N‒H; O‒H
C‒O‒C; P‒O‒C
WAAM-NAB-E.coli
Tansmittance,%
CNAB-E.coli
er
WAAM-NAB
pe
CNAB
4000 3500 3000 2500 2000 1500 1000 500

Wavelength, nm
ot
Fig. 20 FTIR spectra of samples immersed in solutions with/without bacteria for 15 days.
(a) (b) (c)

Cu 2p3
tn
Cu 2p1
Intensity(Counts/sec)
O 1s Cu+
C 1s Cu+
WAAM-NAB
N 1s
S 2p
Al 2p
Al 2s
CNAB
rin
1400 1200 1000 800 600 400 200 0 -200 940 938 936 934 932 930 928 940 938 936 934 932 930 928
Binding Energy ev Binding Energy Binding Energy
Fig. 21 XPS spectra of samples immersed in bacteria-containing solutions (a); (b) and (c) detailed Cu 2p3/2 XPS
spectra of CNAB and WAAM-NAB, respectively.
ep
Pr
Fig. 22 The schematic illustration of corrosion mechanism for CNAB and WAAM-NAB in artificial seawater.
30
ed
iew
Fig. 23 The schematic illustration of corrosion mechanism for CNAB and WAAM-NAB in bacteria-containing
solutions.
Table 1. Arc additive parameters in the experiment.

Current Frequency Swing Voltage Speed Line energy Energy density
Parameters
v
/A /Hz /mm /V /cm/min J/cm J/cm2
Value 60 2.0 10 8.7 10 48.9 1174.5
re
Table 2. Chemical composition (wt%) of 316LSS, CNAB, and NAB wire.
Fe C Si Mn S P Cr Ni Mo
316LSS Bal. 0.014 0.42 1.37 0.66 0.012 16.83 12.42 2.51
Cu Al Fe Ni Mn Zn Sn Pb
NAB-Wire Bal.
er 9.03 4.41 4.59 0.9 0.008 0.004 0.001
CNAB Bal. 9.12 4.76 4.89 1.04 0.005 0.006 0.016

pe
Table 3. Components of the artificial seawater (ASTM D1141, g/L)
NaCl MgCl2 Na2SO4 CaCl2 KCl NaHCO3 H3BO3 SrCl2 NaF
24.53 5.2 4.09 1.16 0.695 0.201 0.027 0.025 0.003
Table 4. Parameters for sample polarization curve fitting

Ecorr(V) icorr(A·cm-2)
ot
CNAB -0.164 1.2×10-4

WAAM-NAB -0.158 7.35×10-5
CNAB―immersion 0.024 6.54×10-9
tn
WAAM-NAB―immersion 0.023 2.68×10-9
Table 5. Equivalent circuit parameters of different NAB alloys immersed in artificial seawater for different times.
alloy 0d 1d 2d 7d 15d 30d
Rs (Ω·cm2) 6.574 8.483 7.684 8.17 8.299 6.857
rin
Qf (μF·cm-2) 267.2 182.9 189.4 158.4 83.44 92.89

nf 0.7376 0.8088 0.8135 0.8302 0.7082 0.6084
Rf (Ω·cm2) 6.829 5.33×102 1.31×103 1.47×103 1.38×103 2.46×103
CNAB
Qct (μF·cm-2) 615.5 369.4 211.3 101.6 78.61 20.5
nct 0.3882 0.4487 0.4189 0.7403 0.7547 0.7975
ep
Rct (Ω·cm2) 544.32 2.20×103 9.13×103 1.44×104 2.57×104 5.45×104

W(Ω·cm-2·S1/2) 20.34 4.09×10-2 - - - -
Rs (Ω·cm2) 7.679 9.24 - 10.31 9.968 8.54
Qf (μF·cm-2) 303.9 172.9 - 60.65 38.47 33.67
Pr
WAAM- nf 0.7255 0.8208 - 0.8599 0.8707 0.9067

NAB Rf (Ω·cm2) 1.49×103 1.10×104 - 1.57×104 2.97×104 6.53×104
Qct (μF·cm-2) 1345 1141 - 69.47 73.1 76.22
nct 0.6332 0.7851 - 0.8988 0.8721 0.86
31
Rct (Ω·cm2) 8.19×102 9.51×103 - 5.42×104 7.21×104 1.08×105
W(Ω·cm-2·S1/2) 7.63 - - - - -
ed
Table 6. Equivalent circuit parameters of scratched NAB alloys immersed in artificial seawater for different times.
15d scratched scratched-3d scratched-6d scratched-10d
Rs(Ω·cm2) 13.56 12.24 12.67 12.79 15.10
iew
Qf (μF·cm-2) 3.11×10-5 1.81×10-5 3.128×10-5 3.045×10-5 2.423×10-5
nf 0.829 0.9949 0.8368 0.5281 0.8193
CNAB Rf (Ω·cm2) 10.12 47.05 8.665 9.121 12.05
Qct (μF·cm-2) 1.084×10-4 1.159×10- 1.111×10-4 1.128×10-4 1.07×10-4
nct 0.8495 4
0.8251 0.8484 0.8458 0.8474
Rct (Ω·cm2) 5.116×104 4
1.963×104 3.703×104 5.108×104 7.874×104
v
Rs(Ω·cm2) 15.21 12.37 15.81 13.31 14.81
re
Qf (μF·cm-2) 1.042×10-4 1.46×10-4 1.215×10-4 1.135×10-4 1.015×10-4
nf 0.8481 444445
0.8101 0.8327 0.8275 0.8325
WAAM-
Rf (Ω·cm2) 46.06 15.04 45.01 50.81 66.21
NAB
Qct (μF·cm-2) 8.165×10-5 1.445×10- 7.94×10-5 8.257×10-5 9.147×10-5
nct 0.8926 5
0.6904 0.8852 0.8803 0.8733
Rct (Ω·cm2) 1.263×105
er 5
4.055×104 5.775×104 8.128×105 1.338×105
Table 7. Equivalent circuit parameters of NAB alloys immersed in the solution with E.coli for different times.
pe
alloys 0d 1d 3d 9d 12d 15d
Rs (Ω·cm2) 5.028 5.737 4.932 5.867 5.210 5.331
Qf (μF·cm-2) 3.34×10-5 7.92×10-5 1.75×10-5 2.59×10-5 2.59×10-5 2.59×10-5
nf 0.5589 0.8575 0.8014 0.7801 0.6311 0.5706
CNAB Rf (Ω·cm2) 4.07×102 2.01×103 4.49×103 5.48×103 5.86×103 5.99×103
ot
Qct (μF·cm-2) 4.5×10-5 3.35×10-5 1.52×10-5 9.29×10-5 6.22×10-5 3.80×10-5

nct 0.5358 0.6424 0.7329 0.8358 0.8302 0.8351
Rct (Ω·cm2) 3.79×104 2.39×105 5.86×105 7.03×105 6.91×105 6.80×105
tn
Rs(Ω·cm2) 7.713 8.91 10.67 9.119 9.495 8.336

Qf (μF·cm-2) 6.138×10-5 6.77×10-5 7.57×10-5 8.58×10-5 8.07×10-5 7.57×10-5
nf 0.8127 0.8425 0.9085 0.9004 0.8767 0.8802
WAAM-
Rf (Ω·cm2) 5.25×103 6.69×103 9.33×103 9.43×103 9.29×103 9.15×103
NAB
rin
Qct (μF·cm-2) 6.951×10-5 7.82×10-5 8.32×10-5 8.76×10-5 8.17×10-5 8.44×10-5

nct 0.6415 0.6705 0.7541 0.8475 0.8602 0.8907
Rct (Ω·cm2) 1.18×104 2.13×105 4.37×105 8.81×106 8.42×105 8.02×105
ep
Table 8. Equivalent circuit parameters of NAB alloys immersed in the solution without E.coli for different times.
alloys 0d 1d 3d 9d 12d 15d
Rs (Ω·cm2) 6.083 7.044 6.252 7.152 6.99 7.295
Qf (μF·cm-2) 1.36×10-5 1.69×10-5 2.07×10-5 3.22×10-5 3.87×10-5 7.798×10-5
Pr
CNAB nf 0.7981 0.7256 0.6742 0.5686 0.7746 0.8402

Rf (Ω·cm2) 5.87×102 1.09×103 1.63×103 5.66×103 7.67×103 1.093×104
Qct (μF·cm-2) 4.24×10-5 8.84×10-5 1.02×10-4 3.65×10-4 3.95×10-5 4.15×10-5
45
32
nct 0.5157 0.6218 0.6681 0.9166 0.8741 0.8402
Rct (Ω·cm2) 5.49×104 1.61×105 2.65×105 4.19×105 3.82×105 3.66×105
ed
Rs(Ω·cm2) 4.873 5.37 5.136 5.679 4.933 5.142
Qf (μF·cm-2) 9.85×10-5 4.52×10-5 2.82×10-5 2.85×10-5 3.02×10-5 3.11×10-5
nf 0.8000 0.8206 0.8239 0.8531 0.8601 0.8597
WAAM
Rf (Ω·cm2) 4.63×102 2.51×103 5.66×103 5.91×103 6.21×103 6.44×103
iew
-NAB
Qct (μF·cm-2) 4.38×10-5 4.35×10-5 4.28×10-5 4.61×10-5 4.61×10-5 4.61×10-5
nct 0.621 0.7858 0.7978 0.7669 0.7915 0.8069
Rct (Ω·cm2) 9.37×104 2.88×105 7.45×105 1.32×106 1.21×106 1.02×106
v
re
er
pe
ot
tn
rin
ep
Pr
33

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Corrosion behavior and antibacterial properties of nickel-aluminum bronze/steel

composite structures fabricated through wire‐arc additive manufacturing

to the experimental requirements. In the WAAM process, NAB filler wires

value was taken.

electrochemical workstation (Gamry Instruments, Ref. 600, USA). A conventional

chloride compared to a standard hydrogen electrode) as a reference electrode. The

at this point is the β1' structure.

NAB is homogeneous as in the CNAB. This is in contrast to the directional growth

average size of 8.7 µm.

3.4 Corrosion product film

3.7 Microbial corrosion morphology

leading to a reduction in cathodic current. In addition, the dilution of biased impurities

peak of WAAM-NAB at 3300 nm was significantly higher than that of CNAB.

the significant findings are drawn as follows:

alloys in chloride solutions, Electrochim. Acta 120 (2014) 39-45.

screening and cell culture monitoring, Electroanalysis 17(23) (2005) 2101-2113.

[60] D. Naumann, Infrared Spectroscopy in Microbiology, Encyclopedia of Analytical Chemistry, Berlin,

(2020) 1143-1148. https://doi.org/10.2320/matertrans.MT-M2020008.

[67] Y. Hedberg, X. Wang, J. Hedberg, M. Lundin, E. Blomberg, I.O. Wallinder, Surface-protein

(a) (b) (c) (d)

(e) (f) (g)

Mass loss /g·m-2

0 20 40 60 80 100 120 140 160 180 200

Intensity (a.u.) Cu+

1000 800 600 400 200 0

Cu ions release profile /μg·L-1

C=O; P=O; P‒O‒C (P‒O‒P)

4000 3500 3000 2500 2000 1500 1000 500

(a) (b) (c)

Table 1. Arc additive parameters in the experiment.

CNAB Bal. 9.12 4.76 4.89 1.04 0.005 0.006 0.016

Table 4. Parameters for sample polarization curve fitting

CNAB -0.164 1.2×10-4

WAAM-NAB―immersion 0.023 2.68×10-9

Qf (μF·cm-2) 267.2 182.9 189.4 158.4 83.44 92.89

Rct (Ω·cm2) 544.32 2.20×103 9.13×103 1.44×104 2.57×104 5.45×104

WAAM- nf 0.7255 0.8208 - 0.8599 0.8707 0.9067

Qct (μF·cm-2) 4.5×10-5 3.35×10-5 1.52×10-5 9.29×10-5 6.22×10-5 3.80×10-5

Rs(Ω·cm2) 7.713 8.91 10.67 9.119 9.495 8.336

Qct (μF·cm-2) 6.951×10-5 7.82×10-5 8.32×10-5 8.76×10-5 8.17×10-5 8.44×10-5

CNAB nf 0.7981 0.7256 0.6742 0.5686 0.7746 0.8402

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