Influence of Copper Distribution in Thermally Sprayed Cu-Bearing

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Coatings on Corrosion and Microbial Activity

Hongshou. Huang 1, Surinder Singh 2, Albert Juhasz 1*, Anthony Roccisano 1, Andrew Siao

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Ming Ang 2*, Nikki Stanford 1*

1 Future Industries Institute (FII), University of South Australia, Mawson Lakes, SA, 5095,

Australia;

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2 Surface Engineering for Advanced Materials (SEAM), Swinburne University of

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Technology, Hawthorn, VIC, 3122, Australia

* Corresponding Author:
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E-mail address: Albert.Juhasz@unisa.edu.au (A. Juhasz); Nikki.Stanford@unisa.edu (N.

Stanford); aang@swin.edu.au (A.S.M. Ang)

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Abstract
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The phenomenon of internal microbiologically influenced corrosion (IMIC) in steel pipes for

natural gas transmission has long been recognized. Yet, durable, economical-effective, and
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environmental-friendly mitigation approaches are still lacking. To this issue, thermal-sprayed

copper (Cu)-bearing coatings were developed and their effectiveness against corrosion and
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microbial activity via tailored Cu distributions have been investigated. Two types of Cu-

containing coatings, stainless steel (SS)-Cu composite coatings and Monel 400 coatings with
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Cu in solid solution were deposited on steel substrates using high velocity oxy-fuel (HVOF)

and wire arc spray (WAS) techniques. The corrosion resistance, long-term Cu-ion dissolution

behavior, and antimicrobial properties of these coatings were systematically investigated.

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Irrespective of the employed thermal spray technique, SS-Cu composite coatings exhibited

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 preferential dissolution of Cu, observed in both potentiodynamic polarization and neutral salt

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spray tests. This effect was attributed to the micro-galvanic effect between Cu and the more

noble stainless-steel laminates, enhancing the corrosive rate of Cu laminates. Due to the high

release rate of Cu-ions, SS-Cu coatings exhibited significant antimicrobial properties towards

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three bacterial species including Escherichia coli, Pseudomonas aeruginosa, and Desulfovibrio

vulgaris. Antimicrobial durability, assessed through long-term salt spray tests, indicated that

Cu laminates located within the sub-layer of coatings allowed continuous Cu-ion release.

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However, localized corrosion propagation toward the substrate led to significantly expedited

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coating failure. In contrast, WAS Monel coatings, characterized by Cu in solid solution,

demonstrated uniform-dominated corrosion but with enhanced corrosion resistance. Although

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the antimicrobial properties of WAS Monel coatings were lower than SS-Cu composite

coatings, bacterial inhibition was observed due to the tailoring effect of coating defects,
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especially via oxidation. The WAS Monel coatings, with high corrosion resistance and a

moderate release rate of Cu, showed promise in providing long-term protection against IMIC

in pipeline environments.
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Keywords: thermal spray, coating, HVOF, wire arc, antimicrobial, corrosion

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1. Introduction
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Internal microbiologically influenced corrosion (IMIC) has been recognized as a significant

factor causing failures of natural gas pipelines [1-3]. However, to date, there still a lack of
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economical-effective and environmental-friendly mitigation strategies [4-6]. Although the

precise mechanism underlying MIC remains elusive, it is widely accepted that the formation
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of biofilms consisting of extracellular polymeric substances and embedded microorganisms-

on metal surfaces plays a crucial role. Biofilms acts as a protective shield to prolong embedded

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 microorganisms against the biocidal effects of antibacterial additives, allowing the MIC to

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manifest [7-10]. Thus, a key factor to address IMIC is the mitigation of bacterial attachment to

pipeline surfaces and the prevention of biofilm formation. Conceivably, this may be achieved

through the development of anti-IMIC coatings, however, the development of durable, cost-

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effective, and eco-friendly coatings remains a significant surface chemistry and fabrication

challenge [5, 11, 12].

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In contrast to organic coatings, metal-based coatings characterized with high bonding strength

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and wear resistance show some promise [11, 13, 14] although conventional corrosion-resistant

coatings, including aluminum and zinc, remain susceptible to MIC [15-17]. Given the intricate
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internal environment of pipelines, characterized by the presence of both corrosive abiotic

(carbon dioxide and hydrogen sulfide) and biotic factors (microorganisms), desirable anti-
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IMIC coatings are required to possess both antimicrobial attributes and elevated corrosion

resistance [1, 2, 13]. The antimicrobial efficacy of Cu-doped materials resulting from the

dissolution of Cu ions has been demonstrated [24-27] although its addition may adversely
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impact coating corrosion resistance [28-30]. Hence, microstructural design is necessary to

achieve the delicate trade-off between Cu ion dissolution and corrosion resistance.
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Microstructural strategies may involve the fabrication of Cu-containing composite coatings

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through the amalgamation of Cu with highly corrosion-resistant constituents. Tian et al. [31-

33] demonstrated the anti-fouling performance of plasma-sprayed Cu-X composite coatings,

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wherein X represents titanium, nickel, or stainless steel (SS). These laminated-structured

composite coatings exhibited controlled release of Cu ions facilitated by micro-galvanic

dissolution of Cu. However, the corrosion resistance and long-term dissolution of antimicrobial
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Cu ions of Cu-bearing composite coatings remains to be elucidated under conditions

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 representative of internal natural gas pipelines, where thin solution layer typically present [6,

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34, 35].

Considering the importance of efficiency and cost-effectiveness in the fabrication of anti-IMIC

coatings for gas pipes, it is imperative to explore more suitable thermal spray techniques and

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determine the optimal Cu additions in Cu-containing composite coatings. An alternative

microstructural strategy involves the retention of Cu in solid solution, which may facilitate

superior corrosion resistance in comparison to composite coatings characterized by preferential

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Cu dissolution [18-20]. A candidate for verification of this hypothesis is the Ni-Cu alloy such

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as Monel 400, however, an understanding of Cu ion release from solid solution, and its

antimicrobial effect are still required [21, 22].

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In this study, two types of Cu-containing coatings, SS-Cu composite coatings with varied Cu
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concentrations and Monel 400 coating with Cu in solid solution were prepared using high

velocity oxy-fuel (HVOF) and wire arc spray (WAS) spray techniques. The corrosion

resistance and antimicrobial properties of these coatings were systematically investigated to

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identify the optimal thermal spray technique and microstructural design strategy to develop

anti-IMIC coatings. HVOF yield high-quality coatings with low porosity (< 1%), low oxidation
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(< 5%), and high bond strength (> 80 MPa) [23], while WAS coatings exhibit higher porosity

and oxidation, but are cost-effective for large-scale production[23, 24].

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2. Materials preparation and experimental methods

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2.1 Materials and sample preparation

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Four HVOF coatings were prepared using commercial 316 SS (-45 +11 µm) and Cu powders

(-75 +31 µm) as feedstock materials. The coatings included pure 316 SS (referred to as HVOF

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 SS), 316 SS-10/20 wt.% Cu composite coating (referred to as HVOF 10Cu and HVOF 20Cu,

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respectively), and pure Cu (referred to as HVOF Cu). For the SS/Cu composite coatings, the

SS and Cu powders were mechanically blended in weight ratios of 90:10 and 80:20,

respectively, using a V-mixer for 20 minutes. HVOF coatings were deposited using a kerosene

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fueled HVOF system (K2, GTV Verschleißschutz GmbH, Germany) with parameters specified

in Table S1 (Supporting material).

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In addition, four WAS coatings were prepared using a twin-wire arc spray system (SmartArc

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PPG Gun, Oerlikon Metco, US) with wires of 1.6 mm diameter. The coatings included pure

316 SS (referred to as WAS SS), 316 SS-Cu composite coating (referred to as WAS SS/Cu),
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pure Cu (referred to as WAS Cu), and pure Monel 400 (referred to as WAS Monel). The

deposition process was assisted with a programmed robotic arm, and the detailed parameters
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for WAS coatings were displayed in Table S2 (Supporting material). Optimization of the

parameters for 316SS-Cu composite coatings was performed to achieve stable arc and a smooth

deposition process. To avoid potential galvanic cell formation between coatings and substrate,
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316 SS plates were used as the substrate. To minimize damage and contamination during the

post-cutting process on coatings, the substrates were machined into button shapes with a
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diameter of 10 mm and a thickness of 2.5 mm. Prior to deposition, the substrates were treated

with degreasing and grit blasting to remove oxidations formed on the substrates.
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2.2 Microstructural characterization

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The cross-sectional microstructures of both HVOF and WAS coatings were characterized using
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an optical microscope (OM, Olympus DSX-1000 digital microscope) and scanning electron

microscopy (SEM, Zeiss Merlin FE-SEM, 15 kV) equipped with energy-dispersive

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 spectroscopy (EDS). Porosity measurements were conducted by Image J software using OM

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images (n>10) at an appropriate magnification. For SEM and OM analysis, samples underwent

standard metallographic procedures and were finished with oxide polishing suspension (OP-

S). X-ray photoelectron spectroscopy (XPS; Kratos AXIS Supra) was performed to quantify

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the oxide concentration and identify the oxide types. To minimize the influence of the passive

film, argon ion sputtering was performed on the samples for 5 minutes before XPS

characterization, ensuring a stable and low concentration of carbon. High-resolution C 1s, O

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1s, Cu 2p, Fe 2p, Ni 2p, and Cr 2p spectra were recorded at a pass energy of 20 eV with 0.05

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eV resolution during XPS analysis. The XPS data were analysed using Casa XPS software after

calibration with the binding energy of aliphatic carbon (carbon bonded with carbon) at 284.8

eV.
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2.3 Corrosion test

2.3.1 Electrochemical corrosion test

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Electrochemical tests, including linear polarization resistance (LPR) and potentiodynamic

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polarization (PD), were conducted on a standard three-electrode cell using a potentiostat

(WaveNano potentiostats, Pine Research). The working electrode, reference electrode, and

counter electrode were represented by test samples, a saturated calomel electrode (SCE), and a
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platinum plate, respectively. A 3.5 % (w/v) sodium chloride (NaCl) solution with an initial pH

of approximately 6.8 served as the electrolyte. Prior to the LPR and PD tests, the samples were
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prepared by grinding and polishing to a 3-m finish, followed by ultrasonic cleaning in ethanol

for 10 minutes. Before conducting the LPR and PD tests, the electrochemical cells were run at
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open circuit potential (OCP) for 1 hour to establish a stable electric double layer. The LPR test

was performed within a range of -10 mV to 10 mV (vs. OCP) at a scanning rate of 0.167 mV/s.

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 PD curves were recorded in the potential range from -200 mV to 800 mV (vs. OCP) at a

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scanning rate of 0.5 mV/s. The corrosion current (Icorr) was determined using the Tafel

extrapolation method. To ensure reproducibility, three analyses were conducted for each

coating material [25].

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2.3.2 Neutral salt spray test

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Neutral salt spray testing (NSS, Ascott S120ip) was conducted on selected coatings, including

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HVOF SS, HVOF 20Cu, WAS SS-Cu, and WAS Monel. To enhance reproductivity and

comparability among different coatings, the coating samples for NSS tests were sealed with

epoxy resin on the bottom and side surfaces. Subsequently, the samples were ground and
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polished up to a 3 μm finish. The NSS tests were performed following the ASTM B117

standard for a duration of up to 500 hours (h) [26]. At specific time points (120 h, 300 h, and
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500 h), corroded samples were visually inspected, and their condition was recorded using a

camera after proper rinsing with water and drying. After the completion of the 500 h NSS test,
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OM and SEM were employed to characterize the corrosion morphology and dissolution

behaviour of Cu.
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2.5 Antimicrobial test

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Antimicrobial properties of thermal sprayed Cu-containing coatings were examined and

compared using a thin film adhering quantitative bacteriostasis test adapted from JIS Z 2801:
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2000[27]. Tests were conducted on three bacterial species: Escherichia coli (E. coli, ATCC

25922), Pseudomonas aeruginosa (P. aeruginosa, ATCC 39327), and Desulfovibrio vulgaris
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(D. vulgaris, ATCC 7757). Both E. coli and P. aeruginosa are facultative anaerobes while D.

vulgaris is an obligate anaerobe capable of reducing sulfate into sulfide through metabolism.

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 For antimicrobial tests, button-like samples of coated materials (10 mm in diameter) were

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prepared by grinding and polishing up to a smooth surface of 3 μm, followed by ultrasonic

cleaning in ethanol for 15 minutes. Prior to inoculation, flame sterilization was performed.

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Bacteria solutions were prepared by growing E. coli, P. aeruginosa, and D. vulgaris to

stationary phase in tryptic soy broth (TSB; E. coli) at 37 °C for 24 h, nutrient broth (NB; P.

aeruginosa) at 26 °C for 48 h, and modified Baar's medium (MBM; D. vulgaris) at 37 °C for

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48 h, respectively. Cell concentrations were then determined by optical density after

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centrifugation (4024 g for 5 minutes) and resuspension in phosphate buffer solution (PBS). To

provide test bacteria with a nominal quantity of nutrients for cell maintenance, culture media
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diluted to 1/500 strength with PBS was utilized as the test media, following JIS Z 2801: 2000

guidelines [27]. Inocula were prepared by diluting harvested cells with 1/500 strength culture
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media to achieve a cell concentration of approximately 105 cells/ml. The surface of test

materials was inoculated with 25 µl of the inoculum and incubated in a humid environment at

room temperature for up to 2 h. The inoculum volume (25 µl) was determined based on the
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surface area of the test samples, following JIS Z 2801: 2000 standards [27]. After varying

incubation times (0, 10, 30, and 120 minutes), viable cells were recovered with 2 ml PBS and
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enumerated using the agar plate method.

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The antimicrobial effect was determined using equation (1) [19, 27], with HVOF SS (WAS

SS) as the reference material. To ensure robust data, triplite assays were conducted for each
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material.

𝑁𝑟 ― 𝑁𝑡
𝐴𝑛𝑡𝑖𝑚𝑖𝑐𝑟𝑜𝑏𝑖𝑎𝑙 𝑒𝑓𝑓𝑒𝑐𝑡 = 𝑁𝑟 × 100 (%) (1)
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Where 𝑁𝑟 and 𝑁𝑡 are the mean number of colonies recovered from reference and test materials,

respectively.

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2.6 Dissolution of Cu ions

Repeated immersion tests were conducted to evaluate the release of Cu ions from various

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coatings. The polished coating samples were immersed in 1 ml of PBS solution using a well

plate. After immersing at room temperature for 24 h, the soaked solution was collected and

diluted with 2% nitric acid to a total volume of 10 ml. This process was repeated ten times for

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each coating. Before each subsequent test, the samples were thoroughly rinsed with de-ionized

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water and dried using nitrogen gas. The concentration of Cu ions in the solution was measured

using ICP-MS (Agilent 8800).

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3. Results
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3.1 Microstructural characterization

Fig. 1 displays the representative cross-sectional microstructures of HVOF 10 Cu coatings,

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characterized by typical lamellar structures with low porosity (1.5 ± 0.2 %). In the optical

micrographs shown in Fig. 1 b, porosity is mainly observed at the inter-splat regions the
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coatings. Additionally, micro-cracks also can be seen at the inter-splat boundary between SS

splats, likely resulting from oxidation (Fig. 1 c and d). In comparison, under the current HVOF
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spray parameters, Cu particles were fully melted, evident from the presence of Cu oxide

inclusions inside the Cu splat as shown in the EDS results (Fig. 1 d). The molten nature of the

Cu splats allowed them to fill in some porosity at the inter-splat boundaries (Fig. 1 c). This led
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to a reduction of porosity with an increase in Cu concentration in the HVOF coatings (Fig.

S1and S2, supporting material).

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Fig. 1 Cross-sectional microstructures of HVOF SS-10Cu coating: (a-b) optical micrograph

with measured coating thickness and porosity; (b) inset from (a) marked by white square; (c-d)
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SEM-BSE microstructures. The SEM-EDS in (d) revealed the distribution of Cu splats and
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their oxidation.

Figure 2 shows the microstructure of the WAS SS-Cu coating. A dense SS-Cu composite
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coating can be observed, and the porosity was found to be relatively low for WAS coatings,

2.4 ± 0.3 %. SEM-EDS results demonstrated that the ratio of SS and Cu splats/layers within
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the WAS SS-Cu coating is approximately 1:1 (by area). The WAS SS-Cu samples were more

lamellar in structure compared to the HVOF due to the WAS splats of SS being fully molten.
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However, the higher particle temperature of SS also resulted in increased oxidation, evidenced

by the observation that WAS SS demonstrating the highest oxidation, 9.9 wt.% (Table 1; Fig.

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 S3, supporting material). High-resolution XPS spectra verified the predominant presence of Fe

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and Cr oxides (e.g., FeO, Fe2O3, Cr2O3, and Cr(OH)3), as displayed in Fig. 3 and Fig. S4

(Supporting material). When compared to HVOF SS and 10Cu coatings (28.2 - 32.7 %), there

was a significant increase in the percentage of Cr hydroxide/oxide (61.8 - 72.4%) measured in

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WAS SS and SS-Cu coatings, indicating extensive Cr oxidation during WAS sprays (Fig. 3

and Fig. S4 a). This observation aligns with the material characterizations using EDS mappings,

as shown in Fig. 2 and Fig. S2 (Supporting material). Furthermore, though EDS mapping

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analysis have confirmed the presence of Cu oxides in both monotonic Cu (Fig. S5, supporting

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material) and Cu-bearing composite coatings (Fig. 1d and 2 d), no Cu oxide peaks were

observed in the high-resolution Cu 2p XPS spectra, as displayed in Fig. 3 d and Fig. S4 d

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(Supporting material). In light of the particle temperature, it is reasonable to infer that Cu oxide

primarily exists as Cu2O, which cannot be distinguished under high-resolution Cu 2p XPS

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analysis [28].

The microstructure of the WAS Monel coating is shown in Fig. 4. This coating shows a higher
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percentage of porosity (5.8 ± 0.5 %) and inter-lamellar cracks compared with WAS SS and

WAS SS-Cu coatings. The oxidation of WAS Monel coating is relatively low, around 3.0 wt.%
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(see Table 1). EDS mapping analysis reveals that these oxides are primarily found as oxide

stringers at the boundaries of splats and as oxide inclusions within splats (Fig. 4 c). Furthermore,
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evidence of Fe oxidation in the inter-splat boundaries is also observed.

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Fig. 2 Cross-sectional microstructures of WAS SS-Cu composite coating: (a) optical

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micrograph with measured coating thickness and porosity; (b-c) SEM-BSE microstructures

illustrating the presence of oxidation and porosity; (d) SEM-EDS microstructures identifying
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the phases and oxidation distribution.

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Table 1 Oxygen content quantified by XPS on cross-section of coatings.

HVOF HVOF HVOF HVOF WAS WAS WAS WAS

Coatings
SS 10Cu 20Cu Cu SS SS-Cu Cu Monel
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Oxygen,
5.1 4.7 4.5 1.2 9.9 5.5 2.5 3.0
wt. %
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Fig. 3 High-resolution XPS spectra: (a-b) Cr and Fe of representative HVOF 10Cu and WAS
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SS-Cu; (c-d) Ni and Cu of representative WAS SS-Cu and WAS Monel, respectively.
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Fig. 4 Cross-sectional microstructures of WAS Monel coating: (a) optical micrograph with

measured coating thickness and porosity; (b-c) SEM-BSE microstructures illustrating the
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presence of oxidation and porosity; SEM-EDS in (c) illustrates oxidation distribution.
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3.2 Corrosion test

3.2.1 Electrochemical corrosion test

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Fig. 5 illustrates the representative potentiodynamic polarization curves of HVOF and WAS

coatings. HVOF SS samples exhibited a typical passive-transpassive curve but with a decreased
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pitting potential due to the presence of porosity (See Fig. S6 and Fig. S7 a, supporting material).

Upon the addition of Cu, the curves of HVOF 10/20Cu coatings indicated a decrease in
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corrosion potential and increase in corrosion current, signifying higher corrosion susceptibility

(Fig. 5 a). In comparison, WAS SS exhibited an even lower corrosion potential than pure Cu
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coatings, and the passive behavior was less distinct compared to HVOF SS (Fig. 5 b). For both

thermal spray techniques (HVOF and WAS), SS-Cu composite coatings displayed similar

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 polarization behavior to their corresponding pure Cu coatings. In the case of WAS Monel

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coatings with Cu in solid solution, polarization curves indicated an enhanced corrosion

resistance.

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Detailed electrochemical parameters determined from polarization curves and LPR tests are

presented in Table 2. The variation of the corrosion current (Icorr) was consistent with the value

of LPR. Overall, both thermal spray techniques exhibited SS-Cu composite coatings with

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corrosion currents (ranging from 1.02 to 4.76 µA/cm2) between those of SS coatings

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(HVOF/WAS SS; 0.09 - 0.21 µA/cm2) and pure Cu coatings (HVOF/WAS Cu; 7.26 - 9.74

µA/cm2). As expected, WAS Monel coatings showed a significantly decreased corrosion

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current (0.79 ± 0.16 µA/cm2) compared to HVOF/WAS SS-Cu composite coatings.
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Fig. 5 Polarization curves of (a) four HVOF coatings and (b) four WAS coatings. HVOF/WAS
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SS and HVOF/WAS Cu coatings are used as the reference materials.

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 Table 2 Parameters determined from linear polarization resistance and poteniodynamic

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polarization tests.

HVOF HVOF HVOF HVOF WAS WAS WAS WAS

SS 10Cu 20Cu Cu SS SS-Cu Cu Monel

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412400 13495 10300 4405 120795 7555 1971 76435
LPR, Ω
± 53174 ± 997 ± 707 ± 1019 ± 40453 ± 1709 ± 490 ± 5635
Ecorr, -201.0 -234.2 -243.5 -259.2 -380.1 -260.1 -285.0 -172.8
mVSCE ± 52.3 ± 5.9 ± 9.2 ± 8.3 ± 26.6 ± 4.3 ± 11.9 ± 26.2

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Icorr , 0.09 1.02 1.99 7.26 0.21 4.76 9.74 0.79
µA/cm2 ± 0.01 ± 0.06 ± 0.12 ± 0.92 ± 0.06 ± 1.10 ± 1.73 ± 0.16

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Note: Ecorr and Icorr are corrosion potential and current, respectively.

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Fig. 6 displays the microstructures of representative Cu-containing coatings after PD tests. It

is evident that Cu was preferentially corroded in both HVOF 10/20 Cu and WAS SS/Cu
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composite coatings, as displayed in Fig. 6 a-d and Fig S7 a (Supporting material). Additionally,

the corrosion of stainless-steel splats (mainly oxidation area) was observed in the WAS SS-Cu

composite coating (Fig. 6 c-d). A similar phenomenon was also observed in the WAS SS
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coating (Fig. S7 c-d, supporting material), which might be the reason for the significant shift

towards the negative direction observed in the polarization curves. In comparison, WAS Monel
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exhibited predominantly uniform corrosion, although localized corrosion could be observed at

the sites of porosity and splat boundary (Fig. 6 e-f). The observation of Fe oxides that primarily
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located at the inter-splat boundaries also confirms that the general corrosion of WAS Monel

occurred in a layered process (Fig. 6 f and Fig. S8 b, supporting material).

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Fig. 6 Topographies of representative (a-b) HVOF 10Cu, (c-d) WAS SS-Cu and (e-f) WAS
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Monel after potentiodynamic polarization tests. (a, c, e) SEM-BSE microstructures, and (b, d,

f) SEM-EDS combined elemental maps.

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3.2.2 Salt spray test

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Fig. 7a displays visual representations of selected samples subjected to salt spray tests for up

to 500 h. It is evident that clear pits can be observed on HVOF SS after 120 h, and with
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increasing testing time, more corrosion products (rust) appeared on the sample surface,

indicating the propagation of pits. WAS SS-Cu exhibited significant corrosion due to higher

Cu addition, and the sample surface was nearly covered by corrosion products after 500 h of
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testing. Microstructural characterization confirmed the preferential corrosion of Cu in both

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 HVOF 20Cu and WAS SS-Cu composite coatings (Fig. 7 b and d). Additionally, corrosion of

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stainless-steel splats (mainly oxidation area) was observed within the WAS SS-Cu coating (Fig.

7 d and e), consistent with the observations from the PD tests (Fig. 6 c-d). In comparison, WAS

Monel demonstrated enhanced corrosion resistance to salt spray tests, with only a colour

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change seen in the local area with corresponding pitting type corrosion found after 500 h of

testing. Microstructural characterization revealed that although general corrosion was the

dominant type, large-sized pits that originated from the porosity could still be observed in the

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Monel, Fig. 7 c.

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Fig. 7 (a) is the visual representations after neutral salt spray tests at the time points of 0 h, 120
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h and 500 h; (b), (c) and (d-e) are SEM-BSE microstructures of HVOF 20Cu, WAS Monel and

WAS SS-Cu after 500 h testing, respectively.

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3.3 Antimicrobial test

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In Fig. 8 for WAS coatings and Fig. S9 in the supporting material for HVOF coatings,

demonstrate visual representations of differences in viable cells after exposure to different

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 surfaces for up to 30 min. It is evident that after only 10 min of exposure to HVOF 10Cu, the

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number of viable cells decreased by more than 90 % compared to HVOF SS, for all three types

of bacteria (Fig. S9, supporting material). When the Cu concentration added to SS-Cu

composite coatings exceeded 20 wt.%, the antimicrobial effect reached almost 100 %,

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comparable to pure Cu coatings. In contrast, WAS Monel samples initially showed a lower

antimicrobial effect than SS-Cu composite coatings within a short incubation period (10

minutes). However, the antimicrobial effect reached nearly 100 % when the incubation time

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was extended to 30 min.

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Fig. 8 Photo of colonies (viable cells) after exposure to different WAS coatings for different
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time in thin film adhering quantitative bacteriostasis tests. Three types of bacteria, Escherichia

coli (E. coli), Pseudomonas aeruginosa (P. aeruginosa), and Desulfovibrio vulgaris (D.
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vulgaris) were utilized.

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 3.4 Repeating immersion tests

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The repeated immersion tests, as shown in Fig. 9 a, demonstrated that the release rate of Cu

ions reached a nearly constant level after the fifth repetition for all four Cu-containing coatings.

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Among them, WAS SS-Cu exhibited the highest release rate of 17.68 ± 2.47 µg·cm-2·d-1 (the

average of the last five repetitions), while WAS Monel showed the least value of 0.65 ± 0.14

µg·cm-2·d-1. The variation in the release rate of Cu ions observed in these repeating experiments

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are consistent with the corrosion current (Table 2). Utilizing the method described by Tian et

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al. [20, 29, 30], the antimicrobial duration of Cu-containing coatings was estimated, as shown

in Fig. 9 b. It is evident that, based on the release rate estimated from the repeating tests, the

antimicrobial effectiveness of Cu-containing coatings could last for more than 8 years when up
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to 20 wt.% Cu was added.
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Fig. 9 (a) Released Cu ions in repeating immersion tests; (b) The predicted duration time based
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on the results of repeating experiments.

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 4. Discussion

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4.1 The dependence of corrosion behaviour on microstructures

Fig. 10 a shows the variation of corrosion current as a function of the Cu concentration in the

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coatings. Irrespective of the thermal spray techniques utilized, the corrosion current increased

almost linearly with the Cu concentration in SS-Cu composite coatings. This suggests that the

enhanced corrosion resistance of SS-Cu composite coatings was attributed to the decrease of

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exposed anodic Cu splat area in SS-Cu compared to monotonic Cu coatings. Similar

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phenomena have also been reported in Ti-Cu composite coatings with varying Cu

concentrations [30]. Based on the microstructural characterization that Cu was the

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preferentially corroded phase in SS-Cu composite coatings (Fig. 6 a-d and Fig. S7 b, supporting

material), the true corrosion current density of Cu splats was determined by normalising for
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the Cu volume fraction (assuming uniform Cu distribution), as shown in Fig. 10 b. It is evident

that Cu splats within HVOF 10/20 Cu coatings exhibited a higher corrosion rate, which might

be attributed to the development of micro-galvanic cells [20, 29]. The volume loss and the pit
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sizes developed during the corrosion tests were measured based on re-constructed 3D

topographies as shown in Fig. 10 c-d and Fig. S10 (Supporting material). The almost linear
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relationship between corrosion current density and volume loss further supports the hypothesis

that copper is preferentially corroded in the SS-Cu composite coatings. The statistical results
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of the width and depth of pits reflect the sizes of Cu splats, with WAS SS-Cu exhibiting the

largest width of Cu splats but a similar thickness in comparison with HVOF 10/20 Cu coatings
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(Fig. 10d).
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This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4613064
 ed
v iew
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er
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Fig. 10 (a) The relationship between corrosion current and Cu concentrations within coatings;

(b) The variation of corrosion current of Cu splats with Cu concentrations in SS-Cu composite

coatings; The values were determined by normalising for the Cu volume fraction; (c) The
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relationship between corrosion current with the volume loss measured on polarization tested

samples; (d) The distributions of pitting depth and width measured on polarization tested
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samples.
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In the HVOF specimens, the preferential dissolution of Cu by micro-galvanic corrosion cells

is due to the difference in corrosion potential between stainless-steel and Cu splats (HVOF SS,

-201.0 ± 52.3 mV SCE, HVOF Cu, -259.2 ± 8.3 mV SCE) [20, 31]. Preferential Cu corrosion
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in WAS SS-Cu was also observed, however, in that case the stainless-steel splats exhibited a

lower corrosion potential (Table 2). The low corrosion potential of stainless-steel splats (in
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both WAS coatings) might be related to the relatively high oxygen content in the WAS SS

specimens (Table 1). Significant Cr and Fe oxidation were observed, see Fig. S4 b-c

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 (Supporting material). The formation of Cr oxides could result in the formation of Cr-depleted

ed
areas that are susceptible to preferential corrosion (Fig. S7 c-d, supporting material), which is

evidenced by the decreased ratio of Fe/Cr in WAS SS, from 3.33 to 1.78 (EDS) after PD tests.

This phenomenon is well documented in the heat affected zone of welded austenitic stainless

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steels [32, 33]. Similar corrosion behaviour has also been reported on of WAS SS coatings by

Zeng et al. [34]. Therefore, in WAS SS-Cu coatings, the corrosion potential can be ranked by

passivity as stainless-steel splats > Cu splats > Cr-depleted area within stainless-steel splats.

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This sequence results on the surface features shown in Fig. 6c-d. In contrast, WAS Monel

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exhibited a significantly decreased corrosion rate, which does not follow the linear relationship

between Cu concentration and corrosion current observed in SS-Cu composite coatings (Fig.
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10 a). This is mainly because the copper is retained in solid solution in the Monel coating and

does not create the micro-galvanic cells as observed in the WAS and HVOF coatings in which
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the copper splats are situated in discrete pockets.
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4.2 The dependence of antimicrobial property and durability on Cu distributions

When considering anti-IMIC coatings for pipeline systems, the antimicrobial durability
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becomes a critical factor to consider. The predicted lifespan using repeating immersion tests

suggests that 20 wt.% Cu addition is sufficient to achieve a desirable duration in theory (Fig. 9
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b). However, the key question is whether Cu-containing coatings can continuously release Cu

ions in the long term to maintain their antimicrobial durability. Previous studies by Tian et al.
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[29]on thermal-sprayed Ti-Cu anti-fouling coatings suggested that the formation of micro-

channels resulting from preferential dissolution enables corrosive media to reach the Cu

laminates in the sub-layer, contributing to a continuous release of Cu ions at a controlled rate.

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Fig. 11 illustrates the representative cross-section microstructures after polarization and salt

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 spray tests. It is evident that in both scenarios, Cu laminates located in the sub-layers can be

ed
accessed by the electrolyte via channels left behind by the dissolved Cu laminates, as indicated

by the corrosion path (Fig. 11 a-d). In WAS SS-Cu coatings, the preferential corrosion of

stainless-steel oxidation (Cr-depleted area) at the splat boundary also facilitates this process.

iew
With the dissolution of Cu splats in the sub-layer of coatings, the surface SS splats peel off,

contributing to a self-polishing effect. However, a significant concern for SS-Cu composite

coatings is the localized dissolution of Cu. As shown in Fig. 11 a-d, corrosion tends to

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propagate to the substrate in localized areas instead of uniformly dissolving layer by layer (Fig.

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11). This could significantly shorten the service time of the coatings.

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ot
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Fig. 11 SEM-BSE microstructures on cross section area of (a-b) HVOF 20Cu, (c-d) WAS SS-
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Cu and (e-f) WAS Monel after poteniodynamic polarization tests (a, c, e) and salt spray tests

for 500 h (b, d, f).

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4613064
 In comparison, WAS Monel, with its high corrosion resistance and a moderate release rate of

ed
Cu ions, might be more promising in yielding durable antimicrobial properties. The feature of

uniform corrosion layer by layer enables coatings to release Cu ions at a relatively constant

rate (e.g., 0.5 µg · cm-2 · d-1) throughout the service time. Additionally, the layer-by-layer

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thinning process of WAS Monel coating also provides an opportunity for physical contact

between the toxic surface and invaded microorganisms, which has been shown to play an

important role in antimicrobial properties [35]. However, during the salt spray test, the

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localized corrosion initiated from the porosity remains a concern from the perspective of long-

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term application (Fig. 7 c and Fig. 11 f).

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4.3 Thermal spray techniques: HVOF versus WAS
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The present work demonstrates the capabilities of both HVOF and WAS in preparing Cu-

containing coatings. HVOF allows for the creation of high-quality SS-Cu composite coatings

with varying Cu concentrations, catering to different application environments. However, the

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relatively large stainless-steel splat sizes in HVOF 10/20Cu coatings showed accelerate

corrosion that could propagated to the bottom of substrate, thereby reducing the coatings'
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service time (Fig. 9 b and Fig. 11 a-b). In comparison, WAS offers significant advantages in

coating large components due to its high efficiency and cost-effectiveness. From a
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microstructural standpoint, WAS coatings feature finer laminates, which slow down corrosion

propagation in depth (Fig. 11 c-d).

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 5. Conclusion

ed
In this study, some novel microstructural design strategies for preparing Cu-bearing anti-IMIC

coatings with high corrosion resistance and durable antimicrobial properties using thermal

iew
techniques of HVOF and WAS have been presented. The corrosion resistance of the coatings

was investigated using both electrochemical tests in a 3.5 wt.% salt solution and neutral salt

spray tests. Antimicrobial tests were conducted against three types of bacteria using the thin

v
film adhering quantitative bacteriostasis method. Results from all tests were benchmarked

re
against standard stainless steel and pure copper coatings. The main conclusions drawn from

this research are as follows:

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1. Two types of Cu-containing coatings, namely SS-Cu composite coatings with varied

Cu concentrations and Monel 400 coatings with Cu in solid solution, were successfully
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prepared using HVOF and WAS techniques.

2. In SS-Cu composite coatings, regardless of the thermal spray techniques used, Cu

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laminates exhibited preferential corrosion due to the formation of micro-galvanic

corrosion cells between the Cu and stainless-steel splats. The corrosion current
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determined from polarization tests showed an almost linear increase with the Cu

concentration in the SS-Cu composite coatings, indicating that the enhanced corrosion
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resistance of these coatings was attributed to the decreased anode area compared to pure

Cu coatings.
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3. SS-Cu coatings demonstrated significantly enhanced antimicrobial properties,

comparable to those of pure Cu coatings, particularly when the Cu concentration added

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exceeded 20 wt.%. Long-term salt spray tests revealed that Cu laminates located in the

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4613064
 sub-layer within SS-Cu composite coatings could be accessed by the electrolyte

ed
through channels left behind by preferentially dissolved Cu laminates, providing a

continuous release of Cu ions. However, accelerated localized dissolution of Cu toward

substrate might lead to a shortened service time.

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4. WAS Monel coatings with Cu in solid solution exhibited uniform corrosion with

significantly enhanced corrosion resistance. WAS Monel coatings were also shown to

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have antimicrobial properties.

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5. Comparatively, the WAS technique demonstrated more advantages in fabricating Cu-
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containing anti-IMIC coatings than HVOF, primarily due to its ability to produce more

typical lamellar microstructures in an efficient and cost-effective manner.

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Overall, the findings from this research offer valuable insights into the development of

effective anti-IMIC coatings with superior corrosion resistance and antimicrobial properties,

providing potential solutions for safeguarding pipelines against microbiologically influenced

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corrosion.
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Supporting Material
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Materials content (Word): Spraying conditions for the different HOVF coatings and their

reference name (Table S1); Spraying conditions for the different WAS coatings and their
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reference name (Table S2); Optical microstructures on cross section of HVOF SS, HVOF SS-

20Cu, HVOF Cu, WAS SS and WAS Cu coatings (Fig. S1); SEM-EDS mappings on cross
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section of HVOF SS and WAS SS (Fig. S2); XPS survey spectra to quantify the oxidation of

examined coatings (Fig. S3); High-resolution XPS spectra of Cr, Fe, Ni and Cu (Fig. S4); SEM-

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4613064
 EDS mappings on cross section of HOVF Cu and WAS Cu (Fig. S5); Topographies of coatings

ed
before electrochemical tests and neutral salt spray tests (Fig. S6); Top-surface microstructures

of HVOF SS, HVOF 20Cu, and WAS SS after polarization tests (Fig. S7); SEM-EDS mapping

of WAS SS-Cu and WAS Monel after electrochemical corrosion tests (Fig. S8); Photo of

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colonies (viable cells) after exposure to different HVOF coatings for 10 min in thin film

adhering quantitative bacteriostasis tests (Fig. S9); 3-D topographies of representative samples

after polarization tests (Fig. S10).

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Acknowledgement
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This research was funded by Surface Engineering for Advanced Materials, SEAM under the

ARC Industrial Transformation Training Centre (ITTC) scheme via Award IC180100005. All
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authors acknowledge the support in instruments and scientific and technical assistance from

Microscopy Australia at the Future Industries Institute, University of South Australia.

Hongshou Huang acknowledges the financial support from China Scholarship Council for his
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PhD Scholarship and the Future Industries Institute for a top up scholarship.
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