coatings

Article
Epoxy Coating Modification with Metal Nanoparticles to
Improve the Anticorrosion, Migration, and Antibacterial Properties
Marina Samardžija 1, *, Ivan Stojanović 2 , Marija Vuković Domanovac 3 and Vesna Alar 2

1 Department of Chemistry, Faculty of Mining-Geology-Petroleum Engineering, University of Zagreb,

10110 Zagreb, Croatia
2 Department of Welded Structures, Faculty of Mechanical Engineering and Naval Architecture,
University of Zagreb, 10000 Zagreb, Croatia; [email protected] (I.S.); [email protected] (V.A.)
3 Department of Industrial Ecology, Faculty of Chemical Engineering and Technology, University of Zagreb,
10000 Zagreb, Croatia; [email protected]
* Correspondence: [email protected]; Tel.: +385-1-5535-912

Abstract: Nanoparticles are capable of making more durable and stronger materials with better
chemical resistance. They are used for a wide range of applications. Likewise, the potential of metal
nanoparticles as antimicrobial agents has been widely studied. In this work, we investigate various
nanoparticles (Al, Ni, Ag) incorporated into epoxy coating. The anticorrosion and antibacterial
properties of the unmodified and modified coatings were evaluated. According to the SEM and EDS
analyses, the coating did not contain agglomerates, which confirms the quality of the dispersion of
inorganic nanoparticles in the coating. After 24 h and 10days immersions in a 3.5 wt.% NaCl solution,
the corrosion behaviour for all nanocomposite was studied by means of EIS investigations. The study
included the evaluation of the inhibition zone of the nanoparticles and the antimicrobial properties of
the nanocomposite. It was found that the nanoparticles of Al and Ag provide excellent antibacterial
properties. The epoxy nanocomposite with Al NP showed the migration of ions in the range from
0.75 to 1 mg/L in a wastewater solution for 30 days, indicating a potential for antimicrobe activity.
The 1% Al NP epoxy nanocomposite showed good anticorrosion and antibacterial properties and
demonstrated great potential for applications in pipelines.
Citation: Samardžija, M.; Stojanović,
I.; Vuković Domanovac, M.; Alar, V.
Keywords: corrosion protection; nanoparticles; epoxy coating; antibacterial activity
Epoxy Coating Modification with
Metal Nanoparticles to Improve the
Anticorrosion, Migration, and
Antibacterial Properties. Coatings 1. Introduction
2023, 13, 1201. https://doi.org/ The 21st century is marked by the study of nanotechnology and the production of
10.3390/coatings13071201 nanostructured materials. Nanoparticles (NPs) are a wide class of materials that includes
Academic Editor: Jinyang Xu particulate substances with sizes between 1 and 100 nm [1].The use of nanoparticles in dif-
ferent fields such as molecular biology, physics, organic and inorganic chemistry, medicine,
Received: 9 June 2023 and material science is of growing interest in future applications [2]. In recent years, sci-
Revised: 1 July 2023
entists and researchers have been motivated to develop coatings with new features, such
Accepted: 3 July 2023
as the possibility of the migration of substances due to the improvement of anticorrosive
Published: 4 July 2023
and antibacterial properties. As a result, nanoparticles began to be incorporated into the
polymer material. The material obtained was defined as a nanocomposite, which implies a
composition of at least two immiscible phases, and one of them in the nanometer scale [3].
Copyright: © 2023 by the authors.
The ability of nanocomposite material to release nanoparticles is considered very harmful
Licensee MDPI, Basel, Switzerland. if applied in the food packaging industry [4], but its application on the surface of drainage
This article is an open access article pipes is a new idea for protection against microorganisms. Cast iron pipes have been widely
distributed under the terms and used in water distribution systems formore than 150 years due to their high mechanical
conditions of the Creative Commons strength and cost effectiveness [5]. With the development of urbanization and industrial-
Attribution (CC BY) license (https:// ization, the amount of wastewater produced and discharged increased significantly year
creativecommons.org/licenses/by/ by year. Consequently, problems such as corrosion, damage, a reduction in the water
4.0/). transport capacity, and an increase in the habitat of pathogenic and opportunistic bacteria

Coatings 2023, 13, 1201. https://doi.org/10.3390/coatings13071201 https://www.mdpi.com/journal/coatings

Coatings 2023, 13, 1201 2 of 15

are becoming serious [6,7]. To achieve corrosion protection, organic coatings and corrosion
inhibitors are widely used, but the limitations of these materials, such as high cost, heavy
contamination, and operational difficulties, has not been completely overcome [8]. Poly-
mer nanocomposite coatings are a new generation of coatings which have recently been
used for the protection of drainage pipes from corrosion due to their superior mechanical
strength, stiffness, improved barrier properties against oxygen and moisture, increased heat,
wear, and use in the simple repair of damaged structures [9,10]. Similarly, a new class of
“nanometallo-antibiotics” consisting of numerous metal NPs has appeared, whichinvolves
investigating their antimicrobial properties [11]. It is clear that some metal nanoparticles are
effective antimicrobial agents against several pathogenic microorganisms, and their action
depends on size, shape, and surface charge [12,13]. Mejía and co-authors [14] developed a
new thin antibacterial coating with long-term effectiveness based on silver release that has
an antibacterial effect. According to the research of Tahir and co-authors, the incorporation
of silver nanoparticles (Ag NP) into the epoxy resin reduces the occurrence of bubbling
and delamination of the coating and improves the durability of the coating [15]. Epoxy
antimicrobial coatings are of great interest for the protection of surfaces, since the survival
of microorganisms on the surface environment can be detrimental to materials [16]. Micro-
bially induced corrosion (MIC) can be defined as the process by which biological agents
(live organisms) cause changes in the material properties, leading to the structural lowering
in quality or value [17]. Considering the proven antibacterial efficacy of metal and metal
oxide nanoparticles in an organic coating with clear known mechanisms of action against
bacteria for silver, silver oxide, titanium dioxide, iron oxide, and zinc oxide, potential
materials with the same effect as nickel and aluminum remain poorly researched [16,18,19].
Nickel is a metal relatively resistant to atmospheric corrosion, but it also has huge
potential for the development of antibacterial properties [20,21]. The bactericidal action of
nickel nanoparticles (Ni NP) has shown a strong effect with particle sizes in the range of
10–100 nm [21]. Aluminum nanoparticles (Al NP) also have high corrosion resistance, but
due to the ability to create a passive oxidation layer their antibacterial potential increases [4].
It can be concluded that certain metal powder nanoparticles have a cytotoxic and genotoxic
effect on bacteria, and their intercalation in the epoxy coating creates the potential for
antibacterial protection. In this study, the effect of the Al NP, Ni NP, and Ag NP in
an epoxy coating on the anticorrosion, migration, and the antibacterial property was
investigated. In our current work, the composition and distribution of particles for these
coatings were characterized using SEM and EDS investigations. The EIS technique was
used to characterize the anticorrosion properties of the modified epoxy coating and epoxy
nanocomposite. The migration of nanoparticles from the epoxy coating into the wastewater
was observed for 30 d, and the possibility of antibacterial action of nanocomposite was
tested according to ISO 22196.

2. Materials and Methods

2.1. Materials
The metallic substrate used during this study was gray cast iron with chemical compo-
sition 2.5 C, 1.5 Si, 1.05 Mn, 0.5 P, 0.07 S, and Fe in balance (wt.%). The epoxy coatings that
we used in this work were based on diglycidyl ether of bisphenol A, and the polyamine
hardener was obtained from Hempel (Umag, Croatia). Aluminum, nickel, and silver
nanoparticles with an average particle size of about 100 nm were provided by Guangzhou
Hongwu Material Technology Co., Ltd., Guangzhou, China. The morphology of the powder
nanoparticles was observed from the SEM micrographs, EDS, and XRF (Figure 1).
According to Figure 1a–c, the Al and Ni NPs showed spherical particles and the
Ag NPs within irregular shapes. All nanoparticles showed different sizes. The small
nanoparticles had a very large surface area to volume ratio, which gave them huge energy
and high reactivity. The agglomerates with average particle sizes from 223.4 to 620.7 nm
were observed in Figure 1a,b. The XRF analysis of the elemental composition of the
nanoparticle powder showed a high proportion of Al, Ag, and Ni nanoparticles (Table 1).
Coatings 2023, 13, x FOR PEER REVIEW 3 of 15

Coatings 2023, 13, 1201 ogy of the powder nanoparticles was observed from the SEM micrographs,
3 ofEDS,
15 and
XRF (Figure 1).

Figure 1. SEM
Figure image
1. SEM and
image andEDS
EDSanalysis ofthe
analysis of the(a,d)
(a,d)
Al,Al, (b,e)
(b,e) Ni, and
Ni, and (c,f)
(c,f) Ag Ag nanoparticles.
nanoparticles.

According
Table to analysis
1. The XRF Figure1a–c, the Al and
of the elemental Ni NPs
composition showed
of the spherical
nanoparticle particles
and the Ag
powder.
NPs within irregular shapes. All nanoparticles showed different sizes. The small nano-
Al NP Ni NP Ag NP
particles had a very large surface area to volume ratio, which gave them huge energy and
Elements wt.% +/− Elements wt.% +/− Elements wt.% +/−
high reactivity. The agglomerates with average particle sizes from 223.4 to 620.7 nm were
Al 98.85 0.24 Ni 99.21 0.25 Ag 98.94 0.32
Cr 0.08
observed
0.01
in Figure1a,b.
Cu
The 0.28
XRF analysis of the elemental
0.05 Cr
composition
0.41
of 0.10
the nanoparti-
Fe 0.03 cle powder
0.43 showedSi a high proportion
0.26 of0.05
Al, Ag, andCoNi nanoparticles
0.33 (Table
0.041).
Residue 1.04 0.01 Co 0.11 0.02 Si 0.33 0.02
Total 100 Table 1.- The XRFResidue
analysis of the0.14 0.01
elemental composition Total
of 100 powder.-
the nanoparticle
Total 100
Al NP Ni NP Ag NP
Elements wt.% 2.2. Preparation
+/− of the Epoxy Coating/Nanocomposite
Elements wt.% +/− Elements wt.% +/−
Al 98.85 0.24 The epoxyNi coating was formulated
99.21 by taking
0.25epoxy paint Agand polyamine hardener in0.32
98.94
the mass ratio of 4:1. Four formulations of prepared coatings are shown in Table 2.
Cr 0.08 0.01 Cu 0.28 0.05 Cr 0.41 0.10
At ambient temperature, various nanoparticles were incorporated into the epoxy
Fe 0.03 0.43 Si
coating under sonicate 0.26
agitation for 20 min with0.05
a delay in theCo
process due to0.33
the cooling of0.04
Residue 1.04 0.01 Co Polyamine0.11
the nanocomposite. 0.02 to the nanocomposite
hardener was added Si and 0.33
mechanically0.02
Total 100 stirred
- using a glass
Residue stirrer. 0.14 0.01 Total 100 -
Before applying
Total the coating,
100the panels of 9.5 cm × 0.9 cm × 15 cm gray cast iron were
abrasively blasted and cleaned with ethanol (70 wt.%). The nanocomposite mixture was
applied using a film applicator with a wet film thickness of 150 µm. The samples were kept
2.2. Preparation of the Epoxy
at room temperature for 24 Coating/Nanocomposite
h, and then another layer of nanocomposites was applied in the
opposite direction. The samples
The epoxy coating was formulated were left at
byroom temperature
taking (25 ◦ C)
epoxy paint for 7polyamine
and days. hardener
in the mass ratio of 4:1. Four formulations of prepared coatings are shown in Table 2.
Coatings 2023, 13, 1201 4 of 15

Table 2. The chemical composition of the tested samples.

Sample Epoxy Coating (g) Hardener (g) m (Al NP) (g) m (Ni NP) (g) m (Ag NP) (g) Thickness (µm)
Epoxy Coating 30 7.5 - - - 249.1
1% Al NP
30 7.5 0.4545 - - 256.1
Nanocomposite
1% Ni NP
30 7.5 - 0.4545 - 266.5
Nanocomposite
1% Ag NP
30 7.5 - - 0.4545 264.9
Nanocomposite

2.3. Characterization of the Epoxy Coating/Nanocomposite

To evaluate the size of the nanoparticles, the quality of dispersion, and the appearance
of the agglomerate of nanoparticles in the nanocomposite, scanning electron microscopy
(SEM) (TESCAN Brno, Brno, Czech Republic) and energy-dispersive X-ray spectroscopy
(EDS) analyses were used.
To investigate the anticorrosion behavior of Al, Ni, and Ag nanocomposites, electro-
chemical impedance spectroscopy (EIS) (VersaSTAT 3, AMETEK Scientific 131 Instruments,
Princeton applied research, Berwyn, PA, USA) was used. These measurements were per-
formed in a three-electrode electrochemical cell in a 3.5 wt.% NaCl solution. The coated
gray cast iron was used as the working electrode, with a test area of 19.75 cm2 , a saturated
calomel electrode was used as a reference electrode, and the graphite electrode was used
as an auxiliary electrode. The frequency scan range of 0.1 to 105 Hz with an amplitude of
10 mV was used. The impedance data were fitted using the ZSimpWin software(AMETEK,
Berwyn, PA, USA) (Version 3.2).
The samples of epoxy coating, 1% Al NP epoxy nanocomposite,1% Ni NP epoxy
nanocomposite, and 1% Ag NP epoxy nanocomposite were placed in contact with sim-
ulation wastewater according to the DIN EN 877 [22]. For the assessment of Al3+ , Ni2+ ,
and Ag+ ions’ migration from the epoxy coating, 10 g of each sample was immersed in
100 mL simulated wastewater for 30 days. In this study, samples were kept in the dark at
a temperature of 40 ◦ C. The temperature for this study was chosen according to the real
conditions in drainage pipes. The mass concentration, electrical conductivity, and pH value
of the wastewater were determined after 10, 20, and 30 days.The mass concentration of
Al3+ , Ni+ , and Ag+ ions in wastewater was determined with the flame atomic absorption
spectrometry (F-AAS) technique (Perkin Elmer Analyst 700, Waltham, MA, USA).The
conductivity and pH values were measured with a pH/EC meter (HI5521–02, HANNA
instruments, Woonsocket, RI, USA).
The antibacterial properties of the Al, Ni, and Ag were investigated with a well-
diffusion method [23]. For this purpose, P. aeruginosa was used as a Gram-negative bacterial
strain, and B. subtills as a Gram-positive bacterial strain. The 24 h aged active bacterial
cultures were poured into the Muller Hinton culture medium. The nanoparticle samples
dissolved in distilled water (100 g/mL) were added from the stock into each well. The zone
of inhibition was measured using a ruler. After 24 h, the appearance of the inhibition zone
was observed.
The antibacterial activities of nanocomposites were tested according to ISO 22196:2011
against P. aeruginosa and B. subtilis [24]. The surface of the epoxy coating, 1% Al epoxy
nanocomposite, 1% Ni epoxy nanocomposite, and 1% Ag epoxy nanocomposite were cut
to size 50 mm × 50 mm and inoculated with 0.4 mL of 105 CFU bacterial suspensions. All
samples were covered with polyethylene foil dimensions of 40 mm × 40 mm (± 1 mm)
and a thickness of 0.06 mm. All samples were placed in a Petri dish and incubated at 35 ◦ C
(±1 ◦ C) and 90% relative humidity (RH) (±5%) for 24 h (±1 h). The number of viable
bacterial cells was determined by plating different dilutions on plate count agar, incubating
the plates for 24 h at 37 ◦ C, and then visually counting the colonies [25]. All experiments
are representative of repeated trials. Sample error bars on plots represent ± SD. The
Coatings 2023, 13, 1201 5 of 15

measurement of the inhibition zone was carried out in four sections (rotation by 45◦ ) using
a ruler with a length of 15 cm. The measurements were repeated three times.

3. Results and Discussion

3.1. SEM and EDS Analysis of Epoxy Coating/Nanocomposite
The morphology of epoxy coating and 1 wt.% of Al, Ni, and Ag nanocomposites
were investigated using SEM analysis. Figure 2a shows the SEM images of epoxy coating
without nanoparticles, which indicates a rough surface morphology with a large addition
of other coating components such as fillers, additives, pigments and similar. The EDS
analysis confirms the presence of aluminum particles in the initial sample (Figure 2b,c).
It was assumed that these microparticles of aluminum were used as a pigment in the
epoxy coating. The presence of these particles in the initial epoxy coating showed small
irregularities and the appearance of agglomerates (Figure 2b). The EDS analysis 6ofofthe
Coatings 2023, 13, x FOR PEER REVIEW 15
initial epoxy coating (Figure 2c) determined the percentage of the aluminum microparticles,
and this was 0.85%.

Figure 2. Cont.
 Coatings 2023, 13, 1201 6 of 15

Figure
Figure 2. The
The SEM
SEM and
and EDS
EDS analyses
analyses ofof (a,b)
(a,b) epoxy
epoxy coating,
coating, (e,f)
(e,f) 1%
1% AlAl NP
NP epoxy
epoxy nanocomposite,
nanocomposite,
(i,j) 1% Ni
Ni NP
NP epoxy
epoxynanocomposite,
nanocomposite,and and(m,n)
(m,n)1%
1%AgAg NPNP epoxy
epoxy nanocomposite.
nanocomposite. TheThe
EDSEDS map-
mapping
ping and element
and element weightweight percentages
percentages of distribution
of distribution of microparticles
of microparticles of (c,d)
of (c,d) Al inAl in epoxy
epoxy coating,
coating, and
and nanoparticles of (g,h) Al, (k,l) Ni, and (o,p) Ag in the nanocomposite.
nanoparticles of (g,h) Al, (k,l) Ni, and (o,p) Ag in the nanocomposite.

With the addition of nanoparticles, the rough surface morphology of nanocomposites

remained the same (Figure 2e,i,m).The action of the sonication process improved the
distribution of the added aluminum particles (Figure 2g). The EDS analysis confirmed
the uniform distribution of Ni and Ag nanoparticles within the epoxy coating, shown
Coatings 2023, 13, x FOR PEER REVIEW 7 of 15
in Figure 2k,o. Furthermore, EDS analysis determined that all nanocomposite samples
contained a certain percentage of nanoparticles that deviated very slightly from the added
1% nanoparticles (Figure 2d,h,l,p).
3.2. EIS Analysis of Epoxy Coating/Nanocomposite
3.2. EIS Analysis of Epoxy Coating/Nanocomposite
The EIS measurements were performed to investigate the effects of the addition of
Al, Ni,The
andEIS
Agmeasurements
nanoparticles on were
theperformed to investigate
corrosion protection the effects
properties of epoxy
of the the addition
coatingof
inAl, Ni, wt.%
a 3.5 and Ag nanoparticles
NaCl on the
solution with corrosion
different protection
immersion properties
times. of thetoepoxy
According coating
the electro-
in a 3.5 wt.% NaCl solution with different immersion times. According
chemical behavior of the various prepared nanocomposites, the model of the equivalentto the electro-
chemical behavior of the various prepared nanocomposites, the model of the equivalent
circuit with three resistance elements was chosen (Figure 3). This model demonstrated
circuit with three resistance elements was chosen (Figure 3). This model demonstrated
electrolyte resistance, Re, coating capacitance, CPEcoat, coating resistance, Rcoat, charge
electrolyte resistance, Re , coating capacitance, CPEcoat , coating resistance, Rcoat , charge
transfer resistance, Rct, and double layer capacitance, CPEdl [26]. The behavior of the CPE
transfer resistance, Rct , and double layer capacitance, CPEdl [26]. The behavior of the CPE
was shown by the parameter phase shift, n(−1 ≤ n ≤ 1); when n = 0, the CPE represented a
was shown by the parameter phase shift, n (−1 ≤ n ≤ 1); when n = 0, the CPE represented
pure resistor, if n = −1, the CPE stood for an inductor, and if n = +1, the CPE represented a
a pure resistor, if n = −1, the CPE stood for an inductor, and if n = +1, the CPE represented
pure capacitor [27].
a pure capacitor [27].

Figure
Figure The
3.3.The equivalent
equivalent circuitsused
circuits usedfor
forfitting
fittingthe
theNyquist
Nyquistand
andBode
Bodeplots
plotsfor
forcoating.
coating.

TheNyquist
The Nyquist andand Bode
Bode plots
plots for for
the the
epoxy epoxy coating,
coating, 1%epoxy
1% Al Al epoxy nanocomposite,
nanocomposite, 1%
Ni epoxy nanocomposite, and 1% Ag epoxy nanocomposite after 24 h and 10 days ofof
1% Ni epoxy nanocomposite, and 1% Ag epoxy nanocomposite after 24 h and 10 days
immersioninin3.5
immersion 3.5wt.%
wt.%NaCl
NaClsolution
solutionare
areillustrated
illustratedininFigure
Figure4a–d.
4a–d.The
Thecalculated
calculatedvalues
values
of the EIS parameters were reported in Table 3. The coating protection efficiency (%CPE)
also listed in the table was calculated using the equation [28]:
𝑅coat with NP − 𝑅coat without NP
%𝐶𝑃𝐸 = (1)
𝑅coat with NP
Where Rcoatwith NP is the resistance of Al, Ni, or Ag nanocomposites, and Rcoatwithout NP is the
resistance of the epoxy coating.
Coatings 2023, 13, x FOR PEER REVIEW 8 of 15

Coatings 2023, 13, 1201 7 of 15

revealed that the n values were close to unity, implying that the interface behaved nearly
capacitively. The addition of nanoparticles increased the value of %CPE. In all nano-
of the EIS parameters were reported in Table 3. The coating protection efficiency (%CPE)
composites, the efficiency improved with time. The reason for such behavior could be
also listed in the table was calculated using the equation [28]:
nanoscale inorganic particles that cause better barrier properties. When metals interact
with their surroundings,%CPE canRcoat
they = be with NP − Rcoat
converted into a more
without NP chemically stable form such
(1)
as oxide, hydroxide, or sulfide, and thus Rprovide better corrosion resistance [30,31].
coat with NP

where Rcoat with NP is the resistance of Al, Ni, or Ag nanocomposites, and Rcoat without NP is
the resistance of the epoxy coating.

Figure 4. The (a,c) Nyquist and (b,d) Bode plots for epoxy coating, 1% Al epoxy nanocomposite,
1% Ni epoxy nanocomposite, and 1% Ag epoxy nanocomposite after (a,b) 24 h and (c,d) 10 days of
exposure to 3.5 wt.% NaCl solution.

Figure After
4. Theimmersion, as shown
(a,c) Nyquist in Bode
and (b,d) Figureplots
4, the
forelectrochemical
epoxy coating,response of the
1% Al epoxy prepared
nanocomposite, 1%
Ninanocomposites showed one-time
epoxy nanocomposite, and 1% Ag constants. The Nyquist diagrams
epoxy nanocomposite for epoxy
after (a,b) coating
24 h and (c,d)had
10 days of
the lowest
exposure value
to 3.5 wt.% Rcoat ,solution.
of NaCl implying that the presence of nanoparticles prolonged the use
of the gray cast iron. The nanocomposite with 1% of Ag NP showed the best corrosion
resistance, followed by the 1% Ni NP nanocomposite and 1% Al NP nanocomposite
(Figure 4a). All samples achieved a constant phase angle value extending from the medium
frequency range (100 Hz) to the high frequency range (105 Hz) after 24 h exposure in
Coatings 2023, 13, 1201 8 of 15

3.5 wt.% NaCl solution (Figure 4b). With increasing immersion time (after 10 days), the
resistance decreased due to the penetration of the electrolyte through the nanocomposite
layer, and the corrosion resistance for 1% Ni and 1% Al nanocomposites became equal
(Figure 4a,c). Figure 4c shows the deviation of the Nyquist diagrams from a perfect
semicircle. This phenomenon is referred to as frequency dispersion, and has been attributed
to the roughness and non-uniformity of a working electrode, fracture structures, and the
formation of porous layers [29]. This behavior can be observed in the Bode diagram, where
the constant area of the phase angle value decreased, indicating that all samples had started
to degrade (Figure 4d).

Table 3. Electrochemical parameters of the EIS experiments for all sample after 24 h, and 10 days of
exposure to 3.5 wt.% NaCl solution at room temperature.

Samples Re , Ω Rcoat , Ω CPEcoat , Ssecn n Rct ,Ω CPEdl , Ssecn n CPE, %

After 24 h
Epoxy Coating 195.9 2.55 × 108 4.8 × 10−10 0.9641 1.76 × 108 2.32 × 10−9 0.9305 -
1% Al NP
116.8 5.68 × 108 6.97 × 10−11 0.9379 2.034 × 108 5.67 × 10−10 0.9505 54.87
Nanocomposite
1% Ni NP
204.1 7.90 × 108 2.72 × 10−12 1 4.42 × 108 1.69 × 10−9 1 67.72
Nanocomposite
1% AgNP
217.1 8.89 × 108 5.95 × 10−12 1 8.81 × 108 2.12 × 10−10 1 71.32
Nanocomposite
After 10 days
Epoxy Coating 153.9 5.87 × 106 7.35 × 10−10 0.924 4.87 × 104 4.19 × 10−9 0.9951 -
1% Al NP
100.0 1.67 × 107 5.63 × 10−10 0.9102 2.35 × 106 3.85 × 10−10 0.9862 64.85
Nanocomposite
1% Ni NP
165.3 2.34 × 107 1.32 × 10−11 0.9589 3.34 × 106 7.53 × 10−10 0.9357 74.91
Nanocomposite
1% AgNP
135.5 2.57 × 107 3.64 × 10−11 0.9525 4.73 × 106 9.23 × 10−10 0.9768 77.16
Nanocomposite

Based on Table 3, the double layer capacitance between the coating surface/electrolyte
solutions (CPEcoat value) increased with time. This showed that the absorption level of
the electrolyte solution in the nanocomposite had increased, but its resistance was still
better than that of the epoxy coating. Further inspection of the table revealed that the n
values were close to unity, implying that the interface behaved nearly capacitively. The
addition of nanoparticles increased the value of %CPE. In all nanocomposites, the efficiency
improved with time. The reason for such behavior could be nanoscale inorganic particles
that cause better barrier properties. When metals interact with their surroundings, they can
be converted into a more chemically stable form such as oxide, hydroxide, or sulfide, and
thus provide better corrosion resistance [30,31].
Figure 5 illustrates the reaction between Al, Ni, and Ag NP and electrolyte, and the
protection mechanism of the Al, Ni, and Ag nanocomposites in contact with corrosive
electrolyte. When metallic aluminum comes into contact with oxygen, it becomes very
reactive. A thin layer of alumina (4 nm thickness) forms in about 100 picoseconds on any
exposed aluminum surface, which acts as a protective covering for further oxidation [32].
The Al NPs form an aluminum oxide layer on its surface in contact with the electrolyte,
according to the following equations [33]:

2Al + 6H2 O → 2Al(OH)3 + 3H2 (2)

2Al + 4H2 O → 2AlO(OH) + 3H2 (3)

2Al + 3H2 O → 2Al2 O3 + 3H2 (4)

ER REVIEW 10 of 1
Coatings 2023, 13, 1201 9 of 15

Figure 5. Protection mechanisms of (a) Al, (b) Ni, and (c) Ag nanoparticles in the epoxy coating in
Figure 5. Protection mechanisms of (a) Al, (b) Ni, and (c) Ag nanoparticles in the epoxy coating in
contact with NaClsolution.
contact with NaClsolution.
The volume of formed aluminum oxides is greater than the volume of nanoparticles,
which can prevent the further penetration of the corrosive medium, prolong the path of
3.3. Antibacterial Activity of the
penetration Al,corrosive
of the Ni, andmedium
Ag Nanoparticles
into the coating, and ultimately delay the onset of
corrosion (Figure 5a) [34,35].
The antibacterial activity
The Ni NPs ofdidAl,
notNi,
showand Agbehavior
passive nanoparticles was tested
in the epoxy coating because against variou
the 3.5 wt.%
bacterial strains: P. NaCl
aeruginosa, and
solution had B.value
a pH subtilise. Figure
of7. Nickel did not6react
represents
with water,the antibacterial
and small amounts of activ
chloride ions can be exposed on its surface. According to Pourbex’s diagram, passive oxide
ity of nanoparticles films
for should
various bacteria
appear in aofwell-diffusion
at a pHvalue 10 [20,36]. From thesetechnique. Arithmetic
results, we can conclude that mean
of measurement resultsonly Niare
NPsgiven with
and a small measurement
part of the formed NiCluncertainty
2 acted to increaseU = corrosion
the 1.5 mm, k = 2, and P
resistance
of nickel nanocomposites. The nickel nanocomposite system did not have the ability to
= 95%, where U is expanded measurement uncertainty, k the presented coverage factor
close the micropores formed in the epoxy coating during exposure to a corrosive medium.
and P is confidence Thelevel.
effectiveness of this coating dropped, as can be seen in Figure 4c,d.
The Ag NPs have the property of releasing Ag+ ions, which gives them the ability
to react with other chemical species in the environment. Since silver is a noble metal
(E◦ /V = 0.79 vs. SHE), its affinity for oxygen will be low, so a layer of AgCl will form on
its surface when exposed to 3.5 wt.% NaCl solution [36,37]. The generation of insoluble
AgCl leads to the formation of a chemical barrier inside the epoxy coating. Ag NPs act as a
chemical barrier against the further penetration of corrosive species from the electrolyte to
the grey cast iron substrate [38].

3.3. Antibacterial Activity of the Al, Ni, and Ag Nanoparticles

The antibacterial activity of Al, Ni, and Ag nanoparticles was tested against various
bacterial strains: P. aeruginosa, and B. subtilise. Figure 6 represents the antibacterial activity
of nanoparticles for various bacteria in a well-diffusion technique. Arithmetic means of
measurement results are given with measurement uncertainty U = 1.5 mm, k = 2, and
P = 95%, where U is expanded measurement uncertainty, k the presented coverage factor,
and P is confidence level.
 The antibacterial activity of Al, Ni, and Ag nanoparticles was tested against v
bacterial strains: P. aeruginosa, and B. subtilise. Figure 6 represents the antibacteria
ity of nanoparticles for various bacteria in a well-diffusion technique. Arithmetic
of measurement results are given with measurement uncertainty U = 1.5 mm, k = 2
Coatings 2023, 13, 1201 = 95%, where U is expanded measurement uncertainty, k the presented 10 ofcoverage
15
and P is confidence level.

6. Zone
Figure 6.
Figure Zoneofofinhibition of (a)ofAl,
inhibition (a)and
Al,(b) Ni, (b)
and andNi,
Ag nanoparticles against B. subtilis,
and Ag nanoparticles against andB.
(c)subtilis,
Al, and
and (d) Ni, and Ag against P. aeruginosa.
and (d) Ni, and Ag against P. aeruginosa.
The results indicated that Al and Ag nanoparticles showed effective antibacterial
activity compared to Ni nanoparticles. The diameter of the inhibitory zone shows that Al
NP had a larger zone of inhibition than Ag NP. In this respect, it was found that the Al
and Ag NP were poisonous to both Gram-positive and Gram-negative bacteria. Nickel
nanoparticles showed a very small inhibition zone, due to the large range of nanoparticle
sizes. Typically, smaller NPs have better interaction with the bacteria due to their ability to
penetrate a cell and inhibit bacteria growth [11,13]. Asghari and co-authors revealed that
P. aeruginosa showed a high survival rate against Ni NPs and therefore can survive at quite
high concentrations of Ni NPs [39]. It was assumed that due to their large size range and
the possibility of agglomeration in aqueous media, Ni NPs could not enter the membrane
of bacterial cells (P. aeruginosa and B. subtilis) to attach to functional groups of proteins to
cause their denaturation [40].

3.4. Migration Ability and Antibacterial Activity of the Nanocomposites

A migration of nanoparticles from epoxy coating is a very important test because it
provides a new property for drainage pipe protection. Figure 7 demonstrated the migration
of Al and Ni nanoparticles from the epoxy coating into simulated wastewater. Released
Ag+ ions from the epoxy coating reacted with Cl− ions from the wastewater to form a white
precipitate of silver(I) chloride. This is the reason why the actual concentration of Ag+ ions
released could not be determined with F-AAS techniques. In Figure 7, the concentration of
Ag+ ions in the wastewater was below the detection limit of the instrument.
 provides a new property for drainage pipe protection. Figure 7 demonstrated the migra-
tion of Al and Ni nanoparticles from the epoxy coating into simulated wastewater. Re-
leased Ag+ ions from the epoxy coating reacted with Cl− ions from the wastewater to form
a white precipitate of silver(I) chloride. This is the reason why the actual concentration of
Coatings 2023, 13, 1201 Ag+ ions released could not be determined with F-AAS techniques. In Figure 11 of7,15the con-
centration of Ag ions in the wastewater was below the detection limit of the instrument.
+

Figure
Figure 7.7.The
The mass
mass concentration
concentration of the of the migration
migration of Al, Ag,of Al,
and NiAg, and Ni nanoparticles
nanoparticles from epoxy
from epoxy coating
coating to simulated
to simulated wastewater.
wastewater.

The
Thenanoparticles
nanoparticles with 1% of
with 1%AlofNPAlshowed significant
NP showed migration,migration,
significant while nanocom-
while nano-
posites with Ag and Ni nanoparticles showed the lowest value of migration from epoxy
composites with Ag and Ni nanoparticles showed the lowest value of migration from
coating to the wastewater (Figure 7). The amount of migrated Al NP gradually increased
epoxy coating to the wastewater (Figure 7). The amount of migrated Al NP gradually
in the beginning, but after 10 days of exposure the wastewater assumed a constant value of
increased
aluminum in the beginning,
concentration but afterall
(1 mg/L).For 10samples,
days of theexposure
pH-value theincreased
wastewater veryassumed
slightly, a con-
stant valuetoof8.791,
from 7.723 aluminum
while theconcentration (1 mg/L).For
electrical conductivity showed all asamples,
significantthe pH-value
increase increased
for the
very
Al NPslightly, from 7.723
nanocomposite, fromto 8.791,
1.085 while
to 2.083 the electrical conductivity showed a significant
mS/cm.
increase for the AlofNP
The migration nanocomposite,
nanoparticles from thefrom
epoxy1.085 to 2.083
coating mS/cm. by the action of
was stimulated
the wastewater.
The migration Aluminum nanoparticles
of nanoparticles werethe
from theepoxy
only ones capable
coating wasofstimulated
forming an byoxide
the action
film on their surface. The resulting oxide film, with its passivity, closed
of the wastewater. Aluminum nanoparticles were the only ones capable of forming an the micropores of the
epoxy and did not allow the oxidation and migration of other nanoparticles located further
oxide film on their surface. The resulting oxide film, with its passivity, closed the mi-
from the surface of the epoxy coating. The incorporation of certain metals and metal-oxides
cropores of the epoxy and did not allow the oxidation and migration of other nanoparti-
in the epoxy polymers also led to the development of ‘active’ materials that prevented
cles locatedoffurther
the growth from theand
microorganisms, surface
henceof the epoxy
preserved coating.ofThe
the quality waterincorporation
pipesduring the of certain
metals and metal-oxides
transportation of wastewater. in According
the epoxytopolymers
ISO 22196,also led to the development
the antibacterial of ‘active’
properties of the
materials
epoxy coating (control sample) and nanocomposites were determined by measuring the quality
that prevented the growth of microorganisms, and hence preserved the
of water pipesduring
reduction in antibacterialtheactivity.
transportation
Consistent ofwith
wastewater. Accordingthe
the ISO guidelines, toreduction
ISO 22196, in the an-
antibacterialproperties
tibacterial activity wasofestimated
the epoxy using the following
coating (control equation
sample) [41]:
and nanocomposites were
(CFU 0h − CFU 24h )
reduction of antibacterial activity = × 100 (5)
CFU 0h

where CFU0h is the bacterial colony forming units obtained for the control samples before
incubation, and CFU24h is the bacterial colony forming units observed for the test conditions
for the nanocomposites after incubation.
The antibacterial activity of the epoxy coating and nanocomposites against P. aeruginosa
and B. subtilis after a 24 h exposition period is presented in Figure 8 and the reduction in
antibacterial activity in Table 4.

Table 4. Average values of bacterial reductions of epoxy coating and 1% Al NP, 1% Ag NP, and 1%
Ni NP in nanocomposite against P. aeruginosa and B. subtilis after 24 h.

Nanocomposite
Epoxy Coating 1% Al NP 1% Ag NP 1% Ni NP
P. aerugionosa 4.17 ± 0.09 61.46 ± 2.64 45.83 ± 4.05 11.46 ± 0.92
B. subtilis 3.44 ± 0.11 55.31 ± 0.16 42.19 ± 1.41 11.25 ± 0.15
 where CFU0h is the bacterial colony forming units obtained for the control samples before
incubation, and CFU24h is the bacterial colony forming units observed for the test condi-
tions for the nanocomposites after incubation.
The antibacterial activity of the epoxy coating and nanocomposites against P. aeru-
Coatings 2023, 13, 1201 ginosa and B. subtilis after a 24 h exposition period is presented in Figure 8 and the
12 of 15 re-
duction in antibacterial activity in Table 4.

Figure 8. Antibacterial activity of epoxy coating, and 1% Al, 1% Ag, and 1% Ni epoxy nanocomposite
Figure 8. Antibacterial activity of epoxy coating, and 1% Al, 1% Ag, and 1% Ni epoxy nanocom-
on (a) P. aerugionosa and (b) B. subtilis during 24 h according to the ISO 22196 standard.
posite on (a) P. aerugionosa and (b) B. subtilis during 24 h according to the ISO 22196 standard.
Based on the evaluation of bacteria (Figure 8), we concluded that after 24 h incu-
Table
bation4. the
Average values
highest liveofcount
bacterial
of P.reductions ofand
aeruginosa epoxy
B. coating
subtilis and
was1% Al NP, 1%
observed onAg
theNP, and 1%
epoxy
Ni NP in nanocomposite against P. aeruginosa and B. subtilis after 24 h.
coating samples and samples containing 1% of Ni NP in the nanocomposite (Table 4). The
nanocomposite with 1% of Al NP exhibited the highest antibacterial effect, with a reduction
Nanocomposite
of 61.46 ± 0.09% for P. aeruginosa and 55.31 ± 0.16% for B. subtilis (Figure 8, Table 4). The
Epoxy Coating 1% Al NP 1% Ag NP 1% Ni NP
1% of Ag NP in the epoxy coating showed the second-greatest antimicrobial potential, and
P. aerugionosa
achieved a 45.83 ± 4.05% cell 4.17 ± 0.09 for P. aeruginosa
reduction 61.46 ± 2.64 45.83±±1.41%
and 42.19 4.05 for11.46 ± 0.92
B. subtilis,
respectively, after 24 h incubation. However, the average leaching potential of Al NP ±was
B. subtilis 3.44 ± 0.11 55.31 ± 0.16 42.19 ± 1.41 11.25 0.15
better than Ag NP in the epoxy coating (Figure 7). In contact with aqueous media, the Al
NP formed
Based on an the
aluminum oxideofand
evaluation smaller
bacteria amounts
(Figure 8), of
wealuminum
concluded hydroxide
that afterand
24 oxyhy-
h incuba-
droxide [34]. The attraction between nanoparticles and bacteria depends
tion the highest live count of P. aeruginosa and B. subtilis was observed on the epoxy on the surface
charge of
coating the nanoparticles
samples and samples andcontaining
the bacteria1%[42].
of Gram-positive bacteria (B. subtilis)
Ni NP in the nanocomposite consist
(Table 4). The
of a thick layer of peptidoglycan, which is embedded in teichoic acid, while
nanocomposite with 1% of Al NP exhibited the highest antibacterial effect, with a reduc- Gram-negative
bacteria
tion (P. aeruginosa)
of 61.46 ± 0.09% forhave a layer of and
P. aeruginosa lipopolysaccharide
55.31 ± 0.16% forB.at thesubtilis
external surface.
(Figure The 4).
8, Table
teichoic acid and lipopolysaccharides impart a negative charge to the surface of bacterial
The 1% of Ag NP in the epoxy coating showed the second-greatest antimicrobial poten-
cells [43]. The negatively charged bacterial surfaces of P. aeruginosa and B. subtilis strongly
tial, and achieved a 45.83 ± 4.05% cell reduction for P. aeruginosa and 42.19 ± 1.41% for B.
attract the resulting highly positively charged oxides, for example Al2 O3 [44]. Better elec-
subtilis, respectively, after 24 h incubation. However, the average leaching potential of Al
trostatic attraction between bacteria and particles will result in better antibacterial action,
NP was better than Ag NP in the epoxy coating (Figure 7). In contact
which is visible in Figures 6c and 8a. Table 4 shows that less antibacterial activity with aqueouswasme-
dia, the Al
evident in NP formed
samples an aluminum
exposed oxide and
to the bacterium B. smaller amounts
subtilis due to theof aluminum
thick outer cellhydroxide
wall,
and oxyhydroxide [34]. The attraction between nanoparticles
which can hinder NP penetration into the thick peptidoglycan layer. and bacteria depends on
the surface charge of the nanoparticles and the bacteria [42]. Gram-positive
In contact with corrosive media, Al NPs react with water molecules and the following bacteria (B.
subtilis) consist occur
redox reactions of a thick
[45]: layer of peptidoglycan, which is embedded in teichoic acid,
while Gram-negative bacteria (P. aeruginosa) have a layer of lipopolysaccharide at the
3+
external surface. TheAl(s)
teichoic O(l) →
+ 6H2 acid and (aq) + 6OH- (aq) + 3H
2Allipopolysaccharides 2 (g) a negative charge
impart (6) to
the surface of bacterial cells [43]. The negatively charged bacterial surfaces of P. aeru-
In the oxidation reaction, the Al3+ ion is formed, which is toxic to bacteria. Also,
ginosa and B. subtilis strongly attract the resulting 3+ highly positively charged oxides, for
the resulting oxidation products can release the Al ion, which will affect the life of the
bacteria [41]. The mechanism of action of Al3+ ions has not been fully clarified yet. Cell
penetration and the adsorption or diffusion of NPs at the cell surface is often the initial step
in the stages involved in some microbial cell inhibition [46]. According to literature [47], an
increased Al3+ concentration can stimulate reactive oxygen species (ROS), which can act as
the main factor in DNA damage in bacterial cells.

4. Conclusions
The influence of nanoparticles in the epoxy coating leads to the modification of the
internal defects in the coating due to the filling of voids and blocking of easy access to
channels. Nanoparticles that could react with a corrosive medium prolong the path of
Coatings 2023, 13, 1201 13 of 15

penetration of corrosive species from the electrolyte to the metal substrate. Likewise, the
resulting corrosion product on the nanoparticle is dangerous for lower organisms and
can be used for the formation of a new property of the coating. These studies showed
that Al and Ag nanoparticles embedded in nanocomposites can significantly improve the
anticorrosive properties and inhibit bacteria, while Ni NPs have lower efficiency. Due to
remarkable properties like high reactivity, the ability to form a homogeneous structure,
bacterial resistance, cost-effectiveness, and unexplored literature, Al NPs attracted our
enormous interest and will continue to serve for detailed analysis so that they can be
applied as a protective additive in epoxy coating for the protection of pipelines.

Author Contributions: Conceptualization, M.S., V.A. and M.V.D.; methodology, M.S. and M.V.D.;
software, M.S.; validation, M.S. and M.V.D.; formal analysis, M.S.; investigation, M.S. and M.V.D.; re-
sources, V.A. and I.S.; data curation, M.S.; writing—original draft preparation, M.S.; writing—review
and editing, M.S.; visualization, M.S.; supervision, V.A., I.S. and M.V.D.; project administration, V.A.
and I.S.; funding acquisition, V.A. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded by “Development of anticorrosion protection system for multipur-
pose pipe use”, Grant Number KK.01.1.1.07.0045. This work was supported by the European Regional
Development Fund under the Operational Program Competitiveness and Cohesion 2014–2020.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: We thank Michaela Hruškova Hasan (University of Zagreb, Faculty of Mining,
Geology, and Petroleum Engineering) for the use of flame atomic absorption spectrometry technique-
sand helpful advice.
Conflicts of Interest: The authors declare no conflict of interest.

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