Engineering Research Express

PAPER You may also like

- Fabrication and calibration of a
Al2O3 and CuO nano particulate-based paints for piezoelectric nanocomposite paint
Samuel Osho, Nan Wu, Mohammad
marine applications Aramfard et al.

- Investigation of fuel consumption on an

operating ship due to biofouling growth
To cite this article: M V Krishna Mohan et al 2022 Eng. Res. Express 4 035056 and quality of anti-fouling coating
M L Hakim, B Nugroho, M N Nurrohman et
al.

- Anti-Fouling Effects of Carbon Nanofiber in

Electrochemical Sensing of Phenolic
View the article online for updates and enhancements. Compounds
Keerakit Kaewket, Chanpen Karuwan,
Somchai Sonsupap et al.

This content was downloaded from IP address 49.204.238.80 on 29/10/2022 at 14:28

 Eng. Res. Express 4 (2022) 035056 https://doi.org/10.1088/2631-8695/ac8fcd

PAPER

Al2O3 and CuO nano particulate-based paints for marine

RECEIVED
17 June 2022
applications
REVISED
20 August 2022
ACCEPTED FOR PUBLICATION
M V Krishna Mohan1,∗ , T V K Bhanuprakash1 and Aditya Mukherjee2
6 September 2022 1
Department of Marine Engineering, Andhra University, Visakhapatnam — 530003, India
PUBLISHED
2
Department of Chemical Engineering, GVP College of Engineering, Visakhapatnam — 530048, India
∗
20 September 2022 Author to whom any correspondence should be addressed.
E-mail: mvkmohan.gf@andhrauniversity.edu.in

Keywords: Al2O3, CuO, nano paint, anti corrosion and anti fouling

Abstract
The present study focuses on the Preparation of Aluminum Oxide, and Copper oxide antifouling coatings
to prevent or reduce corrosion and fouling in ships and marine vehicles. Al2O3 and CuO nanoparticles
were prepared using the ball milling process. The nano paints were prepared using these nanoparticles as
pigment and linseed alkyd resin as a binder. Mild-steel specimens coated with nano paint were immersed
in seawater for 120 days and the properties were studied using Scanning electron microscopy, SEM—
EDAX, X-ray Diffraction, and Fourier transform-infra red spectroscopy. It found an improvement in anti-
fouling exhibited by Al2O3 mild steel plates and also an improvement using CuO when compared to bare
paint. Contact angle measurement showed a marked increase for base paint which indicates its
hydrophobic nature.

1. Introduction

Submerged objects such as ships, offshore structures, and other marine structures are prone to fouling. Hull fouling is
the result of the accumulation of marine growth, resulting in reduced vessel speed, increased bunker consumption,
and the accrual of cleaning costs. This fouling can be substantially reduced by the application of Antifouling (AF)
coatings on the surfaces of marine. However, these AF coatings contain biocides that are extremely detrimental to the
marine environment. Previously anti-fouling coatings employed Tributyltin as a biocide which was tremendously
hazardous to the marine environment [1, 2]. The use of TBT in AF coatings has since been banned and has been
replaced by other biocides such as copper, zinc, etc, along with a wide range of other ‘booster’ biocides [3]. These
biocides, although to a lesser extent than TBT, are also proving to be harmful to the aquatic column as well. Although
biocide-free paints are commercially available, they are not as effective as their biocide-based counterparts. Therefore
the challenge is now to develop AF paints that incorporate a minimal amount of biocides but also offer effective AF
protection. Nano Technology has proven its superiority in its application in Marine, Textile, Construction,
Consumer goods, etc [4]. In the marine industry, the two major issues that can be tackled successfully by
nanotechnologies are corrosion and biofouling [5–7]. Researchers used SiO2, TiO2, ZnO, Al2O3, Fe2O3, graphene
oxide, and V2O5 nanostructures as functional paint pigments [8–12]. Nano-silver vanadate is also used as a promising
antibacterial additive to water-based paints [6]. In this sense, nanoparticles in paint have recently gained popularity.
Paints are a family of fluid-like compounds used to decorate and protect surfaces. Paint is made up of two main
components: pigment (coloring agent) and binder (film-forming agent) [13, 14] and also several nanoparticles are
employed in paint compositions as biocides.

2. Experimental materials and procedure

2.1. Preparation of nano-paint

Al2O3 and CuO in particulate form (100 microns size) were taken and converted into nano size (60–80 nm for
Al2O3 and 65 to 80 nm for CuO) using the standard ball milling process. The preliminary reason for opting ball

© 2022 IOP Publishing Ltd

Eng. Res. Express 4 (2022) 035056 M V Krishna Mohan et al

Figure 1. Nano-particles obtained by ball milling process.

Figure 2. High energy ball-milling equipment.

milling process for this work is because it improves the forging properties of the material; which in turn
improves the superior properties of the material on whole [15]. Figure 1 shows the preparation of nanoparticles
through a ball milling process. The ball milling process was carried out for 14 milling hours using tungsten
carbide balls at 300 rpm speed and the ball to powder ratio is maintained at 10: 1 by volume. Ball milling
equipment used for the study was shown in figure 2 50 grams each of nano paint is prepared by stirring desired
amounts of this nanopowder in the paint formulation. The components that makeup with paint formulation are
shown in table 1.

2.2. Preparations of specimens

All the experiments were performed using mild steel as substrate with dimensions (45 mm × 65 mm × 5 mm).
The substrate surface was cleaned thoroughly by using a wire brush and emery paper. Acetone was applied to
remove any minor particles still present on the surface. The Zinc Yellow primer, which was purchased
commercially, was applied to the substrate using a spray gun. The thickness of the primer was found to be
between 60–70 microns well within the range of acceptable range of 100 microns and allowed to dry for 24 h.
The Coating thickness was observed and recorded using an ultrasonic paint film thickness gauge [16]. The nano
paint prepared in the previous section was stirred using a mechanical stirrer for 1 h. and then applied to the
surface of the substrate. The substrate was allowed to dry for 24 h after which the specimen was immersed in
seawater.

2
Eng. Res. Express 4 (2022) 035056 M V Krishna Mohan et al

Table 1. Composition in paints.

S.no. Material used Weight in grams

1 Linseed Alkyd Resin 30

2 Aluminum stearate 2.5
3 Thickener A 0.5
4 Soya lecithin 3
5 TiO2 Powder 10
6 Mineral turpentine oil 4

2.3. Immersion test of specimens

The coated specimens were immersed in seawater as mentioned from Jan 2022 (Average temperature of 22 °C)
to June 2022 (Average temperature of 34 °C) [17]. These Specimens were periodically withdrawn and inspected
for fouling at stipulated intervals. Sample numbers are given for different compositions of weight. Figures 11(a)–
(c) and figures 14(a)–(c) show the mild steel substrate after coating with CuO nanoparticles-based paint and
Al2O3 nanoparticle-based paint respectively before immersion. Figures 12(a)–(c) and figures 15(a)–(c) show the
mild steel substrate after coating with CuO nanoparticles-based paint and Al2O3 nanoparticle-based paint
respectively after 120 days of immersion. Figure 17(a) shows the mild steel substrate with coating with primer.
Figure 17(b) shows the mild steel substrate without containing nanoparticles and only the base paint.

2.4. Surface morphology

The morphology and chemical composition of the prepared coatings were investigated by a scanning electron
microscope (Jeal 6390 LA / Oxford XMXN) equipped with energy-dispersive x-ray spectroscopy (EDS). The
phase structure and infrared Spectrum were investigated by XR Diffractometers (Bruker D8 Advance) and FTI
Spectrometer (Thermo Nicolet IS50) respectively.

3. Results and discussions

At different magnifications, figure 3 depicts the surface morphology of the substrate on painting with nano
Al2O3 and nano CuO mixed paints. These micrographs indicate the existence of equiaxed Al2O3 and CuO
particles, with Al2O3 particles being spherical with faceted shapes and CuO particles being spherical with smooth
surfaces. This is one of the reasons why the CuO particles had greater adhesive properties to the substrate.
Figures 3(c) and (d) shows the size distribution of the two paints, with the bulk of the Al2O3 particles lying within
the range of 60 nm–96 nm and the CuO particles falling within the range of 60 nm–72.4 nm. It is obvious from
these data that CuO particles had a smaller particle size distribution, which contributed to the strong bonding
between the CuO particles and the substrate as compared to Al2O3 particles. The SEM micrograph of the Al2O3
and CuO nano paint surface (shown in figure 3) demonstrated the existence of nano Al2O3 and CuO mixed with
the paint’s alkyd resin matrix. This is related to the efficiency of the ball milling process used in paint
preparation. The topography of the sample is measured by the Atomic Force Microscope. The mechanical forces
created during milling enable the Al2O3 and CuO nanoparticles and other additives to molecularly mix in the
alkyd resin matrix, resulting in the production of the viscous colloidal paint solution.
The SEM EDAX results of the Al2O3 and CuO nanoparticles paint are shown in figure 4. Figure 4(a) clearly
shows the presence of Al and O particles in the nano paint in the Al2O3 nanoparticle paint. Similar findings were
obtained with the CuO nano paint, as Cu and O particles were found in the results. These findings back up the
previous findings by confirming that the painting was done with these two nanoparticles. In addition, the EDAX
spectra confirmed the presence of elements (Al, O, and Cu) in the painted substrate. The EDAX maps of the
substrate confirmed the uniform distribution of all elements inside the nano paint that was applied to the
substrate.
In the Pattern, x-ray Diffraction, of Al2O3 is shown in figure 5. This shows the Sphalerite, syn (Major
concentration) phase was presented with a cubic crystal structure, F-43m (216) Space group and the angle
2θ = 28.527, 33.121, 47.650, 56.486 degrees, and the other compounds such as Rutile, syn, α-Si O2 Silicon
Oxide, Dolomite, Calcite magnesian and Hematite, syn with the crystal structure Tetragonal(P42/ mnm (136) S.
G), Triclinic (P1(1) S.G), Rhombo.H. Axes (R-3(148) S.G), Rhombo.H. Axes (R-3c (147) S, G), and Rhombo.H.
Axes (R-3c (147) S, G), respectively with minor concentrations. Due to its non-crystalline nature, there are no
peaks related to alkyd resin. The diffraction angles of each of the concentrations are depicted in the figure.
Similarly, for CuO nanoparticles-based paint, a graph is obtained by the number of Counts represented
along the ordinate and Diffraction angle 2θ along with the abscissa. The major concentration in this CuO
nanoparticles-based paint is Rutile, syn Phase with Tetragonal crystal structure, P 42/ mnm (136) Space Group.

3
Eng. Res. Express 4 (2022) 035056 M V Krishna Mohan et al

Figure 3. Surface morphology of nanoparticles at different magnifications (a) & (c); Al2O3 (b) & (d) CuO. (e) AFM Image of Al2O3 (x30
μm); (f) AFM Image of CuO (x 50 μm).

The value of 2θ for Rutile, syn was 27.459, 39.104, 44.081, and 56.676 degrees at the highest peaks. Aragonite,
Sphalerite syn, Quartz, and Calcite Magnesian are the other minerals presented with less level of concentration
with crystal structures Orthorhombic (Pmcn 62 S.G), Cubic (F-43m 216 S.G), Hexagonal (P-3221 154 S.G) and
Rhombo. H Axes (R-3c 167 S.G) Respectively. The diffraction angles 2θ of the above-mentioned low
concentrated minerals are given in figures 6(a)–(b).
Fourier transform-infra red spectroscopy is one of the best techniques for the study of nanomaterials and
also functional coatings. To study the bonding interaction that occurred between the Al2O3 and alkyd resin in
the nanoparticles-based paint as shown in figure 7. The spectrum of Al2O3 shows the characteristic bands due to
alkyd resin (observed at 2847.75, 2322.59, 1620.40, and 1542.01 cm−1).
Fourier transform-infra red spectroscopy of CuO Nanoparticles-based paint is shown in figure 8. CuO
nanoparticles (observed at 2854.49, 1723.14, 1618.93, 1577.87, 1448.76 cm−1). In this study, a graph is obtained

4
Eng. Res. Express 4 (2022) 035056 M V Krishna Mohan et al

Figure 4. Composition of nanoparticles through SEM-EDAX – (a) Al2O3 and (b) CuO.

with a wave number (cm−1) on the x-axis and % transmittance on the y-axis. This study indicated the presence
of nanoparticles is well mixed in the alkyd resin framework in the last paint item.
Furthermore, the hydrophobic surface revealed that the adhesive forces were stronger than the cohesive
forces, indicating that the molecules of the water droplets tend to interact more with the substrate molecules
than with each other, resulting in more water droplet attachments to the mild steel surface and the formation of
lower WCA (figure 9) with two different environments. Also, the contact angle versus step number is shown in
figure 10 in two environments. Despite their opposing natures, hydrophobic and hydrophilic tendencies both
play significant roles in self–cleaning applications. Customizing the surface texture (for example, increased
surface roughness) may result in excellent hydrophobic surfaces with WCA exceeding 90°, The non-polar
molecules that reject water and create droplets may be completely spherical on hydrophobic surfaces and self–
clean them by simply rolling off without touching (also known as low surface wettability). The lower WCA the
better AF properties, and the probability of attachment is less. When the molecules of the surface create an ionic
or hydrogen connection with water, the surface is said to be hydrophilic if the WCA is less than 90°. These
surfaces are prone to wetting because the fluid distributes across a vast region of the surface. Complete wetting
(also known as super–hydrophilic) happens when the WCA is 0° and the droplet spreads continuously to cover
the whole glass substrate. However, for super-hydrophobic surfaces, the WCA is more than 150°, indicating
essentially no contact between the water droplet and the surface, which rationalizes the ‘lotus effect.’ [18–20].
The mean Contact angle with drop phase water (Air) is 97.02 0 (± 0.22) for 18 steps and the mean contact
angle with N, N- dimethyl- formamide (Air) is 55.78 0 (± 4.24) for 24 steps.
Figures 12 and 13 depict photographs of specimens after they have been immersed in seawater for 120 days.
The bare and substrate without nanoparticle surfaces are submerged for a time of 120 days along with coated
substrates and the fouling of marine organisms was visibly noticed as shown in figures 12 and 13. The exposed
substrates showed the development of marine organisms while the growth is less in nanoparticles-based paint.
It may be observed in Figures, 11, 12, 13, 14, 15, 16, and 17 that the Al2O3 and CuO nano paint surface
inhabit the biofouling, consequently, it will in general be used as an antifouling paint. These photographs
indicate that both nanoparticle-based Al2O3 and CuO coatings are effective in controlling fouling, however,
CuO-based paints are more effective. This may be attributed to the fact that copper is a strong biocide as
compared to aluminum. It also may be noted that the nano-based paints appear to offer better protection to the
substrate than their micro-based counterparts. Better antifouling protection by nanoparticle-based coatings is
possibly due to its small particle size and therefore a larger surface area that is potentially available for biocidal
activity.

4. CuO specimens

The samples coated with CuO nanoparticles and microparticles are submerged for a time of 120 days in sea-
water along with the other samples.

5
Eng. Res. Express 4 (2022) 035056 M V Krishna Mohan et al

Figure 5. (a) & (b): x-ray diffraction pattern of Al2O3 painted on substrates.

5. Al2O3 specimens

The samples coated with Al2O3 nanoparticles and samples without nanoparticle surfaces are also submerged for
a time of 120 days along with coated (primer applied) sample and the fouling due to marine organisms was
visibly noticed as shown in the figures given above and no commercial Paints were used as a paint base for
coating in this study in any step or process.

6. Conclusions

The effect of nanoparticles in antifouling paint formulations is likely to improve the efficacy of antifouling
paints. The optimal results of the work are an Antifouling paint that is highly effective, easy to coat, Stable, and
has a satisfactory time frame of realistic usability.

6
Eng. Res. Express 4 (2022) 035056 M V Krishna Mohan et al

Figure 6. (a) & (b): x-Ray diffraction image of CuO painted substrates.

In this work, Al2O3 and CuO nano-paints were coated on a mild steel substrate. The structure, surface
morphology, Al2O3, and CuO particle distribution were investigated. The concluding remarks were classified as
follows:

1. The presence of (Al, O, and Cu) was observed with the SEM-EDAX results.
2. The XRD and FTIR results also observed that in non-crystalline nature, there are no peaks related to alkyd
resin, and the presence of nanoparticles is all around blended in the alkyd system in the applied paint.
3. The nano paint was showing a hydrophobic surface nature with the substrate.

7
Eng. Res. Express 4 (2022) 035056 M V Krishna Mohan et al

Figure 7. Fourier transform-infra red spectroscopy of Al2O3 Nanoparticles based paint.

Figure 8. Fourier transform-infra red spectroscopy of CuO Nanoparticles based paint.

Figure 9. Contact angle with (a) N, N- dimethyl-formamide (Air) (b) Drop phase water (Air).

8
Eng. Res. Express 4 (2022) 035056 M V Krishna Mohan et al

Figure 10. Contact angle versus step number under different environments.

Figure 11. Mild steel substrate after painting with a weight percentage of (a) 0.25 grams of CuO nanoparticles. (b) 0.5 grams of CuO
nanoparticles (c) 1 gm of CuO nanoparticles.

4. The CuO nano paint was showing better anti-fouling and anti-corrosion properties compared with the Al2O3
nano paint and the Al2O3 has better properties when compared to the substrate without nanoparticles and
bare substrate.

Considering the global impact on the effects of marine biofouling, the key findings of this work suggested
that the Al2O3, ZnO, TiO2, CuO, and Fe2O3 nano paint can create new horizons in the maritime industries and
might find potential applications for coating as bottom paints.
Efficient antifouling paints will not only reduce fuel consumption in ocean-going vessels and thereby a
corresponding reduction in greenhouse gases but will also have the following benefits.

9
Eng. Res. Express 4 (2022) 035056 M V Krishna Mohan et al

Figure 12. Mild steel substrate after painting with a weight percentage of (a) 0.25 grams of CuO nanoparticles. (b) 0.5 grams of CuO
nanoparticles (c) 1 gm of CuO nanoparticles after 120 days.

Figure 13. Mild steel substrate after painting with a weight percentage of (a) 0.25 grams of CuO microparticles. (b) 0.5 grams of CuO
microparticles; (c) 1 gm of CuO microparticles after 120 days.

Figure 14. Mild steel substrate after painting with a weight percentage of (a) 0.25 grams Al2O3 nanoparticles. (b) 0.5 grams of Al2O3
nanoparticles (c) 1 gram of Al2O3 nanoparticles.

10
Eng. Res. Express 4 (2022) 035056 M V Krishna Mohan et al

Figure 15. Mild steel substrate after painting with a weight percentage of (a) 0.25 grams of Al2O3 nanoparticles. (b) 0.5 grams of Al2O3
nanoparticles (c) 1 gram of Al2O3 nanoparticles after 120 days.

Figure 16. Mild steel substrate after painting with a weight percentage of (a) 0.25 grams of Al2O3 microparticles. (b) 0.5 grams of Al2O3
microparticles (c) 1 gram of Al2O3 microparticles.

Figure 17. (a) Sample without coating (only with primer) (b) Sample without nanoparticle (Bare Sample).

1. Reducing the propagation of invasive species.

2. As a result of the reduction of invasive species, there would be a likely improvement in the production of
seafood which would improve the livelihood of fishermen.

11
Eng. Res. Express 4 (2022) 035056 M V Krishna Mohan et al

Data availability statement

The data generated and/or analysed during the current study are not publicly available for legal/ethical reasons
but are available from the corresponding author on reasonable request.

ORCID iDs

M V Krishna Mohan https://orcid.org/0000-0003-0595-7605

References
[1] Lejars M, Margaillan A and Bressy C 2012 Fouling release coatings: a nontoxic alternative to biocidal antifouling coatings Chem. Rev.
112 4347–90
[2] Turner A 2021 Paint particles in the marine environment: an overlooked component of microplastics Water Research X 60 100110
[3] Ali A, Jamil M I, Jiang J, Shoaib M, Amin B U, Luo S, Zhan X, Chen F and Zhang Q 2020 An overview of controlled-biocide-release
coating based on polymer resin for marine antifouling applications J. Polym. Res. 27 35
[4] Subbiah G, Premanathan M, Kim S J, Krishnamoorthy K and Jeyasubramanian K 2014 Preparation of TiO2 nano paint using ball
milling process and investigation on its antibacterial properties Mater. Express 4 393–9
[5] Yong H E, Krishnamoorthy K, Hyun K T and Kim S J 2015 Preparation of ZnO nano paint for marine antifouling applications J. Ind.
Eng. Chem. 29 39–42
[6] Holtz R D, Lima B A, Souza Filho A G, Brocchi M and Alves O L 2012 Nanostructured silver vanadate as a promising anti-bacterial
additive to water-based paints’ Nanomed Nano- 201 technol. Biol. Med. 8 935
[7] Callow J A and Callow M E 2011 Trends in the development of environmentally friendly fouling-resistant marine coatings Nat.
Commun. 2 244
[8] Natalio F, Andre R, Hartog A F, Stoll B, Jochum K P, Wever R and Tremel W 2012 Vanadium pentoxide nanoparticles mimic
vanadium haloperoxidases and thwart biofilm formation Nat. Nano Technol. 7 530–5
[9] Krishnamoorthy K, Premanathan M, Veerapandian M and Kim S J 2014 Nanostructured molybdenum oxide-based antibacterial
paint: effective growth inhibition of various pathogenic bacteria Nanotechnology 25 31
[10] Krishnamoorthy K, Premanathan M, Veerapandian M and Kim S J 2014 Nanotechnology 25 31
[11] Sharifi Golru S, Attar M M and Ramezanzadeh B 2014 Studying the influence of nano-Al2O3 particles on the corrosion performance
and hydrolytic degradation resistance of an epoxy/polyamide coating on AA-1050 Prog. Org. Coat. 77 1391–9
[12] Dhoke S K, Sinha T and Khanna A S 2009 Effect of nano-ZnO particles on the corrosion behavior of alkyd-based waterborne coatings
J. Coat. Technol. Res. 6 353–68
[13] Bohannon J 2005 Science ‘smart coatings’ Research Shows the Virtues of Superficiality 309 376–7
[14] Wijewardane S and Goswami D Y 2012 Renew. Sustain Energy ‘List of Chemicals’ Rev. 16 1863
[15] Ealias A M and Saravanakumar M P A review on the classification, characterization, synthesis of nanoparticles and their application
[16] Mukherjee A, Joshi M, Misra S C and Ramesh U S 2019 Antifouling paint schemes for green SHIPS Ocean Eng. 173 227–34
[17] Mukherjee A, Mohan Rao K V and Ramesh U S 2009 ‘Predicted concentrations of biocides from antifouling paints in Visakhapatnam
Harbour J. Environ. Manage. 90 S51–9
[18] Nazhiraha S N M, Goshala S K, Arifina R and Hamzah R 2020 Titania nanoparticles activated tellurizing–silicate glass with controlled
hydrophobic and hydrophilic traits for self-cleaning applications J. Non-Cryst. Solids 530 119778
[19] Pierre P 2013 Photocatalysis, and Water Purification: from Fundamentals to Recent Applications (New York, NY: Wiley) (https://www.
wiley.com/en-us/Photocatalysis+and+Water+Purification:+From+Fundamentals+to+Recent+Applications-p-9783527331871)
ISBN: 978-3-527-33187-1
[20] Zettlemoyer A C 1968 Hydrophobic surfaces J. Colloid Interface Sci. 28 343–69

12