MITIGATION OF MICROBIALLY INDUCED

CORROSION (MIC) OF STEEL IN EXTREME

INDUSTRIAL ENVIRONMENTS

SEMINAR PRESENTATION (MSE-691A)

FINAL REPORT
Submitted By

SUNKAVALLI SAI PRAKASH

(Roll.No.21206263)

Under the supervision of

Prof. RAGHUPATHY YUVARAJ

MSE DEPARTMENT, IIT-KANPUR

DEPARTMENT OF MATERIALS SCIENCE AND ENGINEERING

INDIAN INSTITUTE OF TECHNOLOGY-KANPUR

KANPUR, UTTAR PRADESH- 208016

(A.Y: 2022-2023)
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 INDEX
S.NO TITLE OF THE CONTENT PAGE NO
1. Index ii
2. List of figures iii
3. List of tables iv
4. Acknowledgement v
5. Abstract vi
6. 1. Introduction 1
7. 1.1. Materials susceptible for MIC 2
8. 1.1.1. Cu-based alloys 2
9. 1.1.2. Steels 2
10. 1.1.3. Ti-based alloys 3
11. 1.1.4. Nickel-based alloys 3
12. 1.2.MIC across various industries 3
13. 1.3. Biofouling 4
14. 1.3.1. Stages in biofouling 5
15. 1.4. Micro-organisms responsible for MIC 6
16. 1.4.1. Bacteria 7
17. 1.4.1.1. Sulphate reducing bacteria (SRB) 7
18. 1.4.1.2. Nitrate reducing bacteria (NRB) 8
19. 1.4.1.3. Iron oxidizing bacteria (IOB) 9
20. 1.4.1.4. Manganese oxidizing bacteria (MOB) 9
21. 1.5. Industrial methods to control biofouling 10
22. 1.5.1. Physical methods 10
23. 1.5.2. Mechanical methods 11
24. 1.5.3. Biological methods 11
25. 2. Literature review 12
26. 2.1. Anti-Fouling Behaviour of Silver 12
nanoparticles on Graphene sheet
27. 2.2. Anti-Fouling Behaviour of Silver Nano- 14
particles on Graphene Oxide sheet
28. 2.3. Anti-Fouling Behaviour of Silver Nano- 16
particles in Ni-Matrix on Cu
29. 2.4. Copper-graphene oxide composite 18
coatings for corrosion protection of mild steel
30. 3. Work plan 20
31. 4. Conclusions 21
32. 5. References 22

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 LIST OF FIGURES
S.NO TITLE OF THE FIGURE PAGE NO
1. Figure-1: Electrochemical Nature of Corrosion 1
2. Figure-2: Biofilm on metal surface 2
3. Figure-3: MIC across various industries 4
4. Figure-4: Biofouling on the ship hull portion 5
5. Figure-5: Steps in biofouling 5
6. Figure-6: Sulphate reducing bacteria (SRB) 7
7. Figure-7: Nitrate reducing bacteria (NRB) 8
8. Figure-8: Iron oxidizing bacteria (IOB) 9
9. Figure-9: Manganese oxidizing bacteria 10
10. Figure-10: Physical method of controlling biofouling 10
11. Figure-11: Mechanical method of controlling biofouling 11
12. Figure-12: Biocidal application for biofouling removal 11
13. Figure-13: Nature of the surfaces 12
14. Figure-14: SEM micrographs 13
15. Figure-15: Biofouling behaviour in H. Pacifica bacteria 14
16. Figure-16: Morphology of composite in TEM 15
17. Figure-17: Time-kill curves for (a) graphene oxide and (b) graphene 15
oxide and Ag-particle composite
18. Figure-18: Microstructure of Ag nano particles 16
19. Figure-19: SEM images of coatings 16
20. Figure-20: Electrochemical corrosion behaviour 17
21. Figure-21: SEM images of coatings after SRB exposure 17
22. Figure-22: Growth behaviour of SRB 18
23. Figure-23: Morphology of coatings 19
24. Figure-24: Electrochemical corrosion behaviour 19
25. Figure- 25: Flow sheet of the work plan 21

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 LIST OF TABLES
S.NO TITLE OF THE TABLE PAGE NO
1. Table-1: Industries susceptible to MIC 3
2. Table-2: Microorganisms responsible for MIC 6
3. Table-3: Weight ratios of graphene and silver precursor 13
4. Table-4: Electrochemical corrosion test results before biofouling 17
5. Table-5: Electrochemical corrosion test results after biofouling 17
6. Table-6: Electrodeposition conditions 19
7. Table-7: Electrochemical corrosion test results of As-deposited 20
coatings
8. Table-8: Electrochemical corrosion test results after exposure to 20
3.5% NaCl

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 ACKNOWLEDGEMENT

First and foremost, I offer my sincerest gratitude to my supervisor,

Prof. Raghupathy Yuvaraj who have introduced me to the current topic of microbially induced corrosion
and his valuable suggestions. I am indebted to him for providing me all the necessary support for
successful completion of this course. I acknowledge my family members for their help and support
throughout my life. I also acknowledge the department of Materials science and engineering IIT-Kanpur
for offering all the facilities to enhance my knowledge.

I also would like to express my special thanks to the Instructors of MSE691A

Prof. Shashank Shekhar and Prof. Raghupathy Yuvaraj for spending their valuable time with us in
giving constant support, useful advices and constructive criticism throughout the course in the learning
the presentation skills. I also would like to thank the Teaching assistant Mr. Mohit Pandey for giving
his valuable time for us. I also thank my classmates and friends of MSE-691 course for making me to
learn the presentation skills and also about various research works going on in our Materials science
and engineering department-IIT Kanpur.

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 ABSTRACT

Microbially induced corrosion leads to premature materials failures in industry,

and thus is a cause for concern. For instance, it accounts for various direct and indirect costs in
major industry such as marine, petrochemical, mining, etc. MIC is enhanced corrosion of
metallic materials due to certain microbes in the environment. In MIC, corrosion is often
mediated or promoted by development of corrosion inducing biofilms on substrates, Among a
wide range of metallic materials, Steel is known for its susceptibility to biofouling and MIC.
Bacteria and Fungi are the most widely known for their severity of MIC. Classical methods of
preventing the biofouling such as organic coatings, Biocidal application, physical and
Mechanical cleaning have their limitations such as environmental toxicity, lack of long-term
protectability, frequent maintenance costs, etc.

The present study aims at developing Metal-Matrix Nanocomposites

(MMNC) to prevent biofouling and MIC on steel. Ag Nanoparticles and graphene oxide
nanosheets will be incorporated into various metal matrix and examined with regard to their
anti-fouling and MIC behaviour in simulated and isolated environments conducive to
biofouling and MIC. While Ag nanoparticles are known for their anti-microbial properties, GO
nanosheet are expected to afford both anti-corrosion properties. Metal matrix will vary from
simple Cu-Fe binary system to high entropy alloy-based system based on the electrochemical
corrosion behaviour of the matrix as well as electrochemical compatibility between the matrix
and incorporated Ag NPs and GO nanosheets. Ag NPs and GO nanosheets will be chemically
synthesised and electrophorectically incorporated into metal matrix during electrodeposition.

Keywords: Microbially influenced corrosion, Biofouling, Metal matrix nano composites,

Nano particles.

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1.INTRODUCTION
Corrosion is a form of a failure in metals and alloys which are subjected to
the environment. It is an electrochemical process having the cathode, anode, electrolyte and
the conductor (Figure-1). Generally, corrosion leads to loss of materials, surface appearance,
and structural integrity. Economic losses associated with corrosion account for 4-5% of GDP
of a nation.

Microbially induced corrosion (MIC) is a form of corrosion in which the

electrochemical reactions are mediated by the micro-organisms directly or indirectly. In the
direct method the micro-organisms will catalyse the cathodic and the anodic reactions and in
the indirect methods the metabolites of the micro-organisms will influence the corrosion of
metals. The microbially influenced corrosion constitutes of about 30-40% of the total corrosion
of metals and alloys. The prerequisite for microbially influenced corrosion is the formation of
biofilm (Figure-2) and after that it leads to biofouling and subsequently MIC. Bio-film is highly
heterogeneous in nature in terms of PH, dissolved oxygen concentration and Metabolites of the
micro-organisms. As a result, it leads to the formation of a concentration cell and which in turn
a cause for the galvanic corrosion.

Figure-1: Electrochemical Nature of Corrosion.

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 Figure-2: Biofilm on metal surface.

1.1.Materials susceptible for MIC

In general, all the metals that are employed in industry are susceptible
for MIC and these are: Steels, Ti-Alloys, Ni-based alloys and Cu-based alloys.

1.1.1. Cu-based alloys

Cu based alloys are extensively used in heat exchangers, pumps, valves

and condensers etc. SRB’s if present they may lead to MIC of these by various mechanisms
such as cathodic depolarization, selective dissolution and differential aeration.

1.1.2. Steels

Tubercle formation with pitting underneath is encountered in steel

pipes and tubes, resulting in hampered flow, and plugging problems. Carbon steels are used for
water, oil and gas transport under sub-soil and marine environments. Aerobic bacteria such as
Gallionella, Leptothrix and Acidithiobacillus contribute to MIC resulting from differential
aeration cells. These organisms oxidize ferrous to ferric resulting in the deposition of ferric
oxyhydroxides. Anaerobic bacteria such as Sulfate Reducing Bacteria inhabit the tubercles.

2
 Aerobic bacteria can bring about MIC through formation of slimes,
oxidation of iron and sulphides and generation of acidic metabolites. Hydrated slimes coat the
metal surfaces, creating differential aeration cells. Iron oxidising bacteria oxidise ferrous ions
to less soluble ferric ions, leading to the formation of insoluble tubercles, which consist of
hydrated ferric oxides and biological slimes. \

1.1.2. Ti-based alloys

Titanium is susceptible to biofouling. SRBs and acid-

producing bacteria may generate differential aeration cells leading to destruction of passive
films. Titanium and its alloys used in marine environments are susceptible to biofilm formation
involving manganese and iron oxidising bacteria as well as sulfate reducing halophiles. Surface
passive films on titanium could be disrupted in the presence of anaerobes, leading to
ennoblement and pitting.

1.1.3. Nickel-based alloys

Monel and Inconel are susceptible to MIC. Nickel-based alloys

used in nuclear power plants corrode due to microbial attack under marine environments.

1.2.MIC across various industries

Ranging from marine industry to the medical industry (Figure-3) the MIC
has serious consequences leading to lot of issues such as failure of the structures, reliability
issues and other consequences. The industries and the parts susceptible are given in the table
below (Table-1).

INDUSTRY SUSCEPTIBLE PARTS

Nuclear and Thermal Power plants Cooling water Tubes and Pipes
Chemical Industries Pipelines, Tanks and Heat exchangers
Aviation Fuel Tanks
Mining Underground Machinery
Medical Pacemaker, Contact Lens and Orthopedic
Implants
Marine Ship Hull and Fishing Nets
Food Processing Packing and Conveyor Belts
Table-1: Industries susceptible to MIC.

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1.3. Biofouling

Biofouling is the process of accumulation of unwanted

microorganisms such as microalgae, bacteria, diatoms and also macro-organisms such as
barnacles and bryozoans etc on top of the surface of a metal which is in contact with water or
soil. First the micro-organisms will attach to the surface of the material as a biofilm then they
will secrete a substance called extracellular polymeric substance (EPS) which is a perfect
habitat for their growth and metabolism. As a result, other macro-organisms also will attach to
this biofilm and form causes the biofouling (Figure-4).

Medical
Industry

Nuclear and
Marine
Thermal
Industry
Power Plants

MIC
Food
Chemical
Processing
Industries
Industry

Aviation

Figure-3: MIC across various industries.

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 Figure-4: Biofouling on the ship hull portion.

1.3.1. Stages in biofouling

Figure-5: Steps in biofouling.

1. Formation of initial adsorbed film on surface immersed in water.

5
2. Adhering the micro-organisms like bacteria on the adsorbed film to form a biofilm.

3. Releasing of extra cellular polymeric substances consisting of proteins and polysaccharides

used for fixing micro and macro-organisms.

4. settlement and growth of larva and other macrofouling agent finally leading to biofouling
(Figure-5).

Biofouling on ship hulls causes extra drag force, increases total weight and
increases hydrodynamic drag thereby it leads to increased fuel consumption. In case of fouling
of the medical devices it may lead to problems ranging from nosocomial infections and blood
stream infections to the mortality of person who has incorporated these devices. Membrane
biofouling leads to clogging of the membranes and thereby decrease in the efficiency of
membrane performance.

1.4. Micro-organisms responsible for MIC

Some of the micro-organisms which are causing MIC are given in the table-2 below.
Among these bacteria and fungi are the most influencing due to their nature of easy survival
and reproducibility even in the extreme environments.

MICRO-ORGANISM SCIENTIFIC NAMES

Bacteria ✓ Sulfate Reducing Bacteria (SRB)
✓ DesulfoVibrio
✓ Leptothrix
✓ Acidithiobacillus
✓ Gallionella
Fungi ✓ Penicillium cyclospium
✓ Aspergillus niger
✓ Cladosporium resinae
✓ Paecilomyces varioti
Alge ✓ Blue Green Alge
Microbial Consortia ✓ Symbiotic activity among different
groups of microorganisms
Table-2: Microorganisms responsible for MIC.

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1.4.1. Bacteria

From the viewpoint of MIC, the bacteria which are causing

MIC has been classified into two types such as anaerobic and aerobic bacteria. Anaerobic
bacteria can function and metabolise the absence of oxygen whereas the aerobic bacteria will
function only in the presence of oxygen.

1.4.1.1. Sulphate reducing bacteria (SRB)

SRB is the group of micro-organisms which can reduce the sulphate ion
to the sulphide ion in the absence of oxygen (Figure-6). This bacterium generally cause
corrosion in the marine environment. The main mechanism is by cathodic depolarization
process. The reaction sequence is shown below.

Figure-6: Sulphate reducing bacteria (SRB).

Anode: 4𝐹𝑒 → 4𝐹𝑒 +2 + 8𝑒 −

Water Dissociation/Ionization: 8𝐻2 𝑂 → 8𝐻 + + 8𝑂𝐻 −

Cathodic reaction: 8𝐻 + + 8𝑒 − → 8𝐻2

Cathodic Depolarization resulting from SRB’s: 𝑆𝑂4−2 + 8𝐻 → 𝑆 2− + 4𝐻2 𝑂

Corrosion Products: 𝐹𝑒 +2 + 𝑆 2− → 𝐹𝑒𝑆; 3𝐹𝑒 +2 + 6𝑂𝐻 − → 3𝐹𝑒(𝑂𝐻)2

Overall Reaction: 4𝐹𝑒 + 4𝐻2 𝑂 + 𝑆𝑂4−2 → 3𝐹𝑒(𝑂𝐻)2 + 𝐹𝑒𝑆 + 2𝑂𝐻 − .

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 This is chemo-lithotrophic and chemo-organotrophic bacteria. In the absence
of SRB’s the iron dissolution and hydrogen reduction would occur eventually after some time
they come to an equilibrium. This equilibrium is continuously disturbed by these SRB’s by
scavenging the hydrogen gas that was generated by activating the sulphate ions thereby leading
to depolarization of the cathodic hydrogen evolution reaction.

1.4.1.2.Nitrate reducing bacteria (NRB)

This bacterium will use the nitrate as an electron acceptor and

reduces it to nitrogen via anaerobic process (Figure-7). These bacteria are heterotrophic in
nature. NRB will catalyse this reduction reaction and thereby it aggravates the corrosion
process. This bacterium will be active in the PH range of 7-8.8.

Figure-7: Nitrate reducing bacteria (NRB).

The reaction sequence is given below.

𝐹𝑒 → 𝐹𝑒 +2 + 2𝑒 −

𝑁𝑂3− + 𝑒 − + 2𝐻 + → 𝑁𝑂2− + 𝐻2 𝑂

2𝐻 + + 2𝑒 − → 𝐻2

𝑁𝑂2− + 𝐻2 → 𝑁𝐻2+ + 𝑂2−

𝐹𝑒 +3 + 𝑃𝑂4−3 → 𝐹𝑒𝑃𝑂4

The common bacteria that come under this NRB are: Achromobacter, Bacillus,
Corynebacterium.

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1.4.1.3. Iron oxidizing bacteria (IOB)

IOB (Figure-8) is aerobic bacteria, and this will generally act

as a terminal electron acceptor and this will take the electrons that are generated due to iron
oxidation for their survival and growth. Among all the energy sources available iron oxidation
is the lowest possible Gibbs free energy change for the process. These can be lithotrophic or
heterotrophic depending on the source of their energy and carbon. Examples of this process are
organisms (such as Leptothrix discophora and Sphaerotilus natans), which produce proteins or
enzyme systems that actively catalyze the oxidation of Fe but do not receive any energy
benefits from this.

Figure-8: Iron oxidizing bacteria (IOB).

1.4.1.4. Manganese oxidizing bacteria (MOB)

This bacterium (Figure-9) is common in the drinking water systems. These

will catalyze the Manganese oxidation reaction and finally lead to formation of manganese
oxides. The reaction sequence is given in the below.

𝑀𝑛2+ + 0.5𝑂2 + 𝐻2 𝑂 → 𝑀𝑛𝑂2 (𝑆) + 2𝐻 +

9
 𝑀𝑛2+ + 0.25𝑂2 + 0.75𝐻2 𝑂 → 𝑀𝑛𝑂𝑂𝐻(𝑆) + 2𝐻 +

3𝑀𝑛2+ + 0.5𝑂2 + 3𝐻2 𝑂 → 𝑀𝑛3 𝑂4 (𝑆) + 6𝐻 +

Figure-9: Manganese oxidizing bacteria.

1.5.Industrial methods to control biofouling

In industry there are several methods that have been followed till now. Some of them
are listed below.

✓ Physical methods.
✓ Mechanical methods
✓ Biological methods
1.5.1. Physical methods

Physical methods include those which uses the high velocity water jets
against the fouled surfaces. Due to this impact of high velocity jets the unwanted fouling’s will
get removed and thereby the surfaces will become clean. This process was shown in the below
figure-10.

Figure-10: Physical method of controlling biofouling.

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1.5.2. Mechanical methods

In mechanical methods a high frequency ultrasonic waves

(Figure-11) were used to clean the surfaces contaminated with fouling’s. The frequency is
generally grater than 18KHz. Ultrasound waves can propagate through the fouling medium,
and the mechanical vibration creates an elastic medium of sound and pressure waves that
transfer energy to the medium. The sound waves create oscillating regions with the support of
cavitation. Cavitation bubbles lead to hot spots and increase the local temperatures and
pressures up to 6000K under 10μs. Ultrasound technology that uses sound waves had been
shown to play a crucial impact on different bacteria and barnacle species with their mortality
and growth inhibitory at different frequencies.

Figure-11: Mechanical method of controlling biofouling.

1.5.3. Biological methods

Figure-12: Biocidal application for biofouling removal.

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 In these methods biocides were applied on top of the materials surfaces
thereby they result in killing the micro-organisms present in the biofilms. Due to this affect
they will reduce the fouling of the surfaces. This is depicted in the below figure-12.

2. LITERATURE REVIW

The industrial methods that are being used are having lot of
disadvantages such as frequent maintenance cost, harmful nature of biocides for non-targeted
marine ecosystem. Even the organic paints are not serving the long-term purpose because of
hydrolysis by water after a long time. The development of the coatings generally aims at
modifying the nature of the surface in terms of macro-texture, surface energy, wettability,
surface charge and surface chemical composition. Generally, the coatings which are applied on
the metal surface should have the low contact angle (Hydrophobic surface). This is shown in
the below figure-13.

Figure-13: Nature of the surfaces.

Now a days people are intrested in developing the metallic coatings on the surface of the metal
for anti-fouling and MIC resistance. In the below sections the Metal matrix nano composite
coatings that have been developed are discueesd.

2.1. Anti-Fouling Behaviour of Silver nanoparticles on Graphene sheet

In this current research paper, the graphene silver nano

composite was produced by the hydrothermal synthesis route. Graphene nano material and
silver nitrate were mixed in various proportions (Table-3) and stirred for 30 min to produce
uniform dispersion. The SEM micrograph of the as fabricated nano composite was shown in
the below figure-14.

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 Name of Mass of Mass of Weight ratio of Graphene-Ag nanocomposite
the Graphene (g) AgNo3 (g) graphene:Ag
Ag wt% Average Ag nanoparticle
sample precursor
diameter (nm)
GAg-1 0.2 0.063 3:1 1.3 86.1
GAg-2 0.2 0.20 1:1 1.6 72.1
GAg-3 0.2 0.80 1:4 2.5 76.0
GAg-4 0.2 2.00 1:10 4.9 76.5

Table-3: Weight ratios of graphene and silver precursor.

Figure-14: SEM micrographs.

SEM imaging reveals that the graphene sample consisted of

few-layer graphene (FLG) flakes with pristine surfaces. This is due to the sonochemical-
assisted exfoliation of graphite flakes using the water-ethanol mixture, which gently exfoliates
the graphite, resulting in the preservation of large pieces of pristine graphene on the micron
scale. After the addition of silver nitrate and undergoing hydrothermal reduction with citrate,
the Ag particles are supported on the surface of the micron sized FLG flakes.

To evaluate the antifouling effects of graphene-Ag composites, a static

biofilm assay was carried out using H. pacifica, a common marine fouling bacterium. As shown
in Figure-15, the Graphene Ag materials inhibit the attachment of biofilm from H. pacifica
after an incubation period of 24 h. it shows a decrease in the optical density of crystal violet

13
dye for Graphene Ag samples, in contrast to the untreated control and pure graphene sample.
The surface associated crystal violet dye attaches to the biofilm mass. A higher optical density
reading is concomitant with a higher quantity of bacterial biofilm matter. Figure-15 revealed
that all 4 Graphene Ag samples exhibited potent inhibitory effect on the production of biofilm
by H. pacifica, with an average inhibition of 67.4 ± 1.8% for GAg-1, 86.9 ± 1.3% for GAg-2,
95.6 ± 0.1% for GAg-3 and 99.6 ± 0.1% for GAg-4 (P < 0.05, Student’s t-test). On the other
hand, the graphene material and graphene-free bulk silver exhibited little to no inhibitory effect
on the attachment of biofilm from H. pacifica. These results show that graphene and graphene-
free bulk silver on its own does not possess any antifouling quality.

Figure-15: Biofouling behaviour in H. Pacifica bacteria.

The above results shows that the biofilm Formation tendency

decreases with increase in % of Ag Nano-particles. This has been attributed to the dissolution
of outer cell wall of Bacteria leading to leakage of vital cellular constituents thereby cell death.

2.2. Anti-Fouling Behaviour of Silver Nano-particles on Graphene Oxide sheet

The graphene oxide was made by the process of modified Hummers

method. The silver nano particles were produced my Turkevich method and the composite was
made by preparing a colloidal solution followed by centrifugation technique. TEM micrograph
of the composite is shown in the below figure-16. It shows the monolayer of spherical silver
nano particles attached to graphene oxide. Average size of the silver nano particles was
reported as 10nm diameter. The anti-microbial testing was done by agar diffusion method for

14
four gram positive (Bacillus cereus ATCC 14579, Staphylococcus aureus ATCC 1901,
Corynebacterium fimi NCTC 7547 and Listeria monocytogenes ATCC 6477) and four gram negative
bacteria (E. coli ATCC 8739, Salmonella typhimurium ATCC 14078, Salmonella enteritidis ATCC
13076 and P. aeruginosa-food isolate). In this the pure graphene oxide has no effect on microbial
inhibition whereas the Ag nano particle embedded in the graphene oxide shows a significant
anti-microbial effect.

Figure-16: Morphology of composite in TEM.

Figure-17: Time-kill curves for (a) graphene oxide and (b) graphene oxide and Ag-
particle composite.

The above figure shows the time-kill curves for P. Aeruginosa bacteria at various
concentrations of graphene oxide and Ag-nano particle embedded graphene oxide nano
composite. Figure-17(a) shows that there is no significant anti-microbial nature of graphene

15
oxide and figure-17(b) shows that Ag-nano particle embedded graphene oxide nano composite
shows for concentrations of 2.5 and 5.0 µg/mL.

The Ag nano particles will enter into the bacterial cells by destabilising the cell wall and
membrane and thereby it leads to interaction of Ag nano particles with the DNA, subsequently
it leads to damaging the DNA replication process and resulting in the death of bacteria.

2.3. Anti-Fouling Behaviour of Silver Nano-particles in Ni-Matrix on Cu

In the current paper the Ag nano particles were introduced in the

Ni matrix as metal matrix nano composite coating on the Cu-substrate through dispersing the
controlled amounts of Ag nano particles in Ni matrix via electrodeposition route. Typical
compositions include Ni-0.25%Ag and Ni-0.75%Ag. The electrochemical polarization, anti-
fouling behavior of these coatings were studied.

Figure-18: Microstructure of Ag nano particles.

Figure-19: SEM images of coatings.

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 Figure-18 depicts the characteristics of as-prepared Ag nano particles.
Figure-18(a) shows the Ag nano particle crystal structure. The ring pattern signifies the nano
range of the prepared particles. SEM images of coatings with pure Ni, Ni-0.25 at% Ag and Ni-
0.75 at% Ag is shown in figure-19. It depicts the uniform and defect free nature of the coatings.

Figure-20: Electrochemical corrosion behaviour.

Above figure-20 depicts the electrochemical corrosion behaviour

before and after exposure to SRB for two weeks duration. Tables-4 and 5 signifies the
electrochemical corrosion parameters from this experimentation.

Coating Ecorr (V) Icorr (µA/cm2) Βa (V/dec) Βc (V/dec) Corrosion rate (mpy)
Pure Ni -0.05 3.9 0.053 0.111 1.657
Ni-0.25%Ag -0.035 1.014 0.065 0.151 0.431
Ni-0.75%Ag -0.044 3.21 0.062 0.112 1.364
Table-4: Electrochemical corrosion test results before biofouling.

Coating Ecorr (V) Icorr (µA/cm2) Βa (V/dec) Βc (V/dec) Corrosion rate (mpy)
Pure Ni -0.12 8.736 0.102 0.159 3.712
Ni-0.25%Ag -0.049 1.784 0.115 0.170 0.758
Ni-0.75%Ag -0.047 3.723 0.146 0.118 1.582
Table-5: Electrochemical corrosion test results after biofouling.

Figure-21: SEM images of coatings after SRB exposure.

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 Upon exposure to SRB (Desulfotomaculum nigrificans and Desulfovibrio
desulfuricans) for 2 weeks Ni-0.75 at% Ag was found to have maximum corrosion resistance.
This was attributed to the greater amount of silver nano particles and their anti-microbial
nature. Figure-21 shows the microstructure of coating after biofouling behaviour in the SRB.
In this figure (a), (b), (c) and (d) corresponds to pure Cu substrate, Pure Ni, Ni-0.25 at% Ag
coatings and Ni-0.75 at% Ag respectively. Pure Cu has maximum tendency of biofouling and
it decreased with increase in Ag nano particles.

Figure-22: Growth behaviour of SRB.

The above figure-22 shows the microbial growth behaviour in the presence
of Ag+ and Ag nano particles respectively through optical density measurements. In the above
curves control represents a condition without coating. With increase in the Ag nano particle
content in the medium the SRB cell count was found to decrease. The minimum inhibitory
nanoparticle concentration lies between 10 and 15 mgl−1.

2.4. Copper-graphene oxide composite coatings for corrosion protection of mild steel

In the current research article graphene oxide (GO) was prepared by

modified Hummer’s method. DC current power source was used to deposit both pure Cu and
Cu+ graphene oxide coatings on mild steel (MS) substrate using sodium lauryl sulphate (SLS)
as the surfactant. Table-6 gives the description about the deposited coatings. The figure-23
shows the morphology of the coatings. Cu-GO1, Cu-GO2 and Cu-GO3 corresponds to
deposited coatings from B-1, B-2 and B-3 respectively. Thickness of coating was found to be
25µm. With the addition of GO granular morphology of Cu was modified. The below figure-
24 shows the electrochemical behaviour of As-deposited coatings and after exposure in 3.5%
NaCl solution.
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Plating Bath Bath Constituents Concentration Coating Operating Parameters
(g/L)
Primary Bath 1.CuSO4·5H2O 120 Cu Anode: Platinum foil
(B) 2.SLS 0.288 Cathode: Mild steel
B-1 B+GO 0.125 Cu-GO1 Cathodic current density: 25 mA cm−2
B-2 B+GO 0.25 Cu-GO2 Deposition time: 10 min
B-3 B+GO 1 Cu-GO3 Cl− content (using HCl): 35 ppm
pH: 2.4
Bath temperature: 25 ± 2°C

Table-6: Electrodeposition conditions.

Figure-23: Morphology of coatings.

Figure-24: Electrochemical corrosion behaviour.

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 Sample Ecorr (V) Icorr (µA/cm2) Βa (V/dec) Βc (V/dec) Corrosion rate (mpy)
Bare MS -0.648 295.3 0.09 0.14 135.15
Cu/MS -0.579 62.89 0.32 0.06 57.53
Cu-GO-1/MS -0.537 21.28 0.17 0.11 19.46
Cu-GO-2/MS -0.505 11.13 0.15 0.11 10.18
Cu-GO-3/MS -0.321 7.24 0.11 0.14 6.62
Table-7: Electrochemical corrosion test results of As-deposited coatings.

Sample Ecorr (V) Icorr (µA/cm2) Βa (V/dec) Βc (V/dec) Corrosion rate (mpy)
Bare MS -0.679 316.50 0.99 0.02 144.85
Cu/MS -0.595 68.60 0.20 0.13 62.76
Cu-GO-1/MS -0.545 24.07 0.18 0.12 22.08
Cu-GO-2/MS -0.536 13.23 0.21 0.14 12.11
Cu-GO-3/MS -0.458 10.03 0.19 0.17 9.18
Table-8: Electrochemical corrosion test results after exposure to 3.5% NaCl.

From the above tables-7 and 8 results it is evident that with the incorporation
of GO the corrosion resistance was increased and this was mainly attributed to the impervious
nature of GO to the Cl- attack and the strong [220] texture.

3. WORK PLAN

Steel is a green material used in several industries

despite of having ss many useful engineering properties it is suffering from MIC due the
formation of biofouling on its surface due to its contact with the environment. As the silver
nano particles are having the anti-microbial nature and graphene has the high corrosion
resistance the present work aims at producing the metal matrix nano composite coatings on the
steel substrate. The metal matrix is ranging from a simple Fe-Cu binary system to the High
entropy alloy system based on the electrochemical corrosion behaviour of the matrix as well
as electrochemical compatibility between the matrix and incorporated Ag NPs and GO
nanosheets. Ag nano particles and graphene oxide nanosheets will be chemically synthesised
and electrophorectically incorporated into metal matrix during electrodeposition. The
flowsheet of the work plan is presented in the figure-25 below.

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 Figure- 25: Flow sheet of the work plan.

The electrodeposited coatings will be developed on the steel substrate and they will be
subsequently tested for the biofouling behaviour in SRB and NRB medium. The as deposited
and the samples after fouling exposure test will be characterized for morphology,
microstructure, texture and chemical analysis. Subsequently corrosion studies will also bw
conducted on all these samples. In the corrosion behaviour the polarization, electrochemical
impedance spectroscopy and biofouling characteristics of the coatings will be investigated.
Finally, after collecting all the information a mechanistic model will be developed through the
correlation between the microstructure, composition and corrosion behaviour.

4. CONCLUSIONS
❖ Silver nano particles are exhibiting the excellent anti-microbial properties and graphene
oxide is having good general corrosion resistance.
❖ As a result, these were incorporated in metal matrix leading to excellent resistance to
biofouling and MIC.
❖ Electrodeposition is having good industrial scalability and ease to control the structure
and morphology this will be used as the fabrication method for making this nano
composite coating.

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5. REFERENCES
➢ Biofouling and Mitigation Methods: A Review Gorkem Gizer Umur Önal, Manoj Ram,
Nurettin Sahiner.
➢ Biocorrosion, Biofouling, and Advanced Methods of Controlling Them. T. A. Kochina,
Yu. A. Kondratenko, O. A. Shilova and D. Yu. Vlasov.
➢ Gaines, H.A., J. Eng. Ind. Chem., 1910, vol. 2, p. 128.
➢ Yebra, D.M.; Kiil, S.; Dam-Johansen, K. Antifouling Technology—Past, Present and
Future Steps towards Efficient and Environmentally Friendly Antifouling Coatings.
Prog Org Coatings 2004, 50, 75–104.
➢ Copper-graphene oxide composite coatings for corrosion protection of mild steel in
3.5% NaCl Thin Solid Films Volume 636, 31 August 2017, Pages 107-115.
➢ Microstructure, electrochemical behaviour and bio-fouling of electrodeposited nickel
matrix-silver nanoparticles composite coatings on copper Y. Raghupathy, K.A.
Natarajan, Chandan Srivastava Surface and Coatings Technology Pages 266-275.
➢ Anti-adhesion and antibacterial activity of silver nanoparticles supported Andreia
Fonseca de Fariaa∗, Diego Stéfani Teodoro Martineza, Stela Maris Meister Meirab.
➢ Green synthesis of graphene-silver nanocomposites and its application as a potent
marine antifouling agent Maxine Swee-Li Yee a∗, Poi-Sim Khiew a∗, Wee Siong Chiu
b, Yuen Fen Tan c, Yih-Yih Kok d, Chee-Onn Leong.

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