A study of Graphene coatings as corrosion protective barrier for mild

steel in different chemical environments

Dissertation
Submitted in partial fulfillment of the requirements of
BITS G629T Dissertation

By
Allampalli Satya Sai Pavan
(2013H101012G)
Under the supervision of
Prof. Sutapa Roy Ramanan
Professor Department of Chemical Engineering

BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE, PILANI,

K.K BIRLA GOA CAMPUS

Acknowledgements
I have taken efforts in this project. However it would have not been possible without the kind of
support and help of many individuals. I would like to express my sincere thanks to all of them.
I am highly indebted to my Dissertation guide Prof. Sutapa Roy Ramanan for her guidance,
constant support and motivation.
I would like to express my gratitude towards other members of chemical engineering department
for their kind co-operation and encouragement which helped in completion of my project.
I would like to express my special thanks to my friends and last but not least my parents for their
continuous support and motivation during all times.

Place: BITS-Pilani, Goa Campus

Date: 29/4/2015

Allampalli Satya Sai Pavan

ii

Certificate
This is to certify that the Dissertation entitled A study of Graphene coatings as corrosion
protective barrier for mild steel in different chemical environments and submitted by
Allampalli Satya Sai Pavan ID No. 2013H101012G in partial fulfillment of the requirement of
BITS G629T Dissertation embodies the work done by him/her under my supervision.

Date:

Signature
Sutapa Roy Ramanan
Professor Chemical Engg Dept.

iii

Abstract
Mild Steel is one of cheapest and widely used engineering material. It is used in making chemical storage
vessels, tanks, machine parts of various equipments etc. However it has very low corrosion resistance.
Research has been going on to develop an anticorrosion coating for mild steel which doesnt largely the
change properties of mild steel once coating has been applied. Graphene a single atomic monolayer of
graphite, possess a unique combination of properties that are ideal for anticorrosion coatings. Graphene is
chemically inert and stable in ambient atmosphere up to 400C and can be grown on meter scale and can
be transferred on to metal substrates. Both single-layer and multilayer graphene films are exceptionally
transparent (>90% for layered graphene), so graphene coatings do not bring changes in the optical
properties of underlying metal. Graphene was synthesized using both Hummers and Modified Hummers
method. Graphene was then dispersed in 1- propanol using ultra sonic bath. The potential of graphene
coatings to serve as protective coating for mild steel against corrosion in various environments were
investigated. The graphene coatings were deposited on mild steel surface by dip coating technique. Multi
layers of graphene were coated on metal surface. The corrosion effect of these graphene coatings was
determined by open circuit potential test. Corrosion rates were determined using tafel analysis. Obtained
results indicated that graphene coating was showing anticorrosion coating properties in various
environments like acidic, basic and neutral media. Furthermore graphene was prepared using modified
method and corrosion test was carried in a similar fashion. These results were much better than those
obtained from previous. Multilayered coating (>4 layer coating) was not effective on mild steel surface as
van der Waals forces between two graphene layers come into play and coating was not adhering to mild
steel.

iv

List of Figures and Tables

Table 1: Different forms of corrosion

Table 2: Chemicals and amount of chemicals used in Modified Hummers Method

Table 3: Chemicals and amount of chemicals used in Hummers Method

Figure 4.1: Uncoated metal tested in Distilled Water

12

Figure 4.2: Uncoated metal tested in Tap Water

12

Figure 4.3: Uncoated metal tested in NaCl (Salt Water)

13

Figure 4.4: Uncoated metal tested in NaOH

13

Figure 4.5: Uncoated metal tested in HCl

14

Figure 4.6: Metal coated (1 layer) with graphene (Hummers Method) tested in Distilled
Water
Figure 4.7: Metal coated (1 layer) with graphene (Modified Hummers Method) in Distilled
Water
Figure 4.8: Metal coated (1layer) with graphene (Hummers Method) tested in Tap
Water
Figure 4.9: Metal coated (1layer) with graphene (Modified Hummers Method) in Tap
Water
Figure 4.10: Metal coated with (1layer) graphene (Hummers Method) tested in NaCl
Figure 4.11: Metal coated with (1layer) graphene (Modified Hummers Method) in NaCl

15
15
16
16
17
17

Figure 4.12: Metal coated (1layer) with graphene (Hummers Method) tested in HCl

18

Figure 4.13: Metal coated (1layer) with graphene (Modified Hummers Method) tested in HCl

18

Figure 4.14: Metal coated (1layer) with graphene (Hummers Method) tested in NaOH

19

Figure 4.15: Metal coated (1layer) with graphene (Modified Hummers Method) tested in NaOH

19

Figure 4.16: Metal coated (2 Layer) with graphene (Hummers Method) tested in Distilled
Water
Figure 4.17: Metal coated (2 Layer) with graphene (Modified Hummers Method) tested in
Distilled Water

20

Figure 4.18: Metal coated (2 Layer) with graphene (Hummers Method) tested in Tap Water
Figure 4.19: Metal coated (2 Layer) with graphene (Modified Hummers Method) tested in
Tap Water

21
21

Figure 4.20: Metal coated (2 Layer) with graphene (Hummers Method) tested in NaCl

22

Figure 4.21: Metal coated (2 Layer) with graphene (Modified Hummers Method) tested in NaCl

22

20

Figure 4.22: Metal coated (2 Layer) with graphene (Hummers Method) tested in HCl

23

Figure 4.23: Metal coated (2 Layer) with graphene (Modified Hummers Method) tested in HCl

23

Figure 4.24: Metal coated (2 Layer) with graphene (Hummers Method) tested in NaOH

24

Figure 4.25: Metal coated (2 Layer) with graphene (Modified Hummers Method) tested in
NaOH

24

Figure 4.26: Metal coated (3 Layer) with graphene (Hummers Method) tested in Distilled Water

25

Figure 4.27: Metal coated (3 Layer) with graphene (Modified Hummers Method) tested in Distilled
Water

25

Figure 4.28: Metal coated (3 Layer) with graphene (Hummers Method) tested in Tap Water

26

Figure 4.29: Metal coated (3 Layer) with graphene (Modified Hummers Method) tested in Tap
Water

26

Figure 4.30: Metal coated (3 Layer) with graphene (Hummers Method) tested in NaCl

27

Figure 4.31: Metal coated (3 Layer) with graphene (Modified Hummers Method) tested in NaCl

27

Figure 4.32: Metal coated (3 Layer) with graphene (Hummers Method) tested in HCl

28

Figure 4.33: Metal coated (3 Layer) with graphene (Modified Hummers Method) tested in HCl

28

Figure 4.34: Metal coated (3 Layer) with graphene (Hummers Method) tested in NaOH

29

Figure 4.35: Metal coated (3 Layer) with graphene (Modified Hummers Method) tested in NaOH

29

Table 4: % decrease in corrosion when tested in Distilled Water

30

Table 5: % decrease in corrosion when tested in Tap Water

30

Table 6: % decrease in corrosion when tested in NaCl

30

Table 7: % decrease in corrosion when tested in HCl

30

Table 8: % decrease in corrosion when tested in NaOH

31

Figure 4.36: Plot between corrosion rate and number of coatings

Figure 4.7.1: Bare metal when exposed to NaCl environment
Figure 4.7.2: 3 layer graphene coated metal exposed to NaCl environment
Figure 4.8.1: XRD plot

31
32
32
33

vi

Contents
Title Page

Acknowledgements

ii

Certificate

iii

Abstract

iv

List of Figures and Tables

Table of Contents

vi

1. Introduction

2. Literature Survey
2.1 Corrosion of Material

2.2 Types of Coatings

2.2.1 Metallic Coatings
2.2.2 Inorganic Coatings
2.2.3 Organic Coatings

3
3
3

2.3 Graphene
2.3.1 Introduction
2.3.2 Applications

4
4

2.4 Graphene Potential Candidate for Anticorrosion Coating

2.5 Types of Corrosion Tests

3. Experimental
3.1 Raw Materials
3.2 Synthesis of GO (Modified Hummers Method)
3.3 Reduction of GO using Sodium Borohydride
3.4 Synthesis of GO (Hummers Method)
3.5 Reduction of GO using Sodium Borohydride
3.6 Protocol for Dip Coating
3.7 Protocol for Corrosion Test
3.8 Characterization

7
7
7
8
8
9
10
11

4. Results and Discussion

4.1 Uncoated Metal
4.2 Graphene 1 Layer Coating
4.3 Graphene 2 Layer Coating

12
15
20
vii

4.4 Graphene 3 Layer Coating

4.5 Comparison of Results
4.6 Metal Coupons with more than 3 Layer Coatings
4.7 Characterization of Metal Coupon
4.8 Characterization of Graphene using XRD

25
30
31
32
33

5. Conclusions

34

6. References

35

viii

1. Introduction
Mild steel is cheapest and commonly used construction material. It has been extensively used for many
centuries in many areas for water pipes, vessels, tanks, docks and in process industries etc. Because of its
low nobility and structural defects mild steel corrodes quickly when it is exposed to different
environments (Pierre R et al 2007).
Depending on corrosion environment mild steel can be protected in many ways: by applying different
organic coatings, by using cathodic or anodic inhibitors, cathodic and anodic protection, by using
conductive polymeric coatings, by introducing a stable protective layer of inert metals etc. However,
organic coatings are expensive, inhibitors cannot be applied under certain conditions and polymeric
coatings are relatively thick and may change the physical properties of underlying materials.
Graphene, a single atomic monolayer of graphite, possess a unique combination of properties that can
potentially be ideal for anticorrosion coatings. Graphene is chemically inert and stable in ambient
atmosphere up to 400C (Dhiraj et al 2012) and can be grown on meter scale and can be transferred on
to metal substrates. Both single-layer and multilayer graphene films are exceptionally transparent (>90%
for layered graphene), so graphene coatings do not bring changes in the optical properties of underlying
metal (Blake P et al 2008). However, one thing that is lacking in literature is detailed investigations of
the effect that graphene on the electrochemical response of underlying metals. Little research has been
done on graphene as protection coating for steel. However, pure graphene was not used. Graphene was
mixed with different polymers and its anticorrosion ability was seen.
In this thesis work, graphene was synthesized from graphite oxide by using Hummers and Modified
Hummers method instead of direct growth of graphene layers on metal surfaces by Chemical Vapor
Deposition (CVD) technique. Graphene was then dispersed in 1- propanol using ultra sonication bath.
Graphene coating is amenable to dipping on a clean metal. The heat treatment of coated metal is needed
to obtain a proper protective film.
The proposal of this thesis provides an important insight of how effectively graphene can behave as
anticorrosion coating for mild steel. Quality of graphene produced by Hummers and Modified Hummers
method was evaluated, by comparing corrosion rates of metal coupons.

2. Literature Survey
2.1 Corrosion of Material
Corrosion is defined as the destruction or deterioration of a material because of reaction with its
environment. Corrosion can be fast or slow. For example 18-8 stainless steel is badly attacked in
hours by polythionic acid. Deterioration of metal by physical causes is not called as corrosion it is
referred as erosion. Rusting applies to the corrosion of iron or iron base alloys with the formation of
corrosion products largely containing hydrous ferric oxides. Nonferrous metals therefore corrode does
not rust.
Practically all environments are corrosive to some degree. In general inorganic materials are more
corrosive than organic materials. Higher temperatures and pressures usually involve more severe
corrosion conditions. Materials are susceptible for different types of corrosion such as uniform
corrosion, pitting corrosion and filiform corrosion etc. The type of corrosion depends on metal alloy
composition and the surrounding medium.
Types of Corrosion

Definition

Uniform Attack

It is normally characterized by chemical or

electrochemical reaction that proceeds uniformly
over the entire exposed area.

Galvanic Corrosion

A potential difference usually exists between two

dissimilar metals when they are immersed in
corrosive or conductive solution. Electrons start to
flow due to potential difference and less corrosion
resistant metal starts to get corroded.

Crevice Corrosion

Intensive localized corrosion frequently occurs

within crevices and other shielded areas on metal
surfaces exposed to corrosives. This type of attack
is usually associated with small volumes of
stagnant solution caused by holes, gasket
surfaces, crevices under bolts and rivet heads.

Filiform Corrosion

This is a special type of crevice corrosion. It

occurs under protective films and for this reason it
often referred as underfilm corrosion. This type of
corrosion doesnt affect metals strength. It affects
only surface appearance.

Pitting

Pitting is form of extremely localized attack that

results in holes in the metal. It causes equipment
to fail because of perforation.

Table 1: Different forms of corrosion

2.2 Types of Coatings

2.2.1

Metallic coatings

Metal coatings are applied by dip coating, electro plating, spraying. The selection of a coating
process depends on several factors, including corrosion resistance that is required, the anticipated
lifetime of the coated material and environmental considerations. Hot dipping is carried out by
immersing the metal on which the coating is to be applied, usually steel, in a bath of molten metal
that is to constitute the coating, most commonly zinc, but also aluminum and aluminum-zinc
alloys. In electroplating the substrate or the base metal is made cathode in an aqueous electrolyte
from which the coating is deposited. A wide variety of coatings can be applied by electro plating
for example zinc, cadmium, copper, nickel etc.
2.2.2 Inorganic coatings
Vitreous enamels, glass linings and porcelain enamels are all essentially glass coatings of suitable
coefficient of expansion fused on metals. Glass in powdered form (as glass frits) is applied to a
pickled or otherwise prepared metal surface, then heated in a furnace at a temperature that softens
the glass and allows it to bond to the metal. Several coats may be applied Vitreous enamel
coatings are mostly used on steel, but some coatings are possible on copper, brass and aluminum.
Portland cement coatings have advantage of low cost, ease of application or repair. These
coatings can be applied by centrifugal casing, by toweling or by spraying. Usual thickness ranges
from 5 to 25mm, thick coatings are usually reinforced with wire mesh. These coatings are used to
protect cast iron and steel water pipelines on water or soil side or both. These are also used as
interior of oil tanks and chemical storage tanks.
Chemical conversion coatings are protective coatings formed in situ by chemical reaction with
the metal surface. They include special coatings such as PbSO4 which forms when lead is
exposed to sulfuric acid and iron fluoride which is formed when steel containers are filled with
hydrofluoric acid ( >65% HF)
2.2.3 Organic coatings
Synthetic resins like phenol-formaldehyde formulations which can withstand boiling water or
slightly higher temperatures are used in chemical industry by applying multiple coats, baked on,
for resisting a variety of corrosive media. Silicone and polyamide resins are useful at still higher
temperatures. Alkyd resins, because of favorable cost, fast-drying properties and durability have
found wide applications for protecting the metal surfaces of machinery and home appliances.
Vinyl resins have good resistance to penetration by water. Their resistance to alkali makes them
useful for painting structures that are to be protected cathodically. Epoxy resins are also resistant
to alkali and to many other chemical media and have distinguishing property of adhering well to
metal surface. These epoxy coatings are mainly useful in coatings of ferrous pipelines. Plastic
coatings of vinyl or polyethylene can be applied as adhesive tape, particularly to buried metal
structures. Such tape finds practical use for coating pipe and auxiliary equipment including pipe
connections and valves exposed to soil. One of the most stable plastics in terms of resisting a
wide variety of chemical media is Teflon. It successfully resists aqua medium and boiling
concentrated acids such as HF, H2SO4, and HNO3. It resists boiling concentrated alkalis, gaseous
chlorine and all organic solvents up to 250C.
3

2.3 Graphene
2.3.1 Introduction
Graphene is a thin layer of pure carbon; it is single, tightly packed layer of carbon atoms that are
bonded together in a hexagonal honeycomb lattice. In more complex terms it is an allotrope of
carbon in the structure of planar sp2 bonded atoms with a C-C bond length of 0.142 nanometers
and with an inter planar spacing of 0.335 nanometers.
It is the thinnest known compound to man at one atom thick. It is the lightest known material
(with 1 square meter coming in around 0.77 milligrams), the strongest compound (between 100300 stronger than steel and with a tensile stiffness of 150,000,000), best conductor of heat at
room temperature and best conductor of electricity.
With such kind of exceptional properties it is obvious that Graphene is being currently used in
many fields like biological engineering, optical electronics, ultra filtration, composite materials,
photovoltaic cells, energy storage device.
2.3.2 Applications
2.3.2.1 Biological engineering
With graphene offering a large surface area, high electrical conductivity, thinness and strength, it
would make a good candidate for the development of fast and efficient bioelectric sensory
devices, with the ability to monitor such things as glucose levels, hemoglobin levels, cholesterol
and even DNA sequencing.
2.3.2.2 Optical electronics
Graphene is an almost completely transparent material and is able to optically transmit up to
97.7% of light. It is also highly conductive, as we have previously mentioned and so it would
work very well in optoelectronic applications such as LCD touch screens for smart phones, tablet
and desktop computers and televisions.
2.3.2.3 Ultrafiltration
Another standout property of graphene is that while it allows water to pass through it, it is almost
completely impervious to other liquids and gases (even relatively small helium molecules). This
means that graphene could be used as an ultrafiltration medium to act as a barrier between two
substances.
2.3.2.4 Composite materials
Graphene is strong, stiff and very light. Currently, aerospace engineers are incorporating carbon
fiber into the production of aircraft as it is also very strong and light. However, graphene is much
stronger whilst being also much lighter. Ultimately it is expected that graphene is utilized
(probably integrated into plastics such as epoxy) to create a material that can replace steel in the
structure of aircraft, improving fuel efficiency, range and reducing weight. Due to its electrical
conductivity, it could even be used to coat aircraft surface material to prevent electrical damage
resulting from lightning strikes.
2.3.2.5 Energy storage
One area of research that is being very highly studied is energy storage. While all areas of
electronics have been advancing over a very fast rate over the last few decades, the problem has
always been storing the energy in batteries and capacitors when it is not being used. Graphene
based micro-supercapacitors will likely be developed for use in low energy applications such as
4

smart phones and portable computing devices and could potentially be commercially available
within the next 5-10 years.
2.4 Graphene potential candidate for anticorrosion coating
As graphene possesses some exceptional properties mentioned above, it can be used in many
fields. However there are some special properties which make graphene a potential candidate for
anticorrosion coatings. To date the ability of graphene to serve as effective protection barrier has
not been widely pursued. In such a context, if graphene can be used as a coating on metals, it can
not only provide the opportunity to have an extremely light weight coating that does not
significantly alter optical properties or decrease bulk thermal/electrical conductivity but can
potentially halt the formation of oxide layer on metal surfaces.
Graphene is considered inert under conditions where other protective coatings will undergo rapid
chemical reactions. This property is due to graphene film is impermeable to gas molecules
(Raman Singh et al 2012). Along with high inherent capacity graphene also provides large
surface which means only small quantities of this material is required to coat metal surfaces.
Graphene also provides oxidation resistance while its hydrophobocity prevents hydrogen bonding
with water. Furthermore graphene being thermally stable even at high temperatures (around
400C), where other protective coatings will be thermally degraded makes graphene a possible
candidate for anticorrosion coating at higher temperatures too.
Corrosion can be inhibited or controlled by introducing a stable protective layer made of inert
materials, conductive polymers or even thiol based monolayer. However these protective layers
have many limitations like thiol monolayer cannot be used for temperatures greater than 100C
(Chang et al 2014). Polymeric coatings are relatively thick and will significantly change the
physical properties of the underlying material. Graphene being monolayer of graphite possess a
unique combination of properties as mentioned above which make this material ideal for
anticorrosion coating. Both single and multi layered (up to 4 layers) are exceptionally transparent
(>90% transmittance for 4 layered graphene) thus graphene coatings does not disturb the optical
properties of underlying material.
Combination of all these exceptional properties of graphene gives us a chance to explore
graphene as anticorrosion coating.

2.5 Types of Corrosion Tests

Corrosion tests are mainly divided into electrochemical tests and non electrochemical tests.
Electrochemical tests are non destructive tests and can be completed quickly. Whereas non
electrochemical tests are destructive tests and takes lot of time to determine corrosion rate.
2.5.1 Non Electrochemical Test
These tests include salt spray test, immersion test etc.
2.5.1.1 Salt Spray Test
Salt spray test is a popular test used to check the corrosion resistance of materials and surface
coatings. It is an accelerated test that produces corrosive attack to coated samples. Results are
reported in hours (number of hours without corrosion appearance)
2.5.1.2 Immersion Test
Polished coupons are immersed in corrosive environment for particular time period of 14, 28 and
42 hours. After that these coupons are taken out and dried. Then coupons are weighed to
determine weight loss and corrosion rate.
2.5.2 Electrochemical Test
These tests include Open Circuit Potential,Impedance
2.5.2.1 Open Circuit Potential
The open circuit potential (also referred to as the equilibrium potential, the rest potential, or the
corrosion potential) is the potential at which there is no current; that is, experiments based on the
measurement of the open circuit potential are potentiometric experiments.
2.5.2.2 Impedance
Measurement of impedance of corroding electrode has become important in corrosion prediction
for such diverse applications as coatings and corrosion rate estimation in low conductivity media.
As most commonly practiced an electrode is subjected to small amplitude (5-10 mV) in
sinusoidal variation in the voltage of varying frequency, usually about corrosion potential.

3. Experimental
3.1 Raw Materials
Graphite powder with 99% purity from Sigma Aldrich was used to prepare Graphite Oxide
(GO). KMnO4 99% was obtained from Fisher Scientific. NaNO3 (99% purity) and H2O2 (30%
Analytical Reagent) were obtained from S D Fine Chem Limited. NaBH4 with 99% purity from
Sigma - Aldrich was used as reducing agent to prepare Graphene.

3.2 Synthesis of GO (Modified Hummers Method)

Graphite powder was dried at 60C in a oven for 2 hours. This was done to remove moisture
present in graphite powder. 0.40 grams of graphite powder which was free of moisture and 0.30
grams of Sodium Nitrate were added in a 250ml glass beaker which was placed in an ice bath.
Then 14ml of Sulfuric Acid (98% conc.) was added slowly into 250ml beaker. This mixture was
under continuous magnetic stirring for 2 hours. Sulfuric Acid was added slowly (for 10 minutes)
in order to avoid excess heat. Next 1.8 grams of Potassium Permanganate was added slowly to
above solution while stirring in ice bath. Potassium Permanganate too was added slowly. This
solution was kept on stirring for 2 hours. Then solution was kept ageing for 5 days. At the end of
5th day 5 weight% H2SO4 was added. After 2 hours of magnetic stirring 16ml of H2O2 was added
to above solution and it turned to little yellow (during hydrogen peroxide addition). This light
yellow colored solution was magnetically stirred overnight. The solution then turned into brown
color and it was washed with 3 weight% H2SO4 (100 ml) by centrifugation. Centrifugation was
performed for 10 minutes at 10000 rpm. The solution obtained was Graphite Oxide.

3.3 Reduction of GO using Sodium Borohydride

13ml of graphite oxide was added with 35ml of distilled water into 250ml glass beaker. Then
10ml of 0.15 M Sodium Borohydride aqueous solution was added to above mixture. Temperature
of above solution was maintained at 80C for 2 hours while magnetically stirring. Final solution
was washed with 100ml distilled water by centrifugation. Then graphene is obtained in the form
of solution.
Chemical
Graphite Powder
Sodium Nitrate
Potassium Permanganate
Sulfuric Acid

Quantity used
0.40 grams
0.30 grams
1.80 grams
14ml before ageing
1ml after ageing
3ml during centrifugation
Hydrogen Peroxide
16ml
Distilled Water
19ml after ageing
97ml during centrifugation
35ml during reduction of GO
Sodium Borohydride
57 milligrams
Table 2: Chemicals and amount of chemicals used in Modified Hummers method

3.4 Synthesis of GO (Hummers Method)

2 grams of graphite powder was added to 46ml of H 2SO4 under continuous magnetic stirring in an
ice bath. 1 gram of Sodium Nitrate and 6 grams of Potassium Permanganate were added gradually
and successively. Ice bath was removed and suspension was allowed to come to room
temperature. 92ml of distilled water was added to this mixture. Following this, 20ml of Hydrogen
Peroxide was added and the solution turned bright yellow. The suspension was filtered and filter
cake was washed with distilled water and this solution was subjected to centrifugation.
Centrifugation was performed for 10 minutes at 10000 rpm.

3.5 Reduction of GO using Sodium Borohydride

13ml of graphite oxide was added with 35ml of distilled water into 250ml glass beaker. Then
10ml of 0.15 M Sodium Borohydride aqueous solution was added to above mixture. Temperature
of above solution was maintained at 80C for 2 hours while magnetically stirring. Final solution
was washed with 100ml distilled water by centrifugation. Then graphene is obtained in the form
of solution.
Chemical
Graphite Powder
Sodium Nitrate
Potassium Permanganate
Sulfuric Acid
Hydrogen Peroxide
Distilled Water

Quantity used
2 grams
1 gram
6 grams
46 ml
20 ml
92 ml for dilution of solution
100 ml during centrifugation
Sodium Borohydride
57 milligrams
Table 3: Chemicals and amount of chemical used in Hummers method

Difference between Modified Hummers and Hummers method was in ageing of solution. In
Modified Hummers method solution was kept for ageing (5 days) before addition of Hydrogen
Peroxide. This ageing was done to give more time for oxidation of solution. But in Hummers
method there is no ageing involved.
Graphene obtained from above solution was then dispersed in 1-propanol using ultra sonication
bath. This dispersed solution was used as anticorrosion coating for mild steel.

3.6 Protocol for Dip Coating

Take metal coupon and hang it in dip coating set up with the help of strings
Transfer the above prepared graphene solution to cultured bottle which is placed just
below the metal coupon which is hanging
Dip the coupon in the solution and start the motor, now metal coupon is lifted from the
solution at a speed of 0.0125 m/s
Take out the metal coupon which is hanging and put it in air oven at 75C for 10 minutes
After heat treatment of metal coupon take the metal coupon from the oven and allow it to
cool up to room temperature.
Repeat same steps (according to number of coats required) for multi layered coatings

3.7 Protocol for Corrosion Test

This test is done on CH Instruments, model no. 680
After completion of coating, put metal coupon in glass beaker containing electrolyte (test
solution)
Put Ag/AgCl electrode as reference and Platinum wire as counter electrode
Connect metal coupon (working electrode) with green wire, counter electrode to be connected
with red wire and reference electrode will be connected with white wire.
Start CH Instrument, then amp booster and connect the system with computer
Start CH Instrument software and click on techniques to select Open Circuit Potential Time
Run it for 400 seconds, and click on Controls
Open Circuit Potential
Equilibrium
Potential is displayed
Click on techniques to select Tafel Plot and give initial and final potential values by adding and
subtracting 0.2 to equilibrium potential
Select autosense and click on OK button
Click on play button to run Tafel Plot test for the system
When the run is completed, click on curve fitting to get exact plot
Click on analysis
Special Analysis
New dialogue box will open
Enter the values for molecular weight, valency and density of the metal used
Click on calculate to get the corrosion rate of material
By just changing the chemical in glass beaker (testing cell) we can calculate corrosion of same
metal coupon in different chemical conditions

10

3.8 Characterization
The microstructural characterization of metal coupons which were coated with graphene and
exposed to corrosive environment were carried out using Optical Microscope.
Morphological characterization of Graphene was carried out using X-Ray Diffraction (XRD)

11

4 Results and Discussion

After coating process was done corrosion rate was determined by following above mentioned protocol.
Corrosion test was carried in five different chemical media such as Distilled Water (pH 7.07), Tap Water
(pH 7.77), NaCl (3.5 wt %), HCl (0.1 N) and NaOH (1 M)

4.1 Uncoated Metal

This set of graphs show how uncoated metal behaves in five different media

Fig 4.1: Uncoated metal tested in Distilled Water

Fig 4.2: Uncoated metal tested in Tap Water

12

Fig 4.3: Uncoated Metal tested in NaCl (Salt Water)

Fig 4.4: Uncoated metal tested in NaOH (Basic Environment)

13

Fig 4.5: Uncoated metal tested in HCl (Acidic Environment)

14

4.2 Graphene 1 Layer Coating

Graphene prepared by both methods were coated on metal coupons and tests were carried out in five
different media

Fig 4.6: Metal coated with Graphene (Hummers method) tested in Distilled Water
As compared to uncoated metal corrosion rate is reduced by 90.4%

Fig 4.7: Metal coated with Graphene (Modified Hummers method) tested in Distilled
Water
As compared to uncoated metal corrosion rate is reduced by 85.2%
15

Fig 4.8: Metal coated with Graphene (Hummers method) tested in Tap Water
As compared to uncoated metal corrosion rate is decreased by 68.9%

Fig 4.9: Metal coated with Graphene (Modified Hummers Method) tested in Tap Water
As compared to uncoated metal corrosion rate is decreased by 80%

16

Fig 4.10: Metal coated with Graphene (Hummers Method) tested in NaCl
As compared to uncoated metal corrosion rate is reduced by 68.8%

Fig 4.11: Metal coated with Graphene (Modified Hummers Method) tested in NaCl
As compared to uncoated metal corrosion rate is decreased by 97.4%

17

Fig 4.12: Metal coated with Graphene (Hummers Method) tested in HCl
As compared to uncoated metal corrosion rate is decreased by 6.3%

Fig 4.13: Metal coated with Graphene (Modified Hummers Method) tested in HCl
As compared to uncoated metal corrosion rate is decreased by 60.4%

18

Fig 4.14: Metal Coated with Graphene (Hummers method) tested in NaOH
As compared to uncoated metal corrosion rate is decreased by 90.2%

Fig 4.15: Metal coated with Graphene (Modified Hummers method) tested in NaOH
As compared to uncoated metal corrosion rate is decreased by 78.6%

19

4.3 Graphene 2 Layer Coating

Metal coupons are coated double layer and tested in five different media

Fig 4.16: Metal coated with Graphene (Hummers method) tested in Distilled Water
As compared to uncoated metal corrosion rate is decreased by 91.1%

Fig 4.17: Metal coated with Graphene (Modified Hummers Method) tested in Distilled
Water
As compared to uncoated metal corrosion rate is decreased by 97.8%
20

Fig 4.18: Metal Coated with Graphene (Hummers Method) tested in Tap Water
As compared to uncoated metal corrosion rate is decreased by 80.9%

Fig 4.19: Metal coated with Graphene (Modified Hummers Method) tested in Tap Water
As compared to uncoated metal corrosion rate is decreased by 83.3%

21

Fig 4.20: Metal coated with Graphene (Hummers method) tested in NaCl
As compared to uncoated metal corrosion rate is decreased by 77.8%

Fig 4.21: Metal coated with Graphene (Modified Hummers Method) tested in NaCl
As compared to uncoated metal corrosion rate is decreased by 99.25%

22

Fig 4.22: Metal coated with Graphene (Hummers Method) tested in HCl
As compared to uncoated metal corrosion rate is decreased by 64.8%

Fig 4.23: Metal coated with Graphene (Modified Hummers Method) tested in HCl
As compared to uncoated metal corrosion rate is decreased by 74.1%

23

Fig 4.24: Metal coated with Graphene (Hummers method) tested in NaOH
As compared to uncoated metal corrosion rate is decreased by 97.8%

Fig 4.25: Metal Coated with Graphene (Modified Hummers Method) tested in NaOH
As compared to uncoated metal corrosion rate is decreased by 96.9%

24

4.4 Graphene 3 layer coating

Metal coupons are 3 layered coatings with Graphene and tests were conducted in 5 different media

Fig 4.26: Metal coated with Graphene (Hummers Method) tested in Distilled Water
As compared to uncoated metal corrosion rate is decreased by 92.1%

Fig 4.27: Metal coated with Graphene (Modified Hummers Method) tested in Distilled Water
As compared to uncoated metal corrosion rate is decreased by 98.9%
25

Fig 4.28: Metal coated with Graphene (Hummers Method) tested in Tap Water
As compared to uncoated metal corrosion rate is decreased by 83.3%

Fig 4.29: Metal coated with Graphene (Modified Hummers Method) tested in Tap Water
As compared to uncoated metal corrosion rate is decreased by 90%

26

Fig 4.30: Metal Coated with Graphene (Hummers Method) tested in NaCl
As compared to uncoated metal corrosion rate is decreased by 91%

Fig 4.31: Metal coated with Graphene (Modified Hummers Method) tested in NaCl
As compared to uncoated metal corrosion rate is decreased by 99.4%

27

Fig 4.32: Metal coated with Graphene (Hummers Method) tested in HCl
As compared to uncoated metal corrosion rate is decreased by 68.6%

Fig 4.33: Metal coated with Graphene (Modified Hummers Method) tested in HCl
As compared to uncoated metal corrosion rate is reduced by 86.9%

28

Fig 4.34: Metal Coated with Graphene (Hummers method) tested in NaOH
As compared to uncoated metal corrosion rate is decreased by 99.2%

Fig 4.35: Metal Coated with Graphene (Modified Hummers method) tested in NaOH
As compared to uncoated metal corrosion rate is decreased by 98.8%

29

4.5 Comparison of Results

Metal coupon tested in Distilled Water (pH 7.07)
Metal Surface

Uncoated
1 Layer Coating
2 Layer Coating
3 Layer Coating

CR mpy
(Graphene via
Modified
Hummers Method)
282
39
6.5
3.5

CR mpy
(Graphene via
Hummers Method)
282
27
25

% decrease in
corrosion (graphene
via Modified
Hummers Method)
NA
86
97.6

22.5
98.7
Table4: % decrease in corrosion when tested in Distilled Water (pH 7.07)

% decrease in
corrosion (graphene
via Hummers
Method)
NA
90.4
91.1

92

Metal coupon tested in Tap Water (pH 7.77)

CR mpy
CR mpy
% decrease in
(Graphene via
(Graphene via
corrosion (graphene
Hummers Method) via Modified
Modified
Hummers Method)
Hummers Method)
220
220
NA
Uncoated
1 Layer Coating
44
64
80
2 Layer Coating
36
42.5
83.6
3 Layer Coating
20.5
37
90.6
Table 5: % decrease in corrosion when tested in Tap Water (pH 7.77)
Metal Surface

% decrease in
corrosion (graphene
via Hummers
Method)
NA
70.9
80.6

83.1

Metal coupon tested in NaCl (3.5 wt %)

CR mpy
CR mpy
(Graphene via
(Graphene via
Hummers Method)
Modified
Hummers Method)
667
667
Uncoated
1 Layer Coating
17
208
2 Layer Coating
5
148
3 Layer Coating
3
60
Table 6: % decrease in corrosion when tested in NaCl (3.5 wt %)
Metal Surface

% decrease in
corrosion (graphene
via Modified
Hummers Method)
NA
97.4
99.2

% decrease in
corrosion (graphene
via Hummers
Method)
NA
68.6
77.8

99.5

91

% decrease in
corrosion (graphene
via Modified
Hummers Method)
NA
60.4
76

% decrease in
corrosion (graphene
via Hummers
Method)
NA
6.3
64.8

86.9

68.6

Metal coupon tested in HCl (0.1 N)

CR mpy
CR mpy
(Graphene via
(Graphene via
Hummers Method)
Modified
Hummers Method)
523
523
Uncoated
1 Layer Coating
207
490
2 Layer Coating
135
184
3 Layer Coating
68.5
164
Table 7: % decrease in corrosion when tested in HCl (0.1 N)
Metal Surface

30

Metal coupon tested in NaOH (1 M)

CR mpy
CR mpy
(Graphene via
(Graphene via
Hummers Method)
Modified
Hummers Method)
885
885
Uncoated
1 Layer Coating
189
86.5
2 Layer Coating
27
20
3 Layer Coating
10
7
Table 8: % decrease in corrosion when tested in NaOH (1 M)
Metal Surface

% decrease in
corrosion (graphene
via Modified
Hummers Method)
NA
78.6
96.9

% decrease in
corrosion (graphene
via Hummers
Method)
NA
90.2
97.7

98.8

99.2

4.6 Metal Coupons with more than 3 Layered Coatings

Graphene coatings of 4, 5 and 6 layers were made on metal coupons. At 5 and 6 coatings the corrosion
rate was almost similar. If we add further coatings on it Graphene will not adhere to metal coupon as there
will be more van der Waals forces between two successive coatings. Corrosion test was conducted for
these multilayered coatings in Distilled Water environment and results are plotted as shown below.

Fig 4.36: Plot between corrosion rate and number of coatings

31

4.7 Characterization of Coated Metal Coupons

Coupons which were coated with Graphene by using Dip Coating and exposed to corrosive environment
are characterized using Optical Microscope. The images produced by microscope gave clearer picture of
coupons.

Fig 4.7.1: Bare Metal Exposed to NaCl environment

Fig 4.7.2: 3 Layer Graphene coated metal coupon exposed to NaCl environment

32

4.8 Characterization of Graphene using XRD

Graphene which was synthesized previously was heated up to 100C for 36 hours. Then Graphene
powder was obtained. This powder was subjected to characterization using XRD.

Fig 4.8.1: XRD Plot

From analysis it can be seen that there is sharp peak at 26.5 degrees. There are two small peaks at 42
degrees and 55 degrees.
Glaucio Carley et al (2013), Titash Mondal et al (2012) have reported same results. In their analysis too
Graphene was showing a sharp peak at 26.5 degrees. From this we can confirm that graphene synthesized
here was of good quality.

33

5 Conclusions
From the experimental setup and analysis we found that Graphene prepared by Modified Hummers
method was acting as affective anticorrosion coating compared to Graphene prepared by Hummers
method. When compared to other corrosion inhibitors like vapor phase organic inhibitors, paints etc
Graphene as anticorrosion coating for Mild Steel is giving almost same results. If Graphene is directly
grown on metals by using techniques like Chemical Vapor Deposition (CVD) then we will get much
better results for graphene as anticorrosion coating.
Graphene coatings dont change optical and physical properties of metal. If there are more than 6 layered
coating of graphene on metal surface those coatings will not be affective as van der Waals forces come
into action and coatings will not adhere to previous coatings. Graphene prepare by Modified Hummers
method was of better quality because this method involved ageing. Due to this lot of time for oxidation
reaction was available. But it was not same in the case of Hummers method as there was no ageing of
solution.

34

6 References
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