“Analysis Of Properties And Usage Of

Graphene For Application In Marine

Environment”

Author:
PV Vaithiyalagam Rd, Velan Nagar, Krishnapuram, Pallavaram, Chennai, Tamil Nadu
600117.
Department of Naval Architecture And Offshore Engineering.
www.velsuiv.ac.in/

Abstract
Graphene possesses a lot of extraordinary properties. It is a 2D layer of carbon atoms or graphite which are arranged
in a honey comb pattern. It is just a one atom thick substance having astonishing traits and applications like coatings,
paints and inks. In this case made into graphene coating.

Corrosion protection is an important issue especially in the maritime industry. Graphene coating have attracted a lot
of interest since they have the potential to provide corrosion resistance even if you apply these coatings in thickness of
only a few nanometers. Moreover, its conductive properties are a plus in such applications. Graphene nanofillers are
unique as they can improve the properties of other protective coatings even at low loadings. Those coatings which
contain even a minor amount of graphene show improved resistance to corrosion.

Keywords:Graphene,Corrosion Protection,Graphene Nanofillers,Protective Coatings,Low Loadings.

1
 .Structure

Graphene is a crystalline allotrope of carbon with 2-dimensional properties. Its carbon atoms are densely packed
in a regular atomic-scale chicken wire (hexagonal) pattern.

Each atom has four bonds: one σ bond with each of its three neighbours and one π-bond that is oriented out of
plane. The atoms are about 1.42 Å apart.

Graphene's hexagonal lattice can be regarded as two interleaving triangular lattices. This perspective was
successfully used to calculate the band structure for a single graphite layer using a tight-binding approximation.

Graphene's stability is due to its tightly packed carbon atoms and a sp2 orbital hybridization – a combination of
orbitals s, px and py that constitute the σ-bond. The final pz electron makes up the π-bond. The π-bonds
hybridize together to form the π-band and π∗-bands. These bands are responsible for most of graphene's notable
electronic properties, via the half-filled band that permits free-moving electrons.

Graphene sheets in solid form usually show evidence in diffraction for graphite's (002) layering. This is true of
some single-walled nanostructures. However, unlayered graphene with only (hk0) rings has been found in the
core of presolar graphite onions. TEM studies show faceting at defects in flat graphene sheets and suggest a role
for two-dimensional crystallization from a melt.

Graphene can self-repair holes in its sheets, when exposed to molecules containing carbon, such as
hydrocarbons. Bombarded with pure carbon atoms, the atoms perfectly align into hexagons, completely filling
the holes.

The atomic structure of isolated, single-layer graphene was studied by TEM on sheets of graphene suspended
between bars of a metallic grid. Electron diffraction patterns showed the expected honeycomb lattice.
Suspended graphene showed "rippling" of the flat sheet, with amplitude of about one nanometer. These ripples
may be intrinsic to the material as a result of the instability of two-dimensional crystals, or may originate from
the ubiquitous dirt seen in all TEM images of graphene. Atomic resolution real-space images of isolated, single-
layer graphene on SiO2 substrates are available via scanning tunneling microscopy (STM). Photoresist residue,
which must be removed to obtain atomic-resolution images, may be the "adsorbates" observed in TEM images,
and may explain the observed rippling. Rippling on SiO2 is caused by conformation of graphene to the
underlying SiO2 and is not intrinsic.

2
 Figure 1:Scanning probe microscopy image of graphene

Stability:Ab initio calculations show that a graphene sheet is thermodynamically unstable if its size is less than
about 20 nm ("graphene is the least stable structure until about 6000 atoms") and becomes the most stable
fullerene (as within graphite) only for molecules larger than 24,000 atoms.

Analogs:Analogs (also referred to as "artificial graphene") are two-dimensional systems that exhibit similar
properties to graphene. Analogs can be systems in which the physics is easier to observe and to manipulate. In
those systems, electrons are not always the chosen particles—they might be optical photons, microwave
photons, plasmons, microcavity polaritons or even atoms. Also, the honeycomb structure in which those
particles evolve can be of a different nature than carbon atoms in graphene. It can be, respectively, a photonic
crystal, an array of metallic rods, metallic nanoparticles, a lattice of coupled microcavities or an optical lattice.

Properties:

Graphene has a theoretical specific surface area (SSA) of 2630 m2/g. This is much larger than that reported to
date for carbon black (typically smaller than 900 m2/g) or for carbon nanotubes (CNTs), from ≈100 to 1000
m2/g and is similar to activated carbon.

Electronic:

Graphene is a zero-gap semiconductor, because its conduction and valence bands meet at the Dirac points,
which are six locations in momentum space, on the edge of the Brillouin zone, divided into two non-equivalent
sets of three points. The two sets are labeled K and K'. The sets give graphene a valley degeneracy of gv = 2. By
contrast, for traditional semiconductors the primary point of interest is generally Γ, where momentum is zero.
However, if the in-plane direction is confined, in which case it is referred to as a nanoribbon, its electronic
structure is different. If it is "zig-zag", the bandgap is zero. If it is "armchair", the bandgap is non-zero .

Graphene displays remarkable electron mobility at room temperature, with reported values in excess of 15000
cm2⋅V−1⋅s−1. Hole and electron mobilities were expected to be nearly identical. The mobility is nearly
independent of temperature between 10 K and 100 K, which implies that the dominant scattering mechanism is
defect scattering. Scattering by graphene's acoustic phonons intrinsically limits room temperature mobility to
200000 cm2⋅V−1⋅s−1 at a carrier density of 1012 cm−2, 10×106 times greater than copper.

The corresponding resistivity of graphene sheets would be 10−6 Ω⋅cm. This is less than the resistivity of silver,
the lowest otherwise known at room temperature. However, on SiO 2 substrates, scattering of electrons by optical
phonons of the substrate is a larger effect than scattering by graphene’s own phonons. This limits mobility to
40000 cm2⋅V−1⋅s−1.Charge transport is affected by adsorption of contaminants such as water and oxygen
molecules. This leads to non-repetitive and large hysteresis I-V characteristics.

Electrons propagating through graphene's honeycomb lattice effectively lose their mass, producing quasi-
particles that are described by a 2D analogue of the Dirac equation rather than the Schrödinger equation for
spin-1⁄2 particles.

Superconductivity has been observed in twisted bilayer graphene .

Optics:

Graphene's unique optical properties produce an unexpectedly high opacity for an atomic monolayer in vacuum,
absorbing πα ≈ 2.3% of red light, where α is the fine-structure constant. This is a consequence of the "unusual
low-energy electronic structure of monolayer graphene that features electron and hole conical bands meeting
each other at the Dirac point... [which] is qualitatively different from more common quadratic massive bands."
Based on the Slonczewski–Weiss–McClure (SWMcC) band model of graphite, the interatomic distance,
hopping value and frequency cancel when optical conductance is calculated using Fresnel equations in the thin-
film limit.

3
Although confirmed experimentally, the measurement is not precise enough to improve on other techniques for
determining the fine-structure constant.

Multi-Parametric Surface Plasmon Resonance was used to characterize both thickness and refractive index of
chemical-vapor-deposition (CVD)-grown graphene films. The measured refractive index and extinction
coefficient values at 670 nm wavelength are 3.135 and 0.897, respectively. The thickness was determined as 3.7
Å from a 0.5 mm area, which agrees with 3.35 Å reported for layer-to-layer carbon atom distance of graphite
crystals.

The method can be used for real-time label-free interactions of graphene with organic and inorganic substances.
The existence of unidirectional surface plasmons in the nonreciprocal graphene-based gyrotropic interfaces has
been demonstrated theoretically. By efficiently controlling the chemical potential of graphene, the unidirectional
working frequency can be continuously tunable from THz to near-infrared and even visible. Particularly, the
unidirectional frequency bandwidth can be 1–2 orders of magnitude larger than that in metal under the same
magnetic field, which arises from the superiority of extremely small effective electron mass in graphene.

Graphene's band gap can be tuned from 0 to 0.25 eV (about 5 micrometre wavelength) by applying voltage to a
dual-gate bilayer graphene field-effect transistor (FET) at room temperature.The optical response of graphene
nanoribbons is tunable into the terahertz regime by an applied magnetic field. Graphene/graphene oxide systems
exhibit electrochromic behavior, allowing tuning of both linear and ultrafast optical properties.

A graphene-based Bragg grating (one-dimensional photonic crystal) demonstrated its capability for excitation of
surface electromagnetic waves in the periodic structure using a 633 nm He–Ne laser as the light source.

Saturable absorption:Such unique absorption could become saturated when the input optical intensity is above a
threshold value. This nonlinear optical behavior is termed saturable absorption and the threshold value is called
the saturation fluence. Graphene can be saturated readily under strong excitation over the visible to near-infrared
region, due to the universal optical absorption and zero band gap. This has relevance for the mode locking of
fiber lasers, where fullband mode locking has been achieved by a graphene-based saturable absorber. Due to this
special property, graphene has wide application in ultrafast photonics. The optical response of
graphene/graphene oxide layers can be tuned electrically. Saturable absorption in graphene could occur at the
Microwave and Terahertz bands, owing to its wideband optical absorption property. The microwave saturable
absorption in graphene demonstrates the possibility of graphene microwave and terahertz photonics devices,
such as a microwave saturable absorber, modulator, polarizer, microwave signal processing and broad-band
wireless access networks.

Nonlinear Kerr effect:Under more intensive laser illumination, graphene could possess a nonlinear phase shift
due to the optical nonlinear Kerr effect. Based on a typical open and close aperture z-scan measurement,
graphene possesses a nonlinear Kerr coefficient of 10−7 cm2⋅ W−1, almost nine orders of magnitude larger
than that of bulk dielectrics.This suggests that graphene may be a powerful nonlinear Kerr medium, with the
possibility of observing a variety of nonlinear effects, the most important of which is the soliton.A 2016 study
has shown that the nonlinear refractive index of graphene is negative.Thermal lens spectroscopy can be used for
measuring the thermo-optic coefficient of graphene and inspecting its thermal nonlinearity.

Quantum dots:Several techniques can prepare nanostructured graphene, e.g., graphene quantum dots (GQDs);
these techniques mainly include electron beam lithography, chemical synthesis, electrochemical preparation,
graphene oxide (GO) reduction, C60 catalytic transformation, the microwave assisted hydrothermal method
(MAH),the Soft-Template method, the hydrothermal method, and the ultrasonic exfoliation method.

4
 Figure 2: Photograph of graphene in transmitted light.

Thermal

Thermal conductivity:

Thermal transport in graphene is an active area of research which has attracted attention because of the potential
for thermal management applications. Early measurements of the thermal conductivity of suspended graphene
reported an exceptionally large thermal conductivity of approximately 5300 W⋅m−1⋅K−1, compared with the
thermal conductivity of pyrolytic graphite of approximately 2000 W⋅m−1⋅K−1 at room temperature. However,
later studies have questioned whether this ultrahigh value was overestimated, and instead measured thermal
conductivities between 1500–2500 W⋅m−1⋅K−1 for suspended single layer graphene.The large range can be
attributed to large measurement uncertainties as well as variations in the graphene quality and processing
conditions. In addition, when single-layer graphene is supported on an amorphous material, the thermal
conductivity is reduced to about 500–600 W⋅m−1⋅K−1 at room temperature as a result of scattering of graphene
lattice waves by the substrate, and can be even lower for few layer graphene encased in amorphous
oxide.Likewise, polymeric residue can contribute to a similar decrease for suspended graphene to approximately
500–600 W⋅m−1⋅K−1for bilayer graphene.

It has been suggested that the isotopic composition, the ratio of 12C to 13C, has a significant impact on thermal
conductivity. For example, isotopically pure 12C graphene has higher thermal conductivity than either a 50:50
isotope ratio or the naturally occurring 99:1 ratio.It can be shown by using the Wiedemann–Franz law, that the
thermal conduction is phonon-dominated. However, for a gated graphene strip, an applied gate bias causing a
Fermi energy shift much larger than kBT can cause the electronic contribution to increase and dominate over the
phonon contribution at low temperatures. The ballistic thermal conductance of graphene is isotropic.

Potential for this high conductivity can be seen by considering graphite, a 3D version of graphene that has basal
plane thermal conductivity of over a 1000 W⋅m−1⋅K−1 (comparable to diamond). In graphite, the c-axis (out of
plane) thermal conductivity is over a factor of ≈100 smaller due to the weak binding forces between basal planes
as well as the larger lattice spacing.[81] In addition, the ballistic thermal conductance of graphene gives the
lower limit of the ballistic thermal conductances, per unit circumference and length of carbon nanotubes.

Despite its 2-D nature, graphene has 3 acoustic phonon modes. The two in-plane modes (LA, TA) have a linear
dispersion relation, while the out of plane mode (ZA) has a quadratic dispersion relation. Due to this, the T2
dependent thermal conductivity contribution of the linear modes is dominated at low temperatures by the T1.5
contribution of the out-of-plane mode. Some graphene phonon bands display negative Grüneisen parameters
(GPs). At low temperatures (where most optical modes with positive GPs are still not excited) the contribution

5
from the negative GPs will be dominant and thermal expansion coefficient (which is directly proportional to
GPs) negative. The lowest negative GPs correspond to the lowest transverse acoustic ZA modes. Phonon
frequencies for such modes increase with the in-plane lattice parameter since atoms in the layer upon stretching
will be less free to move in the z direction. This is similar to the behavior of a stretched string that has vibrations
of smaller amplitude and higher frequency. This phenomenon, named "membrane effect", was predicted by
Lifshitz in 1952.

Melting point

A prediction published in 2015 suggested a melting point of ≈4125 K. And more sophisticated modelling has
increased this temperature to at least 5000 K. At 6000 K (the sun's surface having an effective temperature of
5,777 K) graphene melts into an agglomeration of loosely coupled doubled bonded chains, before becoming a
gas.

Mechanical:

The carbon–carbon bond length in graphene is about 0.142 nanometers.Graphene sheets stack to form
graphite with an interplanar spacing of 0.335 nm.

Graphene is the strongest material ever tested,with an intrinsic tensile strength of 130.5 GPa and a Young's
modulus of 1 TPa (150000000 psi). The Nobel announcement gave the strength as 42 N/m; the mass of 1 m2 as
0.77 mg, and the electrical resistance of a square as 31 Ω.

Large-angle-bent graphene monolayer has been achieved with negligible strain, showing mechanical
robustness of the two-dimensional carbon nanostructure. Even with extreme deformation, excellent carrier
mobility in monolayer graphene can be preserved.

The spring constant of suspended graphene sheets has been measured using an atomic force microscope
(AFM). Graphene sheets were suspended over SiO2 cavities where an atomic force microscope (AFM) tip was
used to apply a stress to the sheet to test its mechanical properties. Its spring constant was in the range 1–5 N/m
and the stiffness was 0.5 TPa, which differs from that of bulk graphite. These intrinsic properties could lead to
applications such as NEMS as pressure sensors and resonators.Due to its large surface energy and out of plane
ductility, flat graphene sheets are unstable with respect to scrolling, i.e. bending into a cylindrical shape, which
is its lower-energy state.

As is true of all materials, regions of graphene are subject to thermal and quantum fluctuations in relative
displacement. Although the amplitude of these fluctuations is bounded in 3D structures (even in the limit of
infinite size), the Mermin–Wagner theorem shows that the amplitude of long-wavelength fluctuations grows
logarithmically with the scale of a 2D structure and would therefore be unbounded in structures of infinite size.
Local deformation and elastic strain are negligibly affected by this long-range divergence in relative
displacement. It is believed that a sufficiently large 2D structure, in the absence of applied lateral tension, will
bend and crumple to form a fluctuating 3D structure. Ripples have been observed in suspended layers of
graphene. It has been proposed that the ripples are caused by thermal fluctuations in the material. As a
consequence of these dynamical deformations, it is debatable whether graphene is truly a 2D structure. In 2014
it was shown that these ripples, if amplified through the introduction of vacancy defects, can impart a negative
Poisson's ratio into graphene, resulting in the thinnest auxetic material known.

Graphene nanosheets can be incorporated into a nickel matrix through a plating process to form Ni-
graphene composites on a target substrate. The enhancement in mechanical properties of the composites is
attributed to the high interaction between Ni and graphene and the prevention of the dislocation sliding in the Ni
matrix by the graphene.

Fracture toughness

6
 Despite its strength, graphene is also relatively brittle, with a fracture toughness of about 4 MPa√m.[100]
This indicates that imperfect graphene is likely to crack in a brittle manner like ceramic materials, as opposed to
many metallic materials that have fracture toughnesses in the range of 15–50 MPa√m. Graphene shows a greater
ability to distribute force from an impact than any known material, ten times that of steel per unit weight. The
force was transmitted at 22.2 kilometres per second (13.8 mi/s).

Biological

In 2011 graphene was shown to accelerate the osteogenic differentiation of human mesenchymal stem cells
without the use of biochemical inducers.

In 2015 graphene was used to create biosensors with epitaxial graphene on silicon carbide. The sensors bind
to 8-hydroxydeoxyguanosine (8-OHdG) and is capable of selective binding with antibodies. The presence of 8-
OHdG in blood, urine and saliva is commonly associated with DNA damage. Elevated levels of 8-OHdG have
been linked to increased risk of several cancers.A commercial version of a graphene biosensor has been used as
a protein binding sensor platform.

In 2016 uncoated graphene was shown to serve as a neuro-interface electrode without altering or damaging
properties such as signal strength or formation of scar tissue. Graphene electrodes in the body stay significantly
more stable than electrodes of tungsten or silicon because of properties such as flexibility, bio-compatibility and
conductivity.

Graphene Modification

Soluble fragments of graphene can be prepared in the laboratory through chemical modification of graphite.
First, microcrystalline graphite is treated with an acidic mixture of sulfuric acid and nitric acid. A series of
oxidation and exfoliation steps produce small graphene plates with carboxyl groups at their edges. These are
converted to acid chloride groups by treatment with thionyl chloride; next, they are converted to the
corresponding graphene amide via treatment with octadecylamine. The resulting material (circular graphene
layers of 5.3 angstrom thickness) is soluble in tetrahydrofuran, tetrachloromethane and dichloroethane.

Figure 3: Photograph of single-layer graphene oxide undergoing high temperature chemical treatment, resulting in sheet folding and loss of
carboxylic functionality, or through room temperature carbodiimide treatment, collapsing into star-like clusters.

Refluxing single-layer graphene oxide (SLGO) in solvents leads to size reduction and folding of individual
sheets as well as loss of carboxylic group functionality, by up to 20%, indicating thermal instabilities of SLGO
sheets dependent on their preparation methodology. When using thionyl chloride, acyl chloride groups result,
which can then form aliphatic and aromatic amides with a reactivity conversion of around 70–80%.

Hydrazine reflux is commonly used for reducing SLGO to SLG(R), but titrations show that only around 20–
30% of the carboxylic groups are lost, leaving a significant number available for chemical attachment. Analysis
of such SLG(R) reveals that the system is unstable. Using a room temperature stirring with HCl (< 1.0 M) leads
to around 60% loss of COOH functionality. Room temperature treatment of SLGO with carbodiimides leads to
the collapse of the individual sheets into star-like clusters that exhibited poor subsequent reactivity with amines
(c. 3–5% conversion of the intermediate to the final amide). It is apparent that conventional chemical treatment
of carboxylic groups on SLGO generates morphological changes of individual sheets that leads to a reduction in
chemical reactivity, which may potentially limit their use in composite synthesis. Therefore, chemical reactions
types have been explored. SLGO has also been grafted with polyallylamine, cross-linked through epoxy groups.

7
When filtered into graphene oxide paper, these composites exhibit increased stiffness and strength relative to
unmodified graphene oxide paper.

Figure 4: Boehm titration results for various chemical reactions of single-layer graphene oxide, which reveal reactivity of the carboxylic
groups and the resultant stability of the SLGO sheets after treatment .

Full hydrogenation from both sides of graphene sheet results in graphane, but partial hydrogenation leads to
hydrogenated graphene. Similarly, both-side fluorination of graphene (or chemical and mechanical exfoliation
of graphite fluoride) leads to fluorographene (graphene fluoride), while partial fluorination (generally
halogenation) provides fluorinated (halogenated) graphene.

Graphene Morphology:

Monolayer sheets:In
2013 researchers developed a production unit that produces continuous
monolayer sheets of high-strength monolayer graphene (HSMG).The process is based on
graphene growth on a liquid metal matrix.

Bilayer:Bilayer graphene displays the anomalous quantum Hall effect, a tunable band gap and potential for
excitonic condensation.Bilayer graphene typically can be found either in twisted configurations where the two
layers are rotated relative to each other or graphitic Bernal stacked configurations where half the atoms in one
layer lie atop half the atoms in the other. Stacking order and orientation govern its optical and electronic
properties.

One synthesis method is chemical vapor deposition, which can produce large bilayer regions that almost
exclusively conform to a Bernal stack geometry.

Superlattices:
Periodically stacked graphene and its insulating isomorph provide a fascinating structural element in
implementing highly functional superlattices at the atomic scale, which offers possibilities in designing
nanoelectronic and photonic devices. Various types of superlattices can be obtained by stacking graphene and its
related forms.The energy band in layer-stacked superlattices is more sensitive to the barrier width than that in
conventional III–V semiconductor superlattices. When adding more than one atomic layer to the barrier in each
period, the coupling of electronic wavefunctions in neighboring potential wells can be significantly reduced,

8
which leads to the degeneration of continuous subbands into quantized energy levels. When varying the well
width, the energy levels in the potential wells along the L-M direction behave distinctly from those along the K-
H direction.

Precisely aligned graphene on h-BN always produces giant superlattice known as Moiré pattern.Moiré patterns
are observed and the sensitivity of moiré interferometry proves that the graphene grains can align precisely with
the underlying h-BN lattice within an error of less than 0.05°. The occurrence of moiré pattern clearly indicates
that the graphene locks into h-BN via van der Waals epitaxy with its interfacial stress greatly released.

The existence of the giant Moiré pattern in graphene nanoribbon (GNR) embedded in hBN indicates that the
graphene was highly crystalline and precisely aligned with the h-BN underneath. It was noticed that the Moiré
pattern appeared to be stretched along the GNR, while it appeared relaxed laterally.This trend differs from
regular hexagons with a periodicity of ∼14 nm, which have always been observed with well-aligned graphene
domains on h-BN. This observation gives a strong indication of the in-plane epitaxy between the graphene and
the h-BN at the edges of the trench, where the graphene is stretched by tensile strain along the ribbon, due to a
lattice mismatch between the graphene and h-BN.

Nanoribbons

Graphene nanoribbons ("nanostripes" in the "zig-zag" orientation), at low temperatures, show spin-polarized
metallic edge currents, which suggest spintronics applications. (In the "armchair" orientation, the edges behave
like semiconductors.)

Fiber

In 2011, researchers reported making fibers using chemical vapor deposition grown graphene films. The method
was scalable and controllable, delivering tunable morphology and pore structure by controlling the evaporation
of solvents with suitable surface tension. Flexible all-solid-state supercapacitors based on such fibers were
demonstrated in 2013.

In 2015 intercalating small graphene fragments into the gaps formed by larger, coiled graphene sheets after
annealing provided pathways for conduction, while the fragments helped reinforce the fibers. The resulting
fibers offered better thermal and electrical conductivity and mechanical strength. Thermal conductivity reached
1290 watts per meter per kelvin, while tensile strength reached 1080 megapascals.

In 2016, kilometer-scale continuous graphene fibers with outstanding mechanical properties and excellent
electrical conductivity were produced by high-throughput wet-spinning of graphene oxide liquid crystals
followed by graphitization through a full-scale synergetic defect-engineering strategy.

3D

In 2013, a three-dimensional honeycomb of hexagonally arranged carbon was termed 3D graphene. Self-
supporting 3D graphene was produced that year. Researchers at Stony Brook University have reported a novel
radical-initiated crosslinking method to fabricate porous 3D free-standing architectures of graphene and carbon
nanotubes using nanomaterials as building blocks without any polymer matrix as support.3D structures can be
fabricated by using either CVD or solution-based methods. A 2016 review summarized the techniques for
fabrication of 3D graphene and other related two-dimensional materials. These 3D graphene (all-carbon)
scaffolds/foams have potential applications in fields such as energy storage, filtration, thermal management and
biomedical devices and implants.

In 2016 box-shaped graphene (BSG) nanostructure resulted from mechanical cleavage of pyrolytic graphite. The
discovered nanostructure is a multilayer system of parallel hollow nanochannels located along the surface that
displayed quadrangular cross-section. The thickness of the channel walls is approximately equal to 1 nm.
Potential applications include: ultra-sensitive detectors, high-performance catalytic cells, nanochannels for DNA
sequencing and manipulation, high-performance heat sinking surfaces, rechargeable batteries of enhanced

9
performance, nanomechanical resonators, electron multiplication channels in emission nanoelectronic devices,
high-capacity sorbents for safe hydrogen storage.

Three dimensional bilayer graphene was reported in 2012 and 2014.

In 2017 researchers created a graphene gyroid that has five percent of the density of steel, yet is ten times as
strong with an enormous surface area to volume ratio. They compressed heated graphene flakes. They then
constructed high resolution 3D-printed models of plastic of various configurations – similar to the gyroids that
graphene form naturally, though thousands of times larger. These shapes were then tested for tensile strength
and compression, and compared to the computer simulations. When the graphene was swapped out for polymers
or metals, similar gains in strength were seen.

A film of graphene soaked in solvent to make it swell and become malleable was overlaid on an underlying
substrate "former". The solvent evaporated, leaving behind a layer of graphene that had taken on the shape of
the underlying structure. In this way the team was able to produce a range of relatively intricate micro-structured
shapes.Features vary from 3.5 to 50 μm. Pure graphene and gold-decorated graphene were each successfully
integrated with the substrate.

An aerogel made of graphene layers separated by carbon nanotubes was measured at 0.16 milligrams per cubic
centimeter. A solution of graphene and carbon nanotubes in a mold is freeze dried to dehydrate the solution,
leaving the aerogel. The material has superior elasticity and absorption. It can recover completely after more
than 90% compression, and absorb up to 900 times its weight in oil, at a rate of 68.8 grams per second.

At the end of 2017, fabrication of freestanding graphene gyroids with 35nm and 60nm unit cells was reported.
The gyroids were made via controlled direct chemical vapor deposition and are self-supporting and can be
transferred onto a variety of substrates. Furthermore, they represent the smallest free standing periodic graphene
3D structures yet produced with a pore size of tens of nm. Due to their high mechanical strength, good
conductivity (sheet resistance : 240 Ω/sq) and huge ratio of surface area per volume, the graphene gyroids might
find their way to various applications, ranging from batteries and supercapacitors to filtration and
optoelectronics.

Pillared

Pillared graphene is a hybrid carbon structure consisting of an oriented array of carbon nanotubes connected at
each end to a graphene sheet. It was first described theoretically in 2008. Pillared graphene has not been
synthesized in the laboratory.

Reinforced

Graphene sheets reinforced with embedded carbon nanotubes ("rebar") are easier to manipulate, while
improving the electrical and mechanical qualities of both materials.

Functionalized single- or multiwalled carbon nanotubes are spin-coated on copper foils and then heated and
cooled, using the nanotubes as the carbon source. Under heating, the functional carbon groups decompose into
graphene, while the nanotubes partially split and form in-plane covalent bonds with the graphene, adding
strength. π–π stacking domains add more strength. The nanotubes can overlap, making the material a better
conductor than standard CVD-grown graphene. The nanotubes effectively bridge the grain boundaries found in
conventional graphene. The technique eliminates the traces of substrate on which later-separated sheets were
deposited using epitaxy.

Stacks of a few layers have been proposed as a cost-effective and physically flexible replacement for indium tin
oxide (ITO) used in displays and photovoltaic cells.

Nanocoil:

10
In 2015 a coiled form of graphene was discovered in graphitic carbon (coal). The spiraling effect is produced by
defects in the material's hexagonal grid that causes it to spiral along its edge, mimicking a Riemann surface,
with the graphene surface approximately perpendicular to the axis. When voltage is applied to such a coil,
current flows around the spiral, producing a magnetic field. The phenomenon applies to spirals with either
zigzag or armchair orientations, although with different current distributions. Computer simulations indicated
that a conventional spiral inductor of 205 microns in diameter could be matched by a nanocoil just 70
nanometers wide, with a field strength reaching as much as 1 tesla, about the same as the coils found in typical
loudspeakers, about the same field strength as some MRI machines. They found the magnetic field would be
strongest in the hollow, nanometer-wide cavity at the spiral's center.

A solenoid made with such a coil behaves as a quantum conductor whose current distribution between the core
and exterior varies with applied voltage, resulting in nonlinear inductance.

Challenges:

So far, a cost effective, practical and commercial scale method for graphene’s production has not yet been
developed. Presently, graphene is being produced in small quantities at high prices i.e. $50 to $10,000 per gram.
However, experts are trying to shift focus from application to commercialization of graphene. It is expected to
see graphene coating in the market around late 2017 – 2018.

Market availability and prices:

Some suppliers are charging upto $350/gram. These coatings come in small bottles. Graphene powder is also
available with some suppliers for which you are expected to pay up to $1000/Kg. The rates are subject to change
and depend on the manufacturer & supplier.

Potential of Graphene:

Graphene ship tech makes the future dreadnought:

When thinking in the future weapon will found a lot of engineering and designer racing to Graphene because of
it the strongest material in the world!

We see it when British naval architects and engineers were tasked by the Royal Navy and ministry of defense to
imagine how the future naval ships might look to create “Dreadnought 2050” graphene ships that can become
see-through, electromagnetic weapons with a range of hundreds of miles and torpedoes that travel at 300 knots
,Warships of the future could be built from ultra-strong plastic and graphene , armed with weapons that fire at
the speed of light and operated by crews a fraction of the size needed by current vessels.

11
 Figure 5: Graphene ship tech makes the future dreadnought

Just some of the ideas for warships of the future, in a challenge, issued a procurement group that brings together
experts in naval defense from the government, military, and industry to provide advanced technology against a
backdrop of tightening budgets.

Engineering and designer using graphene as suggested to increase the strength of ships, as well painting all
metal parts by graphene paint to less corrosion it and coating ship hulls to reduce drag, meaning they could sail
faster and use less fuel. Among other features thought up for the ships are drone carrying sensors to replace
conventional masts, to be connected to the ship by a tether made from cryogenically-cooled carbon nanotubes
which would transmit power to aircraft’s motors and also energy weapons such as lasers.

Naval architects also suggested arming the ships with electromagnetic “railguns”, which fire projectiles as far as
today’s cruise missile fly, rows of missile tubes along the ship’s sides which launch hypersonic missiles at
speeds of Mach 5-plus, and super cavitating torpedoes which travel at 300 knots because they are encased in a
bubble of gas which reduces friction.

The operations room would have superfast data connections to the rest of the fleet and aircraft, along with
headquarters, meaning operations could be commanded from thousands of miles away , Using such advanced
technology is expected to cut the number of crew required from about 200 on a contemporary warship to as few
50.

Unique properties of graphene-polymer coating:

Coating formulators have long used inorganic fillers to modify the properties of polymeric coatings, Nanoscale
fillers have been in use for decades, and largely consist of layered clays, carbon nanotubes and derivatives, and
spherical nanoparticles, most commonly silicon dioxide (SiO2). However, most inorganic fillers exhibit poor
compatibility with organic polymer resins, and thus the surfaces of the fillers must often be modified to improve
filler/matrix interactions. Graphene is attractive as a nanoscale filler because it is a carbon-based material that
has improved interactions with organic polymers. Thus, graphene nanosheets and nanoplates and graphene
oxide have been investigated as fillers for various types of coatings.

Applied Graphene Materials (AGM), funded through listing on the UK’s AIM stock market, has already
developed scalable production technology for a range of graphene nanoplatelets (A-GNPs), but uniquely

12
through a continuous synthesis process. To support their focus on developing industry-ready graphene
dispersions, AGM has collaborated with the UK’s Paint Research Association to test modified polyurethane and
epoxy coatings. Initial results, based on small additions of A-GNP10 nanoplatelets, have indicated
improvements in mechanical properties such as scratch resistance but with stand-out gains in reducing moisture
vapor transmission rates and anticorrosion performance. AGM reports improvements in excess of 300% in time
to failure during cyclical salt spray testing.

Researchers at Chung-Yuan Christian University in Taiwan developed electroactive polyimide (EPI)/graphene

nanocomposite (EPGN) coatings via thermal imidization and demonstrated that these coatings provided two-
fold protection against the corrosion of cold-rolled steel (CRS) electrodes compared to that of a neat EPI
coating. The enhanced corrosion protection performance of the EPGN coating was attributed to the redox
catalytic capabilities of amino-capped aniline trimer (ACAT) units existing in the EPGN, which were thought to
induce the formation of passive metal oxide layers on the CRS electrode. In addition, the carboxyl-graphene
nanosheets embedded in the EPGN matrix increased the tortuosity of the diffusion pathway for O 2 molecules,
thus functioning as a gas barrier and significantly hindering oxygen migration.

Graphene is attractive as a nanoscale filler becauseit is a carbon-based material that has improved interactions
with organic polymers.

Almost all Navy ships are made from Marine Steel. Most carbon steel is not well-suited for marine
environments, however, there are several marine grade carbon steels available. AH36, DH36, and EH36 are all
examples of commonly used marine grade carbon steels approved by the American Bureau of Shipping. These
grades will have slightly more alloying elements such as manganese and chromium compared to their ASTM
grade counterparts, which helps achieve higher strength and more corrosion resistance. There are also marine
grades of alloy steel as well. Grades MD, ME, MF, MG, and others can provide the strength that normal alloy
steel is known for, and have also been approved by the American Bureau of Shipping for use in shipbuilding
applications.

Two types of stainless steel are used, but typically not in areas exposed to freezing. SAE 316 stainless steel is a
molybdenum-alloyed steel and is the second most common austenite stainless steel (after grade 304). It is the
preferred steel for use in marine environments because of its greater resistance to pitting corrosion than other
grades of steel without molybdenum.

Several types of aluminum are used in Navy ships, especially for superstructures. On rare occasions you will
find marine birch or other wood, or fibreglass, used on smaller ships.

The usual coatings are marine paint or silicone paint. They resist fouling and marine organisms. Their cost is an
order of magnitude cheaper than graphene(x) for a coating, while providing similar anti-fouling properties.

Graphene is a fairly good coating for marine environments. It is not structural. One variant seems to work well
on aluminum. But it is fairly expensive as a coating.

Reason for using Graphene Coating:

 Excellent mechanical strength

 Thin and light weight material
 High electricity conductivity (mobilities> 200,000 cm2 /Vs)
 Hydrophobic in nature
 Tensile strength of ~1 TPa
 High thermal conductivity
 Corrosion & chemical resistance
 Durable coatings resistant to cracks, oil and water
 High adhesion properties

13
 Graphene over polymer based coatings:

Literature indicates that the annual costs for corrosion including direct and indirect costs, are now approaching
$1 trillion which is ~6% of the national GDP of the United States. Studies indicate that microbially induced
corrosion (MIC) problems account for ~50% of the total corrosion costs. The MIC problem spans a range of
industries including aviation, oil and energy, shipping, and wastewater infrastructure. In fact, MIC is a
ubiquitous problem in the natural environment as indigenous microbes are adept at corroding metallic structures
under ambient temperatures and neutral pH conditions. MIC is caused by a genetically diverse set of microbes
that exist in harmony (encapsulating themselves in a matrix of self-excreted slimy exopolymeric substance), and
form a robust biological film (i.e. biofilm). The biofilm accelerates the corrosion process by modifying the
chemistry of the protective metal oxide passivation layers. Prevention of MIC is cumbersome as it requires
constant detection and monitoring of microbial populations. Moreover, physical methods for eradication of
biofilms (i.e. flushing) are energy-intensive and may in fact aggravate corrosion by dislodging oxide layers on
the metal surfaces.

Metal coatings and alloys have been commercially used to combat corrosion in abiotic environments. However,
when translated to a biotic environment their effectiveness is reduced due to aggressive microbial activity.
Further, they suffer from inherent disadvantages such as environmental regulations that prohibit their use for
corrosion applications (e.g. Cr). Polymer coatings (both natural and artificial) have also been used as an
effective barrier for corrosion applications but can suffer from poor adhesion to the base materials and undergo
rapid microbial degradation. It has been reported that over time, pin-hole defects induced by microbial activity
in polymer coatings grow in size, attract aggressive ions onto metallic surfaces, thereby further accelerating the
electrochemical corrosion process. Moreover, the typical thickness of commercial polymeric coatings disrupts
the functionality (e.g. electrical and thermal conductivity) and dimensional tolerances of target metals.

Graphene (Gr), a two-dimensional sheet of sp2 bonded carbon atoms, can be employed as an ultra-thin
corrosion-resistant coating, as it is mechanically robust, flexible, chemically inert, thermally and electrically
conductive, and can form an impermeable barrier. Further, ultra-thin graphene coatings can be applied without
negatively impacting the functionality (e.g. electrical, thermal conductivity etc.) and dimensions of the
underlying metal. Such graphene coatings have been recently demonstrated as corrosion-resistant coatings for
metals (e.g. Ni, Cu, Fe, and steel alloys) under abiotic environments. However, these studies were based on
relatively short time scales (minutes to hours). Recently, two studies have provided some very interesting
observations on the failure of graphene coatings on copper substrates under abiotic conditions. The reason for
coating failure was attributed to mass transport through the nanoscale defects present on the graphene sheet,
which can be reduced significantly by the use of few-layer graphene. Further, it has been shown that defect
plugging (using passive Al2O3 nanoparticles) caused a significant improvement in the corrosion resistance of
monolayer graphene. In our recent study, we found that 3–4 layer graphene films deposited by chemical vapor
deposition (CVD) offer long-term resistance (~2400 h) to bimetallic corrosion of Ni, especially under microbial
conditions30. In this work, we compare the MIC resistance of graphene to two widely used polymer coatings. In
particular parylene (PA) is one of the most popular barrier coatings used by industry as it has excellent
mechanical properties and provides pin-hole free coatings. Polyurethane (PU) is also widely used to protect
surfaces. A detailed electrochemical analysis reveals that the graphene coating offers ~10-fold improvement in
MIC resistance compared to PU and ~100-fold compared to PA. This finding is remarkable considering that the
average thickness of the graphene coating (1–2 nm) is ~25-fold smaller than PA (40–50 nm), and ~4000-fold
lower than the PU coating (20–80 μm). Analysis reveals that graphene is highly resistant to microbial attack as
compared to the polymer coatings. We perform detailed microbial analysis to comprehend the success of
graphene coatings and the failure of polymer coatings. We also compare as-grown vs. transferred graphene films
and show that transferred films are far more defective than as-grown ones. In addition, we explore the effect of
number of graphene layers and show that few-layered (as-grown) graphene films offer by far the most defect-
free surfaces and are therefore the best suited for microbial corrosion resistance applications. Since many of
graphene’s fascinating properties strongly depend on the concentration and nature of defects,.

14
 Graphene based Marine Coating:

Surfaces of ships and offshore structures are without exception painted with marine coatings. The paints not
only give the ships and platforms a better appearance, but also protect the surfaces from corrosion. Corrosion, as
illustrated in Figure 6(a), is a persisting problem for marine structures that are constantly in contact with sea
water. Every year, corrosion related economic losses in the U.S shipping industry is at $2.7 billion. Corrosion
also results in loss of structural integrity. Statistics shows that 90% of ship failures are attributed to corrosion.
Another protective effects of marine coatings are anti-biofouling. Surfaces that are submerged in the sea water
become rapidly covered by a biofilm of aquatic organisms. This process is called biofouling. Figure 6(b) shows
a biofouling of green seaweed on a ship hull. Biofouling results in increased hydrodynamic drag, lower the
maneuverability of the vessel and increase the fuel consumption. A ship hull with biofouling requires 15-20%
more power for propulsion than a newly painted or maintained hull

Figure 6: a)premature failure of protective coating in ballast

b)biofouling of green seaweed on a ship hull

Despite of many years’ experience and even utilization of modern technologies, the performance of
conventional marine coatings remain far from satisfying. This is particularly true when it comes to longterm
protection of metal from aggressive environment, for which coating failure occurs most often. For the purpose
of anti-biofouling, the dominating copper-based paints, in addition to their negative impact on marine
environment, are only partly effective as they reduce the hard fouling organisms but do not protect against soft
fouling like sea weed. It is therefore essential to develop antifouling marine coatings based on alternative
materials.

Graphene is a “new” material discovered in 2004. This “miracle material” is believed to potentially
revolutionize the world. Graphene is about 100 times stronger than steel and has many other extraordinary
properties, which is a result of its unique molecule structure (illustrated in Figure 2). With the breakthrough of
graphene, we are now enthusiastic to proceed to develop next generation marine coatings. Graphene is
considered as a very promising material to be used for marine coatings due to its extraordinary properties arisen
from its unique structure. Graphene has been proved to be an effective corrosion barrier material because it is
inert under the conditions where chemical reactions of other substrates will take place. Literature study suggests
a bright future for the use of graphene as an anti-corrosion coating material.

15
 Conclusion:

With the breakthrough of graphene, we are now enthusiastic to proceed to develop next generation marine
coatings. Graphene is considered as a very promising material to be used for marine coatings due to its
extraordinary properties arisen from its unique structure. Graphene has been proved to be an effective corrosion
barrier material because it is inert under the conditions where chemical reactions of other substrates will take
place. Also, literature study suggests a bright future for the use of graphene as an antisettlement coating
material.

References:

1) http://coating.ca/graphene-coating/

2) Cooper, Daniel R.; D’Anjou, Benjamin; Ghattamaneni, Nageswara; Harack, Benjamin;

Hilke, Michael; Horth, Alexandre; Majlis, Norberto; Massicotte, Mathieu; Vandsburger,
Leron; Whiteway, Eric; Yu, Victor (3 November 2011). "Experimental Review of Graphene"
(PDF). ISRN Condensed Matter Physics. International Scholarly Research Network. 2012: 1–
56. doi:10.5402/2012/501686. Retrieved 30 August 2016.

3) asuya, D.; Yudasaka, M.; Takahashi, K.; Kokai, F.; Iijima, S. (2002). "Selective
Production of Single-Wall Carbon Nanohorn Aggregates and Their Formation Mechanism".
J. Phys. Chem. B. 106 (19): 4947–4951. doi:10.1021/jp020387n.

4) Bernatowicz, Thomas J; Cowsik, Ramanath; Gibbons, Patrick C; Lodders, Katharina;

Fegley, Bruce; Amari, Sachiko; Lewis, Roy S (1996). "Constraints on stellar grain formation
from presolar graphite in the Murchison meteorite". Astrophysical Journal. 472 (2): 760–782.
Bibcode:1996ApJ...472..760B. doi:10.1086/178105.

5) Fraundorf, P.; Wackenhut, M. (2002). "The core structure of presolar graphite onions".
Astrophysical Journal Letters. 578 (2): L153–156. arXiv:astro-ph/0110585 .
Bibcode:2002ApJ...578L.153F. doi:10.1086/344633.

6) Zan, Recep; Ramasse, Quentin M.; Bangert, Ursel; Novoselov, Konstantin S. (2012).
"Graphene re-knits its holes". Mesoscale and Nanoscale Physics. 12 (8): 3936–3940.
arXiv:1207.1487v1 . Bibcode:2012NanoL..12.3936Z. doi:10.1021/nl300985q.

7) Puiu, Tibi (12 July 2012). "Graphene sheets can repair themselves naturally". ZME
Science.

8) Meyer, J.; Geim, A. K.; Katsnelson, M. I.; Novoselov, K. S.; Booth, T. J.; Roth, S. (2007).
"The structure of suspended graphene sheets". Nature. 446 (7131): 60–63. arXiv:cond-
mat/0701379 . Bibcode:2007Natur.446...60M. doi:10.1038/nature05545. PMID 17330039.

9) Geim & Novoselov 2007.

10) Carlsson, J. M. (2007). "Graphene: Buckle or break". Nature Materials. 6 (11): 801–2.
Bibcode:2007NatMa...6..801C. doi:10.1038/nmat2051. PMID 17972931.

16
11) Fasolino, A.; Los, J. H.; Katsnelson, M. I. (2007). "Intrinsic ripples in graphene". Nature
Materials. 6 (11): 858–61. arXiv:0704.1793 . Bibcode:2007NatMa...6..858F.
doi:10.1038/nmat2011. PMID 17891144.

12) Ishigami, Masa; et al. (2007). "Atomic Structure of Graphene on SiO2". Nano Letters. 7
(6): 1643–1648. Bibcode:2007NanoL...7.1643I. doi:10.1021/nl070613a. PMID 17497819.

13) Shenderova, O. B.; Zhirnov, V. V.; Brenner, D. W. (2002). "Carbon Nanostructures".

Critical Reviews in Solid State and Materials Sciences. 27 (3–4): 227–356.
Bibcode:2002CRSSM..27..227S. doi:10.1080/10408430208500497.

14) Polini, Marco; Guinea, Francisco; Lewenstein, Maciej; Manoharan, Hari C.; Pellegrini,
Vittorio (1 September 2013). "Artificial honeycomb lattices for electrons, atoms and
photons". Nature Nanotechnology. 8 (9): 625–633. arXiv:1304.0750 .

15) Plotnik, Yonatan; Rechtsman, Mikael C.; Song, Daohong; Heinrich, Matthias; Zeuner,
Julia M.; Nolte, Stefan; Lumer, Yaakov; Malkova, Natalia; Xu, Jingjun (1 January 2014).
"Observation of unconventional edge states in 'photonic graphene'". Nature Materials. 13 (1):
57–62. Bibcode:2014NatMa..13...57P. doi:10.1038/nmat3783. PMID 24193661.

16) Bellec, Matthieu; Kuhl, Ulrich; Montambaux, Gilles; Mortessagne, Fabrice (14 January
2013). "Topological Transition of Dirac Points in a Microwave Experiment". Physical
Review Letters. 110 (3): 033902. arXiv:1210.4642 . Bibcode:2013PhRvL.110c3902B.
doi:10.1103/PhysRevLett.110.033902. PMID 23373925.

17) Scheeler, Sebastian P.; Mühlig, Stefan; Rockstuhl, Carsten; Hasan, Shakeeb Bin; Ullrich,
Simon; Neubrech, Frank; Kudera, Stefan; Pacholski, Claudia (12 September 2013). "Plasmon
Coupling in Self-Assembled Gold Nanoparticle-Based Honeycomb Islands". The Journal of
Physical Chemistry C. 117 (36): 18634–18641. doi:10.1021/jp405560t.

18) Jacqmin, T.; Carusotto, I.; Sagnes, I.; Abbarchi, M.; Solnyshkov, D. D.; Malpuech, G.;
Galopin, E.; Lemaître, A.; Bloch, J. (18 March 2014). "Direct Observation of Dirac Cones
and a Flatband in a Honeycomb Lattice for Polaritons". Physical Review Letters. 112 (11):
116402. arXiv:1310.8105 . Bibcode:2014PhRvL.112k6402J.

19) "Spin-dependent hexagonal lattice. : Multi-component quantum gases in spin-dependent

hexagonal lattices : Nature Physics : Nature Publishing Group". www.nature.com. Retrieved
26 September 2015.

20) Bonaccorso, F.; Colombo, L.; Yu, G.; Stoller, M.; Tozzini, V.; Ferrari, A. C.; Ruoff, R.
S.; Pellegrini, V. (2015). "Graphene, related two-dimensional crystals, and hybrid systems for
energy conversion and storage". Science. 347 (6217): 1246501. Bibcode:2015Sci...347...41B.
doi:10.1126/science.1246501. PMID 25554791.

21) Geim, A. (2009). "Graphene: Status and Prospects". Science. 324 (5934): 1530–4.
arXiv:0906.3799 . Bibcode:2009Sci...324.1530G. doi:10.1126/science.1158877. PMID
19541989.

17
22) Geim, A. K.; MacDonald, A. H. (2007). "Graphene: Exploring carbon flatland". Physics
Today. 60 (8): 35–41. Bibcode:2007PhT....60h..35G. doi:10.1063/1.2774096.

23) Kusmartsev, F. V.; Wu, W. M.; Pierpoint, M. P.; Yung, K. C. (2014). "Application of
Graphene within Optoelectronic Devices and Transistors". arXiv:1406.0809  [cond-mat.mtrl-
sci].

24) Jayasena, Buddhika; Subbiah Sathyan (2011). "A novel mechanical cleavage method for
synthesizing few-layer graphenes". Nanoscale Research Letters. 6 (95).
Bibcode:2011NRL.....6...95J. doi:10.1186/1556-276X-6-95. PMC 3212245 . PMID
21711598.

25) Pettes, Michael Thompson; Jo, Insun; Yao, Zhen; Shi, Li (2011). "Influence of Polymeric
Residue on the Thermal Conductivity of Suspended Bilayer Graphene". Nano Letters. 11 (3):
1195–1200. Bibcode:2011NanoL..11.1195P. doi:10.1021/nl104156y. PMID 21314164.

18