FEATURE: Graphene

revolution remains distant

despite increasing
affordability

Graphene is a single-atom-thick later of carbon bonded in a hexagonal lattice (Credit

for all images: Shutterstock)

These range from super high-capacity batteries to

materials so strong and light they could be used to build
a space elevator. As these new forms of carbon start to
become more affordable, they are appearing as structural
reinforcement in consumer products. They are being
added to bicycle frames, tennis rackets and even sports
shoes. Despite this we haven’t seen the revolution in
super-strong and light materials that has sometimes
been suggested.
It has been suggested that graphene and carbon
nanotubes (CNTs) could produce much stronger and
lighter structures, more efficient electrical energy
systems, nano-bots, cheap flexible solar cells, abundant
freshwater and much more. In isolation, sheets of
graphene and individual carbon nanotubes are extremely
strong and stiff, as well as having low density.

Induced cross-linking
Carbon nanotubes have demonstrated 20 times the
strength-to-weight ratio of the strongest carbon fibres.
However, to be used as a structural reinforcement in
composite materials, millions of nanotubes must be
combined to form a fibre. Within these fibres the
nanotubes slide past each other, resulting in relatively
weak fibres. This is a bit like the soft graphite in a pencil,
which is made of layers of graphene that slide past each
other.

Just because a material has incredible strength at the

molecular level, we can’t assume these properties will
transfer to the material’s bulk strength. There is some
encouraging research showing that irradiation of
nanotube bundles can induce cross-linking. However, so
far this only works with a few bundles containing a few
nanotubes. Replacing carbon fibre would require fibres
containing millions of crosslinked nanotubes. It is not
clear whether this will be possible.
Carbon nanotubes are classified as either single-wall
carbon nanotubes (SWCNTs) or multiwall carbon
nanotubes (MWCNTs). MWCNTs are effectively a number
of CNTs of different diameters located inside each other.
The structural properties of CNTs are largely determined
by diameter and defects. Raman spectroscopy is typically
used to characterise SWCNTs, with a number of
excitation modes used to identify tube diameter, purity,
chiral angle and level of structural defects.

There are two main vibration modes identified by Raman

spectroscopy of graphene: G (1,580cm-1) and D
(1,350cm-1). In pure graphene the D mode cannot be
observed directly owing to crystal symmetries but can be
detected as an overture D2 peak. The ratio between the
intensity of the G and D spikes in the spectrum is an
indication of the purity of graphene, with bulk graphite
producing a distinctly different ratio.

The ratio of G/D modes is an indication of defects and is

the standard measure of structural quality, with ratios
over 100 regarded as high quality. MWCNTs usually have
more defects and are difficult to characterise optically.
Chiral angle is the orientation of the hexagonal
arrangements of carbon atoms within the walls of the
tubes. It can be thought of as the direction that a flat
sheet of graphene would be rolled to produce the CNT.
Chiral angle primarily affects electrical properties,
causing CNTs to be metallic or semiconducting.
Delivering strength
The National Graphene Institute and the Aerospace
Technology Institute reported recently that graphene and
CNTs are not yet ready to replace carbon fibre as the
primary reinforcement in composites, but they do have
potential as unstructured additives to resins and plastics.
Graphene can be added to the resin in thermoset
carbon-fibre composites. The carbon fibre provides
stiffness while the graphene improves interlaminar shear
strength and damage tolerance. This can enable reduced
ply thickness. Graphene may also be the primary
reinforcement in small high-performance polymer parts,
providing stiffness and enabling these materials to
replace metal.

For a number of years after being isolated, the cost of

graphene and CNTs was thousands of dollars per gram,
making use as a structural material uneconomic.
Industrial production processes are now coming online
and CNTs are available for a few dollars a gram. As a
result, a range of consumer products is now being
marketed as containing graphene, although they typically
only contain very small quantities.

Sporting chance
The first company to supply carbon nanotube-enhanced
materials commercially was Zyvex Technologies. In 2005
it worked with Easton Sports to produce a baseball bat
featuring carbon nanotubes. Zyvex now supplies a range
of prepreg, resins and adhesives enhanced with carbon
nanotubes and graphene. Compared to carbon fibre
alone, it is claimed that this combination increases tensile
strength by 26%, compressive modulus by 12%, flexural
modulus by 35%, interlaminar shear by 20%, and fracture
toughness is nearly doubled.

The first company to produce a graphene product was

Head with a graphene tennis racket in 2013. Head
claimed the graphene allowed it to reduce weight by 20%
while increasing strength by 30%.

Graphene and CNTs are now used in many products. For

example, Dassi produces a bicycle that it claims is 30%
lighter and twice as strong owing to the addition of just
1% graphene.

According to Dassi, the graphene is first added to the

resin and a prepreg is then created. “We mix graphene
with an epoxy resin we developed ourselves that is then
electronically functionalised to disperse the graphene
evenly within the resin. The carbon weave is then
introduced into the resin mix, which in turn forms the
graphene carbon material in a prepreg that can be used
for laying-up components,” says the company.

It may seem strange that significant performance

improvements are possible when experimental lab
experiments show the bulk strength for larger samples of
graphene is still lower than for carbon fibre. However, the
carbon fibre is still providing the strength and stiffness in
these products. The addition of graphene improves
interlaminar shear strength, fracture toughness, and
carbon-to-resin adhesion. It can also retard crack
propagation.

Reinforcing printed parts

Another interesting application for graphene and CNTs is
as a reinforcement within 3D-printed polymer parts. Print
filaments containing graphene are available commercially
from suppliers such as Directa Plus, Graphene 3D Lab
and Haydale. As well as improved strength and stiffness,
the carbon material also increases thermal conductivity,
which can facilitate higher deposition rates.

It seems that composites can currently be improved by

adding graphene and CNTs. Improvements in interlaminar
shear strength and damage tolerance are possible and
may under certain circumstances reduce mass by up to
50%. However, the order of magnitude improvements in
strength to weight that it has been suggested graphene
and CNTs could one day offer are not currently feasible.
Significant developments would be required to enable
cross-linking of graphene sheets or CNTs so that bulk
material properties could approach the strength of
isolated nano-structures.

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