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From great expectations to

commercial reality:
Graphene-enhanced polymers
and composites
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PureGRAPH®
While graphene is nano-scale thin, its commercial
potential is colossal. Almost from the moment the
nanomaterial was first isolated, and in the decade-
and-a-half since, this potential was widely promoted
by industry, academia and the media, which served
to make graphene something of a household name.
In contrast to the excitement, very few commercial
uses for graphene have been found - leading
some to question whether its potential would ever
be fulfilled.
This situation is now rapidly changing. High-quality,
affordable graphene is now available in tonnage
quantities. The benefits of its use in polymers and
composites has been proven beyond doubt and it is
currently being employed in high-volume industrial
applications.
Genesis
Graphene is a tightly packed layer of carbon
atoms, which are bonded together in a hexagonal
honeycomb lattice. The material was first isolated and
characterised by University of Manchester Professors
Andre Geim and Konstantin Novoselov in 2004.
They found that graphene displays extraordinary
properties. At just one atom in thickness, it is the
thinnest material known. It is 200-times stronger than
steel. It demonstrates an electrical conductivity one
million times that of copper. It outperforms diamond
in terms of its thermal conductivity, is impermeable
even to helium atoms, can stretch to up to 20% of its
length and is highly transparent to light.
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Modifying properties
Moreover, graphene has shown significant promise
as a means to enhance the mechanical, thermal,
electrical and physical properties of plastics and
composites. First Graphene, for instance, has
demonstrated that the addition of just small amounts
of graphene to these materials can enhance their
strength by over 30%, enabling their weight to be
reduced by a similar factor.
Graphene can also be used to increase the thermal
conductivity of polymers and composites. This could
be particularly useful for the production of tooling,
enabling an increase in the rates at which a mould
could be heated and cooled.
Further, research work undertaken recently by a
number of institutions has demonstrated that the
addition of graphene to PU elastomers also increases
their fire-retardance. While most of this work is
understood to be at bench scale in laboratories, First
Graphene has been conducting bulk sample test
work in association with the University of Adelaide on
the potential of its graphene materials (PureGRAPH®)
to increase fire retardancy in polymer compounds,
and the initial results have been impressive.
According to the tests, while a base PU elastomer
burns readily, the addition of approximately 1% w/w
PureGRAPH® to the elastomer increases its limiting
oxygen index (LOI) to 31.6%, meaning that under
normal atmospheric conditions it will not propagate
or support flame .
This promise has fuelled significant research,
not to mention investment , into ways in which
graphene-enhanced polymers and composites can
be commercialised. Until recently, however, use of
these materials has been restricted to high-end
sporting equipment and luxury consumer goods.
That is all about to change. In a significant milestone
for the industry, graphene is now being supplied to
businesses in tonnage quantities for commercial
applications.
Graphene Goes Large
The global mining industry produces 17 billion metric tonnes of
minerals each year, with the iron ore industry alone processing
in excess of 1.6 billion tonnes annually. Inevitably, the equipment
that handles this ore suffers from wear. The industry uses a range
of strategies to prevent this wear and prolong the working life of
its equipment. One such strategy is the use of sacrificial liners for
the protection of steel equipment.
In June 2018, First Graphene started working with newGen
Group to increase the strength and abrasion-resistance of these
liners using its PureGRAPH® 20-µm graphene nanoplatelets.
PureGRAPH® powders were mixed into polyurethane (PU)
elastomer using standard industrial mixing equipment and no
pre-treatment of the graphene additive or other formulation
changes were required.
Liners cast from these enhanced PU resins demonstrated
an increase in tensile strength of 37%, a 50% increase in tear
strength, enhanced elongation and a 100–500% improvement
in abrasion resistance (according to a Taber test). As a result, the
linings last much longer, reducing their need to be replaced and
thereby lowering costs associated with production stoppages.
newGen Group has now launched a range of graphene-
enhanced wear-protection liners for applications including
reclaimer buckets, pipe spooling, dryer chutes and conveyor
applications under its newly created ArmourGRAPH™ brand.
Scaled trials of the liners are underway with its key customers.
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Why has this taken so long, and what problems have had to be overcome?

Efficient production
Firstly, efficient and cost-effective methods for the
production of graphene have had to be developed.
The material and its derivatives can be prepared using
a wide variety of methods that can be defined broadly
as either bottom-up or top-down.
The use of bottom-up processes is generally limited
to the manufacture of thin-film graphene for the
electronics and photonics industries. These processes,
through which graphene materials are directly
synthesised from gaseous carbon sources by chemical
vapor deposition (CVD) or epitaxial growth, cannot
produce quantities of the material large enough for
use in polymers and composites.
By contrast, top-down approaches see graphene
produced through the exfoliation of graphite - a
commodity material - hundreds of thousands of
tonnes of which is mined each year. While these
methods enable the production of large quantities of
graphene, some methods have significant drawbacks.
In particular, the Hummers’ method involves boiling
graphite in concentrated sulphuric and nitric acid plus
potassium permanganate for around 24 hours, which
serves to expand the material and separate graphene
nanoplatelets from it. However, this process causes
significant damage to the nanoplatelet structure and
creates large amounts of corrosive waste.
Graphene can also be exfoliated directly from graphite
by ultrasonic treatment where the separation of
graphene platelets is driven by cavitation waves
in an organic solvent or surfactant solution. Yields
from ultrasonic processing are small and the organic
solvents used are often toxic and expensive to handle.
Mechanical high shear mixing methods can also
be employed for the same purpose. All require the
application of mechanical attrition, which reduces
the thickness of graphite sheets, but also has a similar
effect on their length and width, lowering their
aspect ratio. A high aspect ratio is a key advantage in
graphene materials.

Getting the right mix The need to standardise

Secondly, the large area of graphene materials
induces attractive forces between them, which can
lead to their agglomeration in resinous matrices.
The surfaces of graphene materials do not react
chemically, which means that they do not bond well
with resin materials which can lead to composites
with poor mechanical performance.
Graphene manufacturers are developing strategies
for functionalising – or activating – the surfaces of
graphene materials through the addition of various
chemical end groups.
Conventional functionalisation methods can cause
significant damage to the structure of the material,
leading to defects in the final product. First Graphene
has overcome these problems through the use of its
proprietary electrochemical exfoliation process.
Another major hurdle in the development and
commercialisation of graphene has been that of
standardisation. Some graphene standards are in
the early stages of development. One example is the
graphene and related two-dimensional materials
terminology standard (ISO/TS 80004-13:2017), which
discusses definitions for graphene and other 2D
materials and terms for naming methods for their
production, properties and characterisation. The
aim of this standard is to harmonise communication
across the value chain.
Further, a graphene-related work programme
(NTI/1²) has been set-up at BSI Group and is working
on a number of standards, a Publicly Available
Specification (PAS 1201), entitled Properties of
graphene flakes - Guide is also under development.

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Electrochemical route PureGRAPH® Graphene Powders from First Graphene Ltd

Several graphene manufacturers are utilising
electrochemical exfoliation; First Graphene
in particular, are now achieving excellent and
consistent results by producing graphene via the
electrochemical exfoliation of graphite. First Graphene
uses high-purity graphite (as one-inch chips) directly
from its mines in Sri Lanka.
Before placing it in an electrochemical cell, no pre-
treatment of this graphite is required. An applied
This ensures that, unlike the samples tested
elsewhere, they perform consistently and repeatably
when mixed with a polymer matrix.
PureGRAPH® 20
First Graphene has found that its graphene D50 = 20 µm | Sheet Resistance3 = < 10 Ohm/square | Tapped Density4 = 0.251 gcm-3
nanoplatelets disperse readily in solvent and
polymer media. The electrochemical exfoliation Particle Size Distribution1 Raman Spectroscopy2
process employed by the company imparts low and
7 14000
controllable levels of oxygen functionality onto the
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plate edges. As a result, for most polymer systems, 12000

Relative Intensity
voltage drives ionic species in an electrolyte to standard mixing processes can be used to incorporate 5 10000

% Volume in
intercalate into the graphite, where they force apart the company’s graphene. 4
8000
its constituent layers, creating large, thin sheets of 3
6000
graphene. This process generates a high yield of Now that these technical challenges have been 2
4000
graphene products from graphite. solved, the company has moved quickly to the 1
2000
manufacture of high-quality graphene materials in 0
With a typical thickness of 5-10 carbon layers, the industrial quantities. First Graphene currently has -1 0
0.1 1 10 100 1000 1000 1500 2000 2500 3000
powders contain pristine, high-aspect-ratio platelets an annual production capacity of 100 tonnes and is
Size / µm Raman Shift (cm-1)
of graphene. These have high levels of purity, planning to scale this even further in the coming
featuring less than 0.3% w/w total metals and fewer years. Now suppliers of graphene must work in
than one-part-per-million of silicon contaminants. close partnership with their customers to prove the
benefits and value of their materials in real-world PureGRAPH® 10
Sophisticated finishing steps are used and the end applications.
result is nanoplatelets (called PureGRAPH®) that can
D50 = 10 µm | Sheet Resistance3 = < 10 Ohm/square | Tapped Density4 = 0.124 gcm-3
be then carefully controlled to 5 µm, 10 µm and 20 Particle Size Distribution1 Raman Spectroscopy2
µm. (These are typical additive sizes for use in paints,
coatings, polymers and composites.) 9 14000
8
12000

Relative Intensity
7
10000

% Volume in
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Malvern Mastersizer 3000E. Graphene powder dispersed in water & surfactant.

5

Four-point probe measurement of a 25 µm film collected on membrane filter.

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First steps 3
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4000
1
2000
First Graphene is exploring a number of other high- 0
volume markets for its PureGRAPH® graphene materials. -1 0
0.1 1 10 100 1000 1000 1500 2000 2500 3000
For instance, the company is working with Steel Blue, a

Raman analysis using a large area remote sampling probe.

Size / µm Raman Shift (cm-1)
major global manufacturer of work boots, to increase the
strength and reduce the weight of the composite toe caps
in safety footwear. Prototype testing has been successfully
completed and field trials are currently underway.
PureGRAPH® 5
First Graphene has also shown that the addition of small D50 = 5 µm | Sheet Resistance3 = < 10 Ohm/square | Tapped Density4 = 0.062 gcm-3
amounts of PureGRAPH® for the production of large-area
leisure industry items can increase their flexural strength Particle Size Distribution1 Raman Spectroscopy2
by more than 30%. This enables less material to be used in
12 12000
the manufacture of these items - reducing weight, material

According to ASTM D7481.

costs and the cost of labour associated with their hand 10 10000

Relative Intensity
lay-up. The use of graphene in these applications has other
% Volume in
8 8000
benefits; the nanomaterial creates a water-resistant barrier
and, as it increases the thermal conductivity of the material, 6 6000
its curing behaviour is more consistent.

REFERENCES
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Size / µm Raman Shift (cm-1)

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AUSTRALIA
Corporate Headquarters & Manufacturing Plant
First Graphene Ltd
1 Sepia Close
Henderson
WA 6166
Australia
Phone: +61 1300 660 448
Email: info@firstgraphene.net
Web: firstgraphene.net

EUROPE
Global R&D & Marketing
First Graphene (UK) Ltd
Graphene Engineering & Innovation Centre
The University of Manchester
Sackville Street
Manchester
M13 9PL
United Kingdom
Phone: +44 (0)161 826 2350
Email: info@firstgraphene.net
Web: firstgraphene.net