28 M A R I N E C O AT I NG S
Source: Ilya - stock.adobe.com
GETTING TO GRIPS
WITH GRAPHENE
How a nano-sized carbonaceous additive may significantly improve marine coating practice. By I. A. Rodionov,
M. Gaier, R. Ingham, L. Martins, G. Heddon, M. Algermozi, Graphene Enterprise.
Graphene is evolving as a functional additive and means of en-
vironmental protection in marine coating systems. In this pa-
per, we discuss graphene and compare graphene-based paints
with mineral-based pigmented coatings to build a case for
boosting graphene use in marine coatings so as to make the
production and life cycle of graphene materials more ecologi-
cally friendly and sustainable.
S ince Novoselov et al. successfully exfoliated graphene from
graphite in 2004 [1], applied research on graphene has become
popular in many areas, including smart polymeric coatings. Industrial
coatings, such as marine and automotive types, are composite materi-
als that are reinforced with particulate fillers for imparting toughness,
durability, colour, anti-corrosion protection, and other functions. The
efficacy of a pigment depends on its physico-chemical nature and na-
no-sized fillers have previously been shown to require significantly less
pigment to deliver the same performance as µm-sized fillers [2]. Vari-
ous nano-materials, such as graphene, ceramics and silver, are seeing
increased usage in marine paint formulations due to their benchmark
size-related properties, which are shifting the paint production par-
adigm towards nano-grade fillers, and lessening the impact on the
E U R O P E AN CO AT I NGS J O UR N AL 12 – 2021
environment and reducing mining activities [3]. Unmatched by other
nano-materials in its capacity to boost a paint’s abrasion resistance,
conductive properties, hydrophobicity and barrier characteristics,
graphene is currently in the spotlight of the marine coatings industry,
as one of the least toxic fillers for both improving the overall quality
of marine topcoats and primers and reducing the ecological footprint
of the paint manufacturing process. Adoption of graphene as the spe-
cialty pigment incorporated into paints via wet transfer techniques [4]
may lower the consumption of toxic mineral fillers and thus mitigate
the environmental impact of paint manufacturing operations, and
may well mark the beginning of a new generation of protective coat-
ings. In this article, we establish the key features of graphene-based
coatings and discuss the prospects and opportunities that graphene-
based paints offer the industry.
SETTING STANDARDS FOR GRAPHENE
The 2020s are seeing a shift in graphene production levels, with the
technology becoming more affordable and amenable to large-scale
production – graphene is about to undergo widespread adoption as
a pigment in liquid and powder coatings [5]. Besides notorious mi-
 MA R I NE C O AT I N G S 29

Figure 1: Barrier properties (A) 1.8 % of graphene and (B) 8 % of

wollastonite acting as barrier pigment.

RESULTS AT A GLANCE 5–15% >65%

removal removal
 As little as 1–4 % graphene helps to enhance the barrier and
anti-corrosive characteristics of protective marine coatings, im-
proves high-build and flexibility properties, coating hardness
and mechanical robustness, and leads to an overall 2- or 3-fold
reduction in use of total pigment in the paint formula.

 With the global marine coatings market forecast to expand

to US$14.52 by 2025, graphene will see greater exposure to ma-
rine coatings.

 The long-term benefits of using graphene, such as reduced

levels of pigment use, superior functionality, and small ecologi-
cal footprint will be highly sought after in marine coatings ap- 1.8% Graphene 8% of Wollastonite
plications.

 Graphene can potentially simplify paint production technol-

ogy and cut costs, and can help mitigate workplace hazards.
the type of graphene it is using and to control its quality. PLD- and
flame-synthesised graphene are cost-effective and yield multi-layered
graphene, which is currently set for mass deployment by paint manu-
facturers in the marine, industrial and automotive sectors.

COATING, HEAL THYSELF!

Marine coatings are used to protect onshore/offshore steel structures

cromechanical exfoliation, there are several cost-effective ways to
mass-produce graphene: liquid-phase exfoliation (LPE), chemical va-
pour deposition (CVD) and flame synthesis [6]. The National Physi-
cal Laboratory (NPL), in collaboration with international partners, has
developed an ISO/IEC standard, ISO/TS 21356-1:2021, for measuring
the structural properties of graphene, typically sold as a powder or
as a liquid dispersion. This ISO/IEC standard helps industry to define
and marine vessels. While such “green technologies” are welcome,
they must possess good impact resistance, chemical and corrosion
resistance, and excellent anti-fouling characteristics, all of which can
be achieved by using graphene as a nano-additive. Graphene parti-
cles are nano- to sub-µm-sized and have a nano-lamellar shape which
translates to a specific surface area of more than 2000 m2/g; this is
several orders of magnitude greater than the 1.5 m2/g for wollastonite 

Figure 2: Accelerated corrosion test.

A B
Graphene primer Intershield 300
9A – DF T: 8A – DF T: 9A – DF T: 8A – DF T:
158 µm 269 µm 158 µm 269 µm

Rust
creepage Rust creepage

Scribed Non-scribed Scribed Non-scribed

E U R OP E AN COAT I NGS JOU RN A L 12 – 2021

 30 M A R I N E C O AT I NG S

 (and 3 m2/g for mica), wollastonite being the most abundant filler used
for protective applications. In its role as a hydrophobic pigment mate-
rial, graphene induces a tortuous path for gas and moisture within a
composite coating film [7]. Graphene oxide nano-particles are known
to covalently co-crosslink with the epoxy binders in hybrid systems in
the presence of silamines [8]. This boosts the adhesion of the coat-
ing to the metallic substrates and extends their anti-corrosion per-
formance. Another notable feature of graphene is its self-repairing
ability, which may be critical in remote long-term applications. In liquid
systems, graphene is also known to cause shear-thinning, a fact un-
derpinning its use as a thixotrope in paints [9]. Our company (GIT)
is actively contributing to the development of graphene-based smart
coating technologies.
Several tests conducted by us, as well as multiple industrial and scien-
tific reports, reveal the key functions of graphene in epoxy coatings,
both primers and topcoats, to be those listed below and in Table 1:
ąą Functional pigment concentrations: As little as 1–4 wt.% of gra-
phene unlocks the protective and other functional features that
could be achieved by inorganic primers at 20–60 wt.% pigment.
ąą Toxicity: The European Chemicals Agency (ECHA) has classified gra-
phene as a non-hazardous dusting substance and recently initiated
a “Graphene Flagship” working group to facilitate the commercialisa-
tion of graphene-containing goods for public use in Europe [10, 11].
ąą Barrier properties: Achieved at 2 vol.% graphene. Bisphenol A-
based composition crosslinked with phenalkamine; samples were
incubated in a salt fog chamber for three weeks, dried for 48 hours,
then examined by a tape adhesion test (Figure 1).

Figure 3: Coating scratch resistance. The sharp steel pin with Figure 4: Coating flexibility. 1: Wollastonite, barytes, phthalo-
the 5000 g weight was positioned at a 90° angle to the coated blue; 2: TiO 2 rutile; 3: wollastonite, barytes, FeO red; 4: wollas-
substrate and then pulled for approx. 10 cm along the sample tonite, barytes, graphene.
while the plate remained immobile.

Intershield 300 Graphene primer no cracking

Damaged finish

Wider Shallow
scratch scratch
(~3 μm) (~2 μm) 1 2 3 4

Intershield 300 Primer coating

coating DF T 251 μm
DF T 136 μm

Table 1: Positive Impacts of the application of the graphene-based pigments to the polymer coating manufacturing process.

Paint manufacturing sector Issue How application of graphene solves the issue

Production floor Usage of toxic chromate chemistries and other fillers for anti- Substitution with graphene, retains the paint efficiency
corrosive protection.

Production floor - Large amounts of filler powders, time consuming addition Reduce the amount of powders, use graphene in
process the tints with other pigments
- Energy exhausting grinding step
- Multiple types of fillers required

Storage Vast amount of space required to store pigments and fillers dry Significantly reduce amount of pigment to be stored,
and safe without cross-contamination as less filler required for production

Procurement - Freight costs depend on total weight of pigment to be Reduce load on the transportation,
delivered ess toxic for transportation.
- GHG emissions associated with freight transportation

Health and safety Large amounts of hazardous chemicals used to produce prim- Graphene poses lesser risks [10] as the conventional toxins
ers and certain topcoat products and may sustain the vital functions of the conventional chem-
istries without health risks applied

E U R O P E AN CO AT I NGS J O UR N AL 12 – 2021
 MAR I NE C OAT I NG S 31
ąą Corrosion resistance: Each tested paint was sprayed in trip-
licate onto sand-blasted substrates measuring 6 by 16 cm (Fig-
ure 2). Graphene-based primer containing from 1 to 3 %wt gra-
phene was coated at DFTs 158 and 159 µm, and the aluminum
primer controls were coated at DFTs 90 and 70 µm. A linear
10 cm scribe was made on each plate with a sharp knife and
0.5-cm holes were drilled to connect copper wires to plates. The
samples were then weighed and immersed in 0.5 M aqueous
NaCl at 20–23 °C. The accelerated corrosion test was run for 192
hours with the aid of a EPS 600 Electrophoresis Power Supply
operating at a voltage of 1 V and an applied current of 190 mA,
as measured by the multimeter. The samples were dried and
their weights measured and they were then subjected to the
rust creepage test (ASTM D1654) and adhesion strength by tape
test (ASTM D3359).
ąą Scratch resistance / Hardness: As little as 1–3 % graphene
confers hardness and abrasion resistance comparable to those
of metallic primers and ice-breaker paints (Figure 3).
ąą Flexibility: Graphene helps to improve the flexibility of the filled
paints, irrespective of the type of binder/pigment package (Fig-
ure 4).
Concerns about the biohazard posed by graphene in both ma-
rine and on-shore environments are also being addressed, as the
ECHA has officially recognised very limited evidence of toxicity [11],
and this is paving the way to mass use by the paint industry [10].
Several of the recent marine coating applications of graphene in-
clude its use as a proven effective anti-scratch and hydrophobic
additive in marine anti-fouling [12] and ice-phobic systems [13], as
well as graphene-filled anti-corrosive barrier primers on liquefied
natural gas vessels.
HURDLES REMAIN
However, there are still several technological hurdles to wider
adoption of graphene-based fillers:
ąą Residual auto-catalytic corrosion caused by graphene applied
alone: a mono-layer of graphene on a steel substrate can cata-
lyse cathodic corrosion of the substrate, and hence corrosion
inhibitors are recommended.
ąą Poor dispersibility in aqueous media, due to the hydrophobicity
of graphene.
Find out more!
Marine coatings
290 search results for marine coatings!
Find out more: www.european-coatings.com/360
E UR OP E AN COAT I N GS JOUR N AL 12 – 2021
ADVERTISEMENT
Karl Hendrik
Schluckebier
Product Manager
Zeppelin Systems
“Reduce potential hazards
to a minimum”
Zeppelin Systems specialises in plant engineering for the hand-
ling of high-quality bulk materials. The company supports its
customers from plant design to realization. In addition,
it develops components for key plant functions that are also used
in third-party plants. This also includes mixers,
such as the CMQ container mixer.
How can dust explosion occur during mixing and how does the
container mixer respond to the requirements of dust explosive
materials? Even everyday products such as flour, plastics or additives
can generate a dust explosion if they come into contact with heat and
oxygen in a certain concentration as a dust-air mixture. It is therefore
important to reduce potential hazards to a minimum in advance of
the mixing process. The patented container mixer CMQ from Zep-
pelin Systems, with its additional ATEX equipment with monitored
grounding, proves that it can meet the requirements of dust-explo-
sive substances and offers the user the highest level of safety.
In addition to safety standards, good dispersion is also particu-
larly important, what kind of performance does the container
mixer provide here? The mixing tool ensures fast material move-
ment as well as good dispersion while keeping mixing resistance low.
This protects the products and can reduce the temperature rise to a
minimum, for example to les than 2 degrees Celsius per minute for
a powder coating mixture. Another advantage of the mixing arm is
its airfoil shape. It causes a high suction effect on the material. This
results in a high lifting force and optimum formation of the mixing
drum for faster mixing. Thus, the user obtains his desired mixing re-
sult within three to four minutes.
Why is good and fast cleaning of the mixer so important and how
does the product design of the CMQ help? If deposits collect on
the mixing head, mixing tool or in the mixing container, adulteration
can occur in subsequent mixes, rendering the mix unusable for fur-
ther use. Compared to conventional container mixers, Zeppelin Sys-
tems has optimised these critical components to simplify the cleaning
process many times over and save valuable time. E.g. the mixing head
of the container mixer CMQ is designed in such a way that - unlike
conventional, usually trough-shaped mixing heads - it consists of a flat
plate, which makes cleaning very easy and fast. Also, the large dis-
tance from the mixing tool to the bottom of the mixer makes it much
more accessible and thus easier to clean. The shape and polished sur-
face of the CMQ’s mixing tool also minimises deposits. At only 17 kg
for a 1,000-liter mixer, the tool is very light, allowing users to disas-
semble and replace it quickly and easily. With all these measures, the
operation of the mixer reduces cleaning time by up to 80 %. This not
only increases productivity, but also machine availability, saving five- 
figure sums per year.
 32 M A R I N E C O AT I NG S

 Table 2: Break-down of the environmental impact potentials mod- ąą Additional chemical modifications of graphene aimed at further in-
elled for the standard anti-corrosive epoxy-based technology. creasing the bio-compatibility of graphene particles.

SUSTAINABLE MANUFACTURE OF GRAPHENE PAINTS

MAETP GWP ADP
Pigment/Additive
in kg 1,4-DBeq/kg in kg CO2eq/kg in kg Sbeq/kg
Several companies are now able to produce graphene by the ton on
a daily basis and with batch-to-batch repeatability, and recent devel-
Bisphenol A epoxy 2,577.3 3.94 0.04671
opments in graphene processing now enable the efficient dispersion
of graphene into paints in production-scale settings [4]. The model
Xylene 263.4 1.64 0.02978
production of a graphene-based anti-corrosion primer system is illus-
trated in Table 1 – such systems otherwise typically require the use of
Acrylic additive 339.7 0.44 0.00483 up to 40–70 wt.% mineral fillers, which incur significant costs in terms
of energy consumption, health and safety procedures, and overall
Barium sulphate technological complexity of the manufacturing process. Implemen-
(product of barium 30,280 1.20 0.00563 tation of graphene as the specialty pigment in paint manufacturing
sulfide) may, at very least, halve the filler consumption and reduce the paint
production hurdles.
Titanium dioxide 3,320.9 2.04 0.00138
LESS ENERGY NEEDED FOR PRODUCTION AND SUPPLY
Zinc oxide 620.7 0.78 0.00061
Studies show that, among others, the production and supply of raw
Bentonite 112.8 0.039 0.00026 materials are the greatest factors governing the environmental im-
pact of a paint over its life cycle (see Table 2). An alternative graphene-
Pumice 3.04 0.0084 0.00004 based primer, produced with the same resin/diluent/additive master-
batch, would contain a total of 10–20 wt.% of pigment, a nearly 3-fold
Graphene (product of reduction compared to the conventional mineral-based technology,
23.4 0.023 0.00020 and would in turn require less energy input for pigment processing,
graphite)
taming workplace toxicity hazards, as well as be less toxic to aquatic
Zinc phosphate (prod- life during the paint’s life cycle, with the final material matching or sur-
uct of phosphoric acid 4,530.1 2.21 0.20100 passing high-solids mineral systems in terms of performance.
and zinc oxide)
SMALL ENVIRONMENTAL FOOTPRINT
Strontium chromate
(product of strontium A small environmental footprint is another long-term benefit of incor-
6,067.6 5.49 0.03100
carbonate and sodium porating graphene into the paint manufacturing process. Common
dichromate) pigments and additives for marine protective primers are barium sul-
fate, titanium dioxide, acrylics, zinc oxide, bentonite, strontium com-

Figure 5: Comparison of the environmental impact potential of graphene-based and mineral-based primers.

Graphene based primer Inorganic primer

100 % 100 %

80 % 80 %

60 % 60 %

40 % 40 %

20 % 20 %

0% 0%
MAETP GWP ADP MAETP GWP ADP

 Bisphenol A epoxy  Xylene  Bisphenol A epoxy  Pumice

 Acrylic additive  Graphene  Acrylic additive  Titanium dioxide
 Barium sulfate  Titanium dioxide  Barium sulfate  Zinc oxide
 Xylene  Zinc phosphate
 Silica sand  Strontium chromate
 Bentonite

E U R O P E AN CO AT I NGS J O UR N AL 12 – 2021
 MAR I NE C O AT I N G S 33

pounds, etc. A basic comparative life cycle assessment was conducted MARINE ECOTOXICITY NEEDS A HIGHER WEIGHTING
on the raw materials required for making 1 kg of an inorganic primer
and a proposed graphene-based primer model (Table 3). Mineral filler Global warming potential and abiotic depletion potential are meas-
loadings for the traditional epoxy-based formula and the graphene- ures of carbon dioxide emissions and depletion of non-renewable
based primer were inspired by the open-source guidelines from resources. Marine aquatic toxicity potential is a combination of envi-
Cardolite, while levels of graphene in the graphene-based coatings ronmental fate, ecological exposure, and ecotoxicity effect factors [2].
formulas were inspired by the open-source scientific publications [4]. The analytical results show that the potential is mainly impacted by
The purpose of the assessment was to quantify the theoretical envi- the following raw materials: barium sulfate, zinc phosphate, strontium
ronmental impact of both model systems in terms of marine aquatic chromate, and bisphenol A epoxy production. In view of the fact that
ecotoxicity potential (MAETP), global warming potential (GWP), and these coatings are being produced for use in marine environments,
abiotic depletion potential (ADP). The MAETP, GWP, and ADP values marine ecotoxicity should be assigned a high weighting as an environ-
in Table 3 are simulations based on the production of each raw mate- mental impact factor.
rial as determined with the aid of OpenLCA software. The “Ecoinvent A combination of graphene’s low environmental impact, intensive
3.5Cut-Off Unit Processes Regionalised” LCA database was used and functional properties, and ever-growing accessibility make it a must-
“CML 2 baseline 2000” was selected as the life cycle impact assess- have for protective smart paints – if not as a bulk filler, then as a nec-
ment method. essary functional additive. This outlines the graphene-based pigments
Barium sulfate, titanium dioxide, zinc phosphate and strontium chro- as a green alternative to the traditional mineral pigments and fillers.
mate dominated graphene nano-platelets across all three environ-  
mental factors (MAETP, GWP and ADP), in the comparison based on
the wt.% composition of the pigment used for achieving same-level REFERENCES
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Table 3: Graphene-based primer vs. inorganic primer compo- Mechanical and Thermal Behavior of Glass-Basalt Hybrid Nano Com-
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[3] Peng, T., et al., Polymer Nanocomposite-based Coatings for Corro-
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[kg 1,4-DBeq /kg
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product]

Global warming
potential (GWP) 2.99 2.92
[kg CO2eq/kg product] Ilia Rodionov
Graphene Enterprise
Abiotic depletion ilyar@grapheneenterprise.ca
potential (ADP) 0.033 0.035
[kg Sbeq/kg product]

E U R OP E AN COAT I NGS JOU RN A L 12 – 2021