garmortech.

com

Delivering inexpensive, high-quality graphene

Jeff Bullington, Chief Technology Officer
Company Summary
• Manufacture high-quality, low-cost graphene
oxide (GO)
What We Do • Expertise in handling/dispersing GO for
composite materials
• Value-added methods

• Polymeric (thermal and electrical)

• Films (UV protection)
Target Markets • Corrosion inhibition
• Cement
• Electronic inks and paste

• PhD Chemists and chemical engineers

Personnel
• Specialists in dispersion and blending technologies

• 6317 McCoy Rd, Suite 100

Headquarters Orlando, FL 32822 USA
• 10,000 ft2 manufacturing facility

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Graphene Graphene
“the basic building block”
Geim et al (2004)
Nobel Prize (2010)
Graphene: flat monolayer of carbon
atoms arranged in a 2D hexagonal
lattice

• Stronger than steel

• Lighter than steel
• 20X harder than diamond
• More conductive than copper

Impressive properties of
graphene arise from the unique Buckyballs Carbon Nanotubes Graphite
Smalley et al (1985) Lijima et al (1991)
chemical bonds Nobel Prize (1996)

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Graphene Applications
Thin-film Graphene
(10+ years in the future)

Cell Phones Flexible Displays Integrated Circuits

Flake graphene
(address today’s markets)

Coatings Paint Additive Plastics Additive

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Graphene Oxide Powder: An ideal additive
Composites
Graphene Oxide (GO) Host
• Polymers
• Fiberglass
• Cement
• Coatings
0.01 – 5wt% 95 - 99.99wt%
Polymer Fiberglass Cement Coatings

Physical property enhancement using low loadings

• GO-Polymer composites show 100% increase in tensile strength1,2
• GO-Fiberglass composites: 1,200X improvement in flexural fatigue lifetime at 0.02wt% loading3
• Cement composites: 60-80% improvement in mechanical properties at only 0.02wt% loading4
• Graphene-coatings: reduced rate of corrosion5 and hardness improvement

GRAPHENE
Great results + 10 years of R&D → why isn’t it used today?

1. Potts et al. Polymer 52 (2011) 5-25

2. Kuilla et al. Prog. Polym. Sci. 35 (2010) 1350–1375 4. Lv et al. Mag. Concrete Res. 65 (2013) 1246-1254
3. Yavari et al. Appl. Mater. Inter. (2010) 2738-2743 5. Dennis et al. Amer. Cer. Soc. Buill. 92 (2013) 18-24.

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 Two “solutions” for any “solution”
Graphene Oxide
• Material produced from our process without
any post-treatment
• Dried in air at ambient temperature
• 4-8% Oxygen
• Polar/hydrophilic
• Ideal for polar hosts and cement

Reduced GO
• Graphene oxide that has been subjected to a
reduction step to remove oxygen
• 1-2% Oxygen
40nm 50nm
• Non-polar/Hydrophobic
• Ideal for non-polar hosts
• Ideal for corrosion protection

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 Garmor GO vs. Hummers GO
Garmor Process
• Edge oxidation of GO flake
• Enhanced electrical properties due to
preserved sp2 orbitals
• Scales to large volume production using
off-the-shelf equipment.
• Chemical reduction can be performed
under mild conditions.
• Process uses green reagents and
produces virtually no waste.
Hummers Process
• Irreversible oxidation of surface and edges
of GO flake
• Oxidation permanently distorts GO thereby
changing the chemical mechanical, and
electrical properties.
• Process uses toxic reagents and produces
hazardous waste.

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Edge Functionalized Graphene
Oxide
Analytical Testing Results Result Units
Poured 154.4 kg/m3
Bulk Density
Tapped 199.4 kg/m3
pH 3 -23.2 mV
Zeta Potential pH 7 -43.1 mV
pH 10 -43.4 mV
d10 1.2 µm
Particle Size
d50 4.2 µm
Distribution (powder)
d90 14.6 µm
Acid Number 9.25 mg/KOH
Moisture Content 3.969 %MC

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Edge Functionalized Graphene
Oxide
Analytical Testing Results Result Units
Carbon 94.25 % At
XPS Analysis Oxygen 5.19 % At
Nitrogen 0.56 % At
Carbon 94.29 % At
SEM Oxygen 5.63 % At
Total Impurities 0.08 % At
BET Analysis Surface Area 204.2 m2/g

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IR Spectroscopy

Annotated ATR spectra comparing Hummers-produced graphite oxide,

graphite, and Garmor’s EOGO material. All of the samples show
absorption in the –OH stretch region. The C=O stretch (dotted line) in
EOGO is masked by the broad graphene peak. Additional C-H and C-O
stretches attributable to carboxylic acids are observable in the spectrum
for our material.
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Raman Spectroscopy

G peak
-1
500 1583 cm

400
2D peak
Intensity (a.u.)

-1
2715 cm
D peak
300 -1
1353 cm

D peak
200 1619 cm
-1
D+G peak
-1
2941 cm

100

0
1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000

Raman Shift (cm-1)

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Applications – Cement/Concrete

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Sample Fabrication

GO-Cement or
Graphene Oxide Host materials Concrete
(GO)
•Cement
•Aggregate

0.01 – 1wt% 99 - 99.99wt%

(Diameter:10cm,
Hight:20cm)
ASTM C39

13
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Composite Testing-Compressive

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Composite Testing-Flexural

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Slump Test of Dry-Mixed Concrete
7
Slump Test
6
• Increased workability
5
• GO acting as water

Slump (in)
4
reducer as well as
strength enhancer 3

2
• Can use lower W/C
1
ratio for further strength
improvement 0
0 0.01 0.02 0.03 0.04 0.05 0.1
GO Loading BWOC (%)

Slump was accomplished as specified in under ASTM standard C143

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GO-Concrete:Compressive
Strength
8000
7000
6000
Strength (psi)

5000
4000
3000
Comp. - Control - W/C 0.5
2000
1000 Comp. - 0.05% GO - W/C 0.45
0
0 5 10 15 20 25 30
Cure Time (Days)

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GO-Concrete Flexural Strength
1400

1200

1000
Strength (psi)

800

600 Flex. - Control - W/C 0.5

400
Flex. - 0.05% GO - W/C 0.45
200

0
0 5 10 15 20 25 30
Cure Time (Days)

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GO-Concrete: Water Content Effects
40%
35%
Compressive
30% Flexural
% Improvement

25%
20%
15%
10%
5%
0%
7 Days - W/C 28 Days - W/C 7 Days - 28 Days -
-5%
Constant Constant Constant Constant
-10% Workability Workability

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Conclusion
– Mixing technique and GO loading is critical in
achieving improved properties
• GO loading optimization;
– just the right amount
– Too much is detrimental

• Dry-mixing requires only moderate shear-mixing

– Just stirring or shaking powders is insufficient
– Rolling pin-type hand-mixing was done
– Scalable mixing method

– Water reduction power of the GO works

synergistically with the increased strength imparted
by the GO

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Applications – Polymers

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GO/Polymers: Electrical Conductivity
Graphene offers ballistic conduction (6,000 S/cm)
• More conductive than copper and silver (and cheaper!)
• Conductivity can be tailored by loading percentage
• Low loadings facilitate processability

Conductive graphene coatings for FRP tanks, pipelines, inks, and 3D printing

Electrostatic Control Antennas, RFIDs, Security tags Conductive Parts

• Additional applications: EMI/RFI shielding, sensors, displays, solar cells

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GO/Polymers: Electrical Conductivity

GO*: Graphene oxide prepared via competing methods

Garmor GO: greater conductivity at lower loadings

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GO/Polymers: Mechanical Strength
Graphene: one of the strongest materials
• Young’s Modulus = 1TPa (6X greater than steel)
• Ultimate tensile strength = 130 Gpa (325X greater than steel)
• High-strength and lightweight
• Graphene as thick as saran wrap can support the weight of an
elephant balanced on a pencil

Graphene composites: from consumer goods to aerospace components

Head Tennis Racquet Automotive Parts Aerospace Parts

• Additional applications: cement, carbon fiber replacement, military gear, drones, laptops

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GO/Materials: Thermal Conductivity
Graphene: Excellent thermal conductivity Pristine GO
1800°C annealed GO

• GO Films: 1,400 W/m•K (Diamond: 1,000 to 2,000 W/m•K, 2200°C annealed GO

2850°C annealed GO

Copper: 400 W/m•K)

• Adding GO to epoxy increases thermal conductivity by 100X
• Low percolation threshold (as little as 0.1wt% GO) can yield
substantial improvement in polymer thermal conductivity

Miniaturization of circuitry creates issues for thermal management

Cell Phone Cooling Microelectronics Avionics

GO composites offer a low-cost, effective solution!

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GO/Polymers: Flame Retardant
Graphene: Excellent thermal conductivity
• Addition of GO to polymers reduces the total heat release and peak heat release rate
during combustion
• Some GO/polymer blends exhibit self-extinguishing traits

GO/polymer nanocomposites were developed at 1, 5, and 10 wt % GO with polycarbonate (PC),

acrylonitrile butadiene styrene (ABS), and high-impact polystyrene (HIPS)

Increasing amounts of GO decrease the heat release rates

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GO/Fiberglass: Fatigue Life
Graphene: Inhibits direct crack propagation
• 0.02wt% GO sprayed on fiberglass laminate:
• 1200X increase in uniaxial flexural fatigue life
• 3 to 5X increase in tension fatigue life
• 20-30% increased flexural strength
• Strong interfacial bond to epoxy
• Simple process could be easily adapted to existing layups

Garmor pursuing continual testing for commercial and military applications

Fiberglass Forming in Vacuum Bag Flexural Testing Neat Fiberglass and GO Fiberglass

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THANK YOU

6317 McCoy Rd, Ste. 100, Orlando, FL 32822

407-540-0452
jbullington@garmortech.com