Fabrication and Testing of Graphene Infused Acrylic Paint

Karinne Bernanke

Austin Fan

Eric Shen

Hunter Voltz

Dr. Stern

Dr. Hankinson

December 4, 2019
 Abstract
Graphene was integrated into an acrylic paint containing chlorinated copper
phthalocyanine in an attempt to provide the paint with electrical conductive properties. After
spray painting the modified paint onto an acrylic sheet, its surface electrical resistance and
thermal conductivity was measured through various means to conclude that the graphene does
retain its electrically conductive properties when suspended in paint. It was also determined that
the electrical conductivity of the paint correlated positively with the concentration of graphene in
the paint. The thermal testing led to inconclusive results for the graphene’s effect on thermal
conductivity.
 Introduction
As high-tech wireless products become more prevalent in the market, there are a growing
number of potential applications for conductive paints in areas such as e-textiles and circuit
building1. However, current market paints lack the electrical conductivity desired. A potential
solution to this problem is the integration of graphene into the paint.
Graphene’s sp2 hybridized carbon-carbon structure lends a planar structure with uniquely
high electrical conductivity properties. The structure is demonstrated in Figure 1 below.
However, not pictured in the diagram is the ability for the pi electrons in each double bond to
delocalize across the whole plane of the graphene. This delocalization ability is what provides
graphene with its unique property of electrical conductivity.

.
Figure 1: The structure of graphene lends to its electrical conductivity. The pi electrons in each double bond can be delocalized.

Because of graphene’s unique electrical conductivity, we believe the integration of

graphene into paint will increase its thermal and electrical conductivity because of graphene’s
innate high conductivity properties as a result of its structure.
The graphene used in the experiment was acquired from two different sources, and, as
such, were two different qualities and types of graphene. As a result, differing results between
the two different graphene types were expected.
 Previous Research
Graphene oxide (GO) and reduced graphene oxide (rGO) have both been studied as
infusions in household paints. In one study, GO infused paint was found to exhibit corrosion
resistance, inhibit bacterial growth and inhibit fouling on its surface.2 In another,
commercially-available acrylic art paint was infused with rGO and painted on printer paper,
showing strong promise in conductive paper applications.3 We were most interested in testing
electrical conductivity of graphene-infused paint and modeled much of our experimental
procedure after the latter paper. While rGO tends to offer less-than-ideal graphene properties, it
is by far the cheapest and most available form of graphene on the market. Using rGO in our
experiment also makes our results commercially relevant, as there are rGO-infused paints on the
market that takes advantage of the conductive properties of graphene we are investigating.
In the paper we have modeled each sample’s sheet resistance was measured using the Van
der Pauw method. It was found that samples with higher multi-layer graphene (MLG)
concentrations had better conductivity than those with lower concentrations, and samples with a
concentration of 20% MLG had resistances in the kΩ/sq range. It was found that the trend of
better conductivity with higher MLG concentration continued until the MLG began to compose a
majority of the paint, at which point much of the MLG failed to adhere to the substrate after
curing.3 We were primarily interested in how the concentration and grade of rGO affect the
electrical resistance and conductivity of the paint sample and our experiment addresses
concentrations from 10% MLG to 80% MLG.

Procedure
It was decided to make 40g of total product for each ratio of MLG:Paint solids. As was stated in
literature, the total amount of solids was to be 3% of the total product. This means a total of 1.2g
total paint solids, which was split between MLG and paint solids according to desired ratios. The
calculations of required MLG, paint solids, and stock solution for several MLG:Paint solid ratios
are shown in Table 1 below.
 The fabrication of the paint began with the mixing of a copious amount of stock solution:
a 10% paint solids in acetone solution. Second, the necessary amount of MLG and acetone was
mixed for each desired ratio. The corresponding stock solution was then added to that mixture to
achieve the desired MLG:Paint Solid ratio. This 40g total mixture was bath sonicated for 5
minutes as shown in Figure 1 and left to mechanical tumbling until the mixture was ready to be
spray-painted.

Table 1: The table of amounts of MLG, paint solids, and stock solution necessary for each MLG:Paint Solids ratio

MLG:Paint Solids MLG content (g) Paint Solids (g) Total MLG/Acetone Stock Solution Required (g)
Solution (g)

0:100 0 1.2 N/A N/A

10:90 0.12 1.08 29.2 10.8

20:80 0.24 0.96 30.4 9.6

35:65 0.42 0.78 32.2 7.8

50:50 0.6 0.6 34 6

65:35 0.78 0.42 35.8 4.2

80:20 0.96 0.24 37.6 2.4

With the mixture prepared, an airbrush attached to a pressurized CO2 gas tank was used
to spray the paint mixture onto a 11cm wide rectangle on an acrylic sheet. The acrylic was
sprayed until a uniform dark sheet of paint coated its surface. This process is shown in Figure 2.
The samples were then cured and readied for electrical testing.

Figure 3: Spray painting the MLG-paint mixture onto the acrylic sheet (left), Two different-ratio samples on acrylic sheet (right)

For electrical testing, the Van Der Pauw Method was used. The Van der Pauw method
utilizes four probes positioned individually at the corners of the sample. A current is forced
through two probes along an edge of the sample, and the voltage is measured across the two
probes on the opposite edge. The Van der Pauw resistivity is a ratio of the voltage to the current,
and the sheet resistivity was found according to the formula below.

π·RV dP
Equation 1. Rsheet = ln(2)

Simple initial resistivity testing was conducted with a two-probe multimeter at distances of 5, 10
and 20 cm along the center of each sample where the paint was assumed to be the most uniform.

Experimental Results
We first conducted a preliminary testing of resistivity. We used a multimeter with two
probes, placing at incremental distances apart to read the resistance shown on the multimeter. We
tested resistivity with the probes at 5cm, 10cm and 20cm apart. The results were collected and
plotted below:
Figure 3. Two-Point Resistance for MLG Samples

Figure 4. Two-Point Resistance for Phi4 Samples

The resistance of each sample is plotted against the distance of the probe. Note that the result of
MLG 10:90 sample was excluded from this graph as the resistance value was too large for the
multimeter to measure. On the vertical axis, the resistance is plotted on logarithmic scale for
better visualization of the data and the trend. We could observe that graphene from both
manufacturers shows a linearly increase in resistivity as the distance between the probe increase
in logarithmic scale, or an exponential growth in resistance as the distance increase.

Next, the resistance data from the 10cm distance were organized by type of graphene and
the resistance of the samples was plotted against the concentration of graphene in the sample.

Figure 5. Two-Point Resistance at 10cm Distance

Again the resistance of the sample was plotted on a logarithmic scale. We observed that
the resistance of both makes of the paint samples demonstrate downward sloping trend as the
concentration of graphene increases. We can also see that the Phi4 samples has a lower resistance
value at all concentrations, on the order of 10 times smaller. It is then same to conclude that
generally speaking the Phi4 graphene is 10 times more conductive than the MLG samples.

We also used the more inclusive Van der Pauw method to measure the 2-dimensional
resistivity of our samples. Those measurements are tabulated in Table 1.
Table 1. Van der Pauw Resistance Measurements and Calculated Sheet Resistances in Ω/sq

For each sample, the resistance along both the long edge and the short edge were taken. The
probe we used displayed the current and voltage across the two mearing end probes. The
resistance were then calculated and recorded in the charts. The Van der Pauw correction factor is
then taken by calculating the ratio of the resistance and plug into an online calculator. As seen
above the general trend agreed with the preliminary testing. As the graphene concentration in the
paint sample increases the 2-D surface resistivity decrease. And the Phi4 samples have a much
lower resistivity than the MLG sample. However there are many outliers in this result. We can
see certain amounts of uncertainties across the board. fluctuating in the result is partly due to the
small current we run through the sample.

Conclusion
Much of the time this past semester was spent on designing the experiment and the
methods in which we would test electrical and thermal properties as well as deciding on the best
materials to use to get the most accurate results. We were able to perfect the procedure with
multiple trials and have started the data gathering to determine whether graphene increases the
paints thermal and electrical conductivity properties. Our trend lines suggest that generally the
higher concentration of graphene in paint reduces the resistivity, increasing conductivity of the
paint. The paint infused with MLG is shown to be more resistive than the paint infused with Phi4
graphene. MLG is less costly than the Phi4 graphene and is more accessible, possibly opening
doors to a very cheap and easy solution to increase the conductivity of paint.
Two different kinds of graphene were used in this experiment. More types of graphene
must be mixed into the paint to accurately identify which type of graphene affects the
conductivity the most and which graphene is most financially effective. If the team can find a
graphene type that is cheap and also effective, the chances of the paint created in the lab being
able to compete against other conductive paints on the market today is higher. In the experiment,
an acrylic substrate was used as it was cheap and accessible. The acrylic worked very well for
electrical testing but when it came to thermal testing, the melting temperature of acrylic was
overlooked and the thermocouple testing resulted in melting of the acrylic. In the future, a new
substrate such as wood or glass would be better for thermal conductivity measurements. Also,
the procedure includes applying the paint to substrate via air brush. Realistically paint will be
applied via paintbrush, therefore the method of application should vary. The airbrush requires
many layers to fully cover the substrate and one coat of paint applied by a paintbrush may
uncover unexpected results.
Next semester, more measurements must be made along with more batches of paint with
various changed variables. Changing to a new substrate would allow for data concerning the
thermal conductivity of the paint, and more data to be gathered on the electrical resistivity. Our
current data at this moment is not abundant enough to confidently support or disclaim our
hypothesis. Next semester, students must reiterate the procedure with changed substrates, types
of graphene, and application methods to gather enough data to stand with our hypothesis.
 References
1. “Being Creative with Electrically Conductive Paint.” American Coatings Association,
American Coatings Association,
www.paint.org/article/creative-electrically-conductive-paint/.
2. Krishnamoorthy, Karthikeyan, et al. “Corrigendum to ‘Graphene Oxide Nanopaint’ [Carbon
72 (2014) 328–337].” Carbon, vol. 84, 2015, p. 510., doi:10.1016/j.carbon.2014.12.057.
Retrieved from https://www.sciencedirect.com/science/article/pii/S0008622314001407.
3. Mates, Joseph E., et al. “Durable and Flexible Graphene Composites Based on Artists’ Paint
for Conductive Paper Applications.” Carbon, vol. 87, 2015, pp. 163–174.,
doi:10.1016/j.carbon.2015.01.056. Retrieved from
https://www.sciencedirect.com/science/article/pii/S0008622315000810.