Conductive Coatings: Using Carbon Nanotubes

Conductive
Coatings
Using Carbon Nanotubes
n recent years, requirements for modern coatings have dramatically increased. Besides optical
appearance, new functionalities like improved
mechanical properties, anti-static behavior or
electrical conductivity are desired. To achieve
this, several materials can be incorporated into the coating film. For enhanced electrical conductivity, substances
like copper or silver particles, conductive organic polymers, or carbon black can be used. In many cases, such
materials have to be used in the form of nanoparticles to
achieve even distribution inside the film and low percolation thresholds.
There are several synthesis routes known to produce
such nanoparticles, but they often result in either low
yields or in materials that need further processing to show
optimum performance. This can lead to high material
TABLE 1 | Two-component clearcoat based on Bayhydrol
A 145.
Material
Content [g]
Component A
Bayhydrol A 145
BYK-011
BYK-346
BYK-425
Water
82.5
1.8
0.9
0.2
14.6
Component B
Bayhydur 3100
Dowanol MPA
24.7
5.3
Note: Ratio A:B = 3.3:1, adjust pH to 8.2 to 8.5
TABLE 2 | One-component clearcoat based on Worleesol
61 A.
Material
Worleesol 61 A
Cymel 327*
Butyl glycol*
Dimethylethanolamine
Water
BYK-020
BYK-333
Content [g]
47.7
8.6
3.9
2.4
36.7
0.5
0.2
Note: * Premix curing conditions, 20 min flash-off, 30 min at

130 C, adjust pH to 8.2 to 8.5
prices, and in combination with increasing raw material

costs, the overall costs can become prohibitive for some
applications. An example of this would be the use of silver.
The average price of silver has been steadily increasing
during the last few years, and silver nanoparticles are
even more expensive. For coatings applications, most
companies now focus on non-metallic compounds, like
carbon materials, to achieve electrical conductivity.
Carbon exists as different allotropes, e.g., diamond,
graphite, fullerenes and carbon nanotubes. While diamond consists of sp3 hybridized carbon with a cubic crystal lattice, all other known allotropic forms contain sp2
hybridized carbon atoms, and thus they are preferred for
electrical conductivity. Since their observation in 1991 by
Iijima, carbon nanotubes have been the focus of considerable research.1 Scientists have since reported remarkable
physical and mechanical properties for this fascinating
allotrope of carbon.2
By T. Tinthoff, N. Hanitzsch, M. Pickave, J. Tecklenburg, N. Willing and M. Berkei | BYK-Chemie GmbH, Wesel,
Germany
16
JANUARY 2012 | w w w . p c i m a g . c o m
From unique electronic properties to mechanical properties that exceed any current material, carbon nanotubes
offer tremendous opportunities for the development of new
material systems. In particular, the excellent electrical conductivity of carbon nanotubes combined with their high
aspect ratio offer potential for the development of functional
coatings. This article reports on recent advances in using
additives based on carbon nanotubes to enhance the electrical conductivity of several coating systems.
FIGURE 1 | Clear coatings based on Bayhydrol D155 with different concentrations of MWCNT (0%, 0.5%, 1%, 2% from left to right).
Experimental
All coatings were applied on glass panels or PET foils with

wire bars at 75 m wet film thickness. After a curing procedure, all panels were stored for 24 h in an acclimatized
chamber, and surface resistivity was measured three
times at each panel.
Starting formulations are shown in Tables 1-3. Multiwall carbon nanotubes from different suppliers were used
in the form of aqueous dispersions.
FIGURE 2 | Surface resistivity of different clear coatings with different

concentrations of MWCNT 1.
TABLE 3 | One-component clearcoat based on Bayhydrol
D155.
Material
Content [g]
Bayhydrol D 155
50.0
Cymel 327
Butyl glycol
Dimethylethanolamine
Water
BYK-025
BYK-307
7.8
4.0
2.0
35.6
0.3
0.3
Note: Curing conditions 20 min flash-off, 30 min at 130 C,

adjust pH to 8.2 to 8.5
Worleesol 61 A
Bayhydrol A 145
Bayhydrol D 155
0.5
MWCNT 1 Content in %
A possible explanation for this finding follows. The

MWCNT were incorporated into the coatings in the form
of dispersions in which the carbon nanotubes were homogeneously dispersed and stabilized by wetting and dispersing
additives. This perfect distribution was trans1.00E+13
ferred
into
the coating system. In the two-component
1.00E+12
system,
curing started directly after application, which
1.00E+11
kept 1.00E+10
the carbon nanotubes in a very well-dispersed state.
It resulted
in a higher percolation threshold since many
1.00E+09
MWCNT
were in an isolated position and were not con1.00E+08
tributing
to the percolation network. The baking systems
1.00E+07
started
curing after the flash off time and while applying
1.00E+06
heat.1.00E+05
This enabled the MWCNT to agglomerate on a very
small1.00E+04
scale to achieve percolation. It can also be described
as a 1.00E+03
kind of self-organization, and it seems that the resin
1.00E+02
chemistry
also contributed to this process. Unfortunately,
1.00E+01
we could
not yet clearly see differences in distribution by
REM1.00E+00
microscopy to prove this theory.
Black MWCNT 1
In addition to theControl
influenceCarbon
from the
resin chemistry or MWCNT 2
curing process, there was a significant contribution due
to the particle size, aspect ratio and surface chemistry of
the conductive pigment itself. We used two different kinds
of multiwall carbon nanotubes. The first one, MWCNT
1, exhibited some structural defects and some oxygencontaining groups on the surface. The second one, MWCNT
Surface Resistivity
To determine the performance of multiwall carbon nanotubes (MWCNT) in different aqueous coating systems,
we used a two-component clearcoat based on Bayhydrol
A 145, and two one-component baking systems based
on Worleesol 61 A or Bayhydrol D155, respectively. The
A 145 system started curing immediately after application, while curing of the baking systems was initiated
by elevated temperature. The two baking systems offer
different resin chemistries; alkyd/melamine in Worleesol
61 A and polyester/melamine in Bayhydrol D155. The
difference between the three systems had an influence on
the distribution of MWCNT inside the coating, resulting in
different percolation thresholds.
In all coatings, dosages of 0.5% to 8.0% MWCNT (calculated on solid resin) were incorporated, and films were
applied on glass and PET substrates using wire bars to
achieve 75 m dry film thickness. Films with 0.5% to 2%
MWCNT were already quite dark but still translucent,
while higher MWCNT concentrations resulted in nontransparent coatings (Figure 1).
As seen in Figure 2, the lowest percolation thresholds
were observed in the D155 system, followed by the Worleesol 61 A system. Even at low MWCNT concentrations
of 0.5% to 2%, anti-static properties were achieved, and
concentrations of 2% to 4% MWCNT resulted in electroconductive coatings with surface resistivity below 105 W.
Surface Resistivity
Results and Discussion
1.00E+14
1.00E+13
1.00E+12
1.00E+11
1.00E+10
1.00E+09
1.00E+08
1.00E+07
1.00E+06
1.00E+05
1.00E+04
1.00E+03
1.00E+02
1.00E+01
1.00E+00
PA I N T & C O A T I N G S I N D U S T R Y
17
Surface
Resistivity
Surface
Resistivity

Conductive Coatings Using Carbon Nanotubes
1.00E+14
1.00E+13
1.00E+14
1.00E+12
1.00E+13
1.00E+11
1.00E+12
1.00E+10
1.00E+11
1.00E+09
1.00E+10
1.00E+08
1.00E+09
1.00E+07
1.00E+08
1.00E+06
1.00E+07
1.00E+05
1.00E+06
1.00E+04
1.00E+05
1.00E+03
1.00E+04
1.00E+02
1.00E+03
1.00E+01
1.00E+02
1.00E+00
1.00E+01
1.00E+00
2, had less structural defects and a less polar surface, as

well as a slightly longer particle length. As a comparison,
we used a conductive carbon black, which offered a polar
surface and particle agglomerates with low aspect ratios
compared to MWCNT. Figure 3 shows that MWCNT 2
offered lower percolation thresholds compared to MWCNT
1 in the D155 system. To achieve the same level of surface
resistivity, one would have to use between 8% to 10% carbon black, 2.5% MWCNT 1 or 1.5% MWCNT 2. This effect
becomes even more predominant in the Bayhydrol A 145
system where MWCNT 1 gave almost no surface resistivity
improvement. Due to their more polar particle surface, the
carbon nanotubes kept their well-dispersed status inside
the two-component clearcoat system and even at high
concentrations of 8%, there was almost no
improvement
Worleesol
61 A
in conductivity. The MWCNT 2 had a higher
aspectA ratio
Bayhydrol
Worleesol 61145
A
and resulted in a percolating network, exhibiting surface
Bayhydrol
Bayhydrol D
A 155
145
6
resistivity of 10 W at a MWCNT 2 concentration of 6%.
155
It is obvious that the performance ofBayhydrol
carbon D
nanotubes as well as any other conductive pigment strongly
depends on several parameters. First, is the interaction
between the conductive pigment and the coating matrix.
If the affinity of the resin to the conductive pigment is
too high and the conductive pigment stays in a perfectly
dispersed
the
0
0.5 status,
1
2 formation
4
6 of a 8percolating network
is0hindered.
Therefore,
the
conductive
MWCNT
1
Content
in
%
0.5
1
2
4
6
8 pigments should be
used in the form of dispersions to guarantee a good initial
MWCNT 1 Content in %
dispersion status. In addition, the wetting and dispersing
additives used have to guarantee good stabilization as
Surface
Resistivity
Surface
Resistivity

FIGURE 3 | Surface resistivity of clearcoat system based on Bayhydrol

D155
with 1.5% different conductive pigments.
1.00E+13
1.00E+12
1.00E+13
1.00E+11
1.00E+12
1.00E+10
1.00E+11
1.00E+09
1.00E+10
1.00E+08
1.00E+09
1.00E+07
1.00E+08
1.00E+06
1.00E+07
1.00E+05
1.00E+06
1.00E+04
1.00E+05
1.00E+03
1.00E+04
1.00E+02
1.00E+03
1.00E+01
1.00E+02
1.00E+00
1.00E+01
Control Carbon Black MWCNT 1
MWCNT 2
1.00E+00
Control Carbon Black MWCNT 1
MWCNT 2
FIGURE 4 | Structural differences between agglomerated carbon black

(left) and a skein of carbon nanotubes (right) shown by SEM micrographs.
FIGURE 5 | SEM image of a coating surface containing

0.1% carbon nanotubes.
1 m
well as suitable compatibility towards the coating matrix.

Percolation will take place when the conductive pigments
are allowed to agglomerate on a molecular state, still
keeping a good distribution. Strong flocculation has to
be avoided; otherwise the necessary amount of conductive pigments would be too high. There has to be a good
balance between optimum distribution and minimum
agglomeration.
The second point to be considered is to use conductive
pigments with high aspect ratios to achieve percolation
at low concentrations. Therefore we believe that carbon
nanotubes can offer a strong benefit compared to carbon
blacks due to their structural uniqueness (Figure 4).
Compared to organic anti-statics (for example, those
based on quaternary ammonium salts), conductive pigments offer permanent anti-static or electro-conductive
behavior to coatings. Quaternary ammonium salts can
create a thin water film on the surface due to their high
polarity, but their ions can migrate out of the coating matrix, often resulting in decreasing performance
over time. Carbon nanotubes, especially, can overcome
this drawback due to their high aspect ratio and their
entanglement tendency. Figure 5 shows the surface of
a clearcoat with 0.1% carbon nanotubes. The carbon
nanotubes appear on some spots on the surface and disappear into the matrix again to form a three-dimensional
network. This guarantees good surface conductivity, and
the carbon nanotubes are strongly fixed into the matrix.
Conclusion
To increase the conductivity of coatings, carbon nanotubes can offer an interesting alternative to the classical
conductive pigments like carbon black or metallic particles. To get the optimum benefit from this fascinating
material they should be incorporated into the coating in
the form of dispersions to guarantee optimum distribution. In addition, the right wetting and dispersing additives have to be used to enable percolation and compatibility with the coating matrix. Further investigations will
be done to enable coatings manufacturers to predict the
interaction between coating ingredients and the carbon
nanotubes and the resulting performance. n
References
200 nm
200 nm
200 nm
200 nm
18
JANUARY 2012 | w w w . p c i m a g . c o m
1
2
Iijima, S. Nature 354 (1991) 5658.

Collins, P.G.; Avouris, P. Scientific American2836 (2000)
6269.

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Conductive

TABLE 1 | Two-component clearcoat based on Bayhydrol

Note: Ratio A:B = 3.3:1, adjust pH to 8.2 to 8.5

TABLE 2 | One-component clearcoat based on Worleesol

Note: * Premix curing conditions, 20 min flash-off, 30 min at

130 C, adjust pH to 8.2 to 8.5

prices, and in combination with increasing raw material

All coatings were applied on glass panels or PET foils with

FIGURE 2 | Surface resistivity of different clear coatings with different

TABLE 3 | One-component clearcoat based on Bayhydrol

Note: Curing conditions 20 min flash-off, 30 min at 130 C,

A possible explanation for this finding follows. The

Results and Discussion

Conductive Coatings Using Carbon Nanotubes

2, had less structural defects and a less polar surface, as

FIGURE 3 | Surface resistivity of clearcoat system based on Bayhydrol

FIGURE 4 | Structural differences between agglomerated carbon black

FIGURE 5 | SEM image of a coating surface containing

well as suitable compatibility towards the coating matrix.

Iijima, S. Nature 354 (1991) 5658.

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