Communication

Comparison of Covalently and Noncovalently

Functionalized Carbon Nanotubes in Epoxy
Lei Liu, Krishna C. Etika, Kang-Shyang Liao, Lance A. Hess,
David E. Bergbreiter, Jaime C. Grunlan*

Carbon nanotubes typically require the use of a dispersing or stabilizing agent to prevent
significant aggregation during incorporation into a polymer matrix. These additives must be
strongly associated, either covalently or physically, to achieve their purpose. In this study,
multi-walled carbon nanotubes (MWNTs) were
dispersed into an epoxy matrix using polyethyl-
enimine (PEI) as a dispersant that was either cova-
lently attached to the nanotubes or physically
mixed to result in only noncovalent interaction.
Epoxy composites containing covalently modified
MWNTs exhibited greater storage modulus and
reduced electrical conductivity.

Introduction (e.g., clay)[28] that interacts strongly enough with the

nanotubes (and matrix/solvent) to break intertubular
Carbon nanotubes are considered to be an ideal inclusion bonds. It is widely accepted that this method can preserve
for polymer composites due to their exceptional electrical the electrical properties of nanotubes. On the contrary,
and mechanical behavior.[1,2] Despite their promise, strong covalent functionalization can dramatically improve
intertubular van der Waals attractions often prevent the interfacial interaction between the nanotubes and
nanotubes from exfoliating and hence compromise their polymer matrix via direct chemical bonding, which is
significant potential.[3,4] In order to transfer the properties stronger than noncovalent interactions. Examples of
of nanotubes to the composite, proper nanotube stabiliza- covalent modification of nanotubes include oxida-
tion is needed. Improved dispersion, exfoliation, and tion,[13,14,18,20] fluorination,[8,14,15,19,21,31] in situ polymeriza-
compatibility of nanotubes can be achieved by using tion,[6,10,12,14,23] and polymer chain attachment.[7,14,17,22,23] A
covalent[5–23] or noncovalent approaches.[5,6,18,23–30] Non- notable drawback for covalent functionalization is the
covalent functionalization requires the addition of a disruption of the surface conjugated p network, which leads
polymer,[29,30] surfactant,[6,24,25,27,30] or secondary particle to the reduction of electrical conductivity.[23,32] This is
especially true when a higher degree of functionalization is
achieved, such as nanotube fluorination, which can reach
L. Liu, K. C. Etika, L. A. Hess, J. C. Grunlan
approximately C2F.[31] For applications requiring electrical
Department of Mechanical Engineering and Materials Science
conductivity (EMI shielding,[33] sensing,[34] electrostatic
and Engineering Program, Texas A&M University, College Station,
Texas, TX 77843-3123, USA
dissipation,[35] etc.), damaging the nanotube’s ability to
E-mail: [email protected] transport electrons must be avoided.
K.-S. Liao, D. E. Bergbreiter The formation of an electrically conductive nano-
Department of Chemistry, Texas A&M University, College Station, tube pathway in a polymer composite is characterized
Texas, TX 77842-3012, USA by the percolation threshold, which is the minimum

Macromol. Rapid Commun. 2009, 30, 627–632

ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/marc.200800778 627
 L. Liu, K. C. Etika, K.-S. Liao, L. A. Hess, D. E. Bergbreiter, J. C. Grunlan

concentration of conductive filler required to form a three- PEI, with a number average molecular weight of 10 000 g
mol 1
dimensional network.[36] Covalently functionalized nano- and weight average molecular weight of 25 000 g
mol 1, were
tubes have been shown to simultaneously raise the purchased from Aldrich (Milwaukee, WI). Bisphenol-F based epoxy
resin (D.E.R. 354) with epoxide equivalent weight of 167–
percolation threshold in epoxy composites and improve
174 g
equiv. 1 was provided by the Dow Chemical Company
mechanical properties.[37,38] In one study, MWNTs were
(Midland, MI). 1-Methyl tetrahydrophthalic anhydride (ECA-100,
reacted with 3-glycidoxypropyltrimethoxysilane and sub-
Dixie Chemical) and an amine catalyst, N,N-dimethylbenzylamine
sequently introduced into an epoxy matrix.[39] A uniform (99%, Aldrich) were used as the curing agent and catalyst,
dispersion of nanotubes was achieved and the modulus respectively. Covalent attachment of PEI molecules to the surface
increased by about 12% over the sample containing of MWNTs was achieved using an established procedure.[42] In a
unmodified nanotubes (for nanotube loading at typical preparation, 2 g of MWNTs and 10 g of PEI were mixed in
0.25 wt.-% or above), but electrical conductivity decreased 100 ml of N,N-dimethylformamide (DMF) and the covalent
by nearly eight orders of magnitude relative to unfunctio- functionalization occurred after sonication for 30 min, followed
nalized MWNT-filled epoxies. Many studies have been by stirring at 50 8C for 3 d. The reaction product was found to
carried out to understand the surface chemistry of contain 8 wt.-% PEI, in the case of low conductivity MWNTs, and is
nanotubes and their contribution to the property enhance- denoted as C-MWNT-PEI, whereas the noncovalently functiona-
lized nanotubes are denoted as N-MWNT-PEI. The same procedure
ment of the composite.[13,40,41] Despite all of this work,
used with the higher conductivity MWNTs resulted in 6 wt.-% PEI
there has not been a study to directly compare the effect of
attachment. In all cases, noncovalently stabilized MWNTs had the
one agent that is covalently and noncovalently combined same amount of PEI to allow for direct comparison.
with nanotubes. This requires a molecule that can act as a The MWNT-filled composites were made by suspending an
surfactant and can also be covalently attached to the appropriate amount of nanotubes and PEI in 100 ml of acetone
nanotube surface in a relatively simple way. In a recent with sonication at 50 W for 20 min using a VirTis Virsonic 100
study, the influence of nanotube covalent acid oxidation Ultrasonic Cell Disrupter (SP Industries, Warminster, PA). Epoxy
and noncovalent surfactant adsorption on the thermal and resin, curing agent, and amine catalyst were then dissolved in
electrical properties of polyvinyl alcohol (PVA)/nanotube acetone and mixed with the MWNT suspension. This mixture was
composites was studied.[18] Unfortunately the two types of mechanically stirred for 5 min at 1 720 rpm followed by 30 min at
nanotube stabilization resulted in significant differences 3 100 rpm and sonicated in a water bath for 1 h. Acetone was
removed by rotation evaporation at 60 8C and the mixture was
in composite composition, which made direct comparison
cured in a glass mold for 1 h at 95 8C, followed by 3 h at 150 8C. The
of the two systems very challenging.
weight ratio of epoxy resin to the curing agent was kept at 5:4,
The present study takes advantage of a recently while the amine catalyst was maintained at 1 wt.-% of the total
developed technique to covalently attach polyethyl- solids.
enimine (PEI) to multi-walled carbon nanotubes (MWNTs).[42]
This ‘‘graft to’’ method maintains the intrinsic physical
Characterization
and chemical properties of the polymer after the
reaction.[43] Epoxy composites containing PEI covalently Sheet resistance (<120 000 V/sq) of the epoxy composites was
functionalized to nanotubes were compared to composites measured with a home-built four-point probe apparatus consist-
ing of an Agilent E3644A DC power supply (Agilent Technologies,
containing a physical mixture of PEI and MWNTs. In other
Inc. Englewood, CO), Keithley Model 2000 digital multimeter
words, the nanotubes and PEI used in both composites are
(Keithley Instruments, Inc. Cleveland, OH), and an SP4-62180TRS
identical. In one system PEI was used as a surfactant to aid
four-point probe head (Lucas Labs, Gilroy, CA). Composites with
the dispersion of nanotubes and in the other system PEI higher resistance (>120 000 V/sq) were measured with a
was chemically bonded to achieve the same purpose. The VOYAGER Surface Resistivity Meter (SRM)-100 (PINION Products
influence of interaction type (covalent or noncovalent) on Corporation, Los Fresnos, TX). Dynamic mechanical analysis was
the electrical and mechanical properties of the composites done with a Q800 (TA Instruments, New Castle, DE) using a
was directly evaluated. The results confirm that covalent temperature ramp of 5 8C
min 1 at a frequency of 1 Hz.
bonding degrades conductivity, while enhancing disper- Thermomechanical analysis was performed with a Q400 (TA
sion and modulus relative to noncovalent bonding. Instruments, New Castle, DE) using a 5 8C
min 1 temperature
ramp.

Experimental Part Results and Discussion

Materials and Composite Preparation Figure 1 shows SEM images of freeze-fractured cross-
Two types of MWNTs were used in this study. Low conductivity sections of epoxy containing 1 wt.-% of pristine MWNTs,
MWNTs (ID, 5–10 nm; OD, 20–30 nm; length, 10–30 mm) were N-MWNT-PEI, and C-MWNT-PEI. Without any functiona-
purchased from Cheap Tubes (Brattleboro, VT). Higher conductiv- lization, the nanotubes exist as numerous heavily
ity MWNTs (ID, 5–10 nm; OD, 20–30 nm; length, 0.5–200 mm) and aggregated bundles [Figure 1(a) and (b)], while covalent

Macromol. Rapid Commun. 2009, 30, 627–632

628 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/marc.200800778
Comparison of Covalently and Noncovalently Functionalized Carbon Nanotubes in Epoxy

conductivity of these composites, as

shown in Figure 2. Both covalent and
noncovalent functionalization of nano-
tubes reduce the electrical conductivity
of the composites relative to those with
no stabilization for MWNTs with 8 wt.-%
PEI. Composites containing covalently
functionalized nanotubes show no con-
ductivity enhancement, even when the
nanotube concentration reaches 1 wt.-%.
This is believed to be due to the
formation of chemical bonding on the
surface of nanotubes during functiona-
lization, which scatter electrons. Another
likely factor is the grafted PEI preventing
intimate contact between nanotubes.
Composites containing noncovalently
functionalized nanotubes showed
improved conductivity relative to C-
MWNT-PEI/epoxy composites. PEI, being
only physically adsorbed in the case of
noncovalent stabilization, is free to
diffuse away from the nanotubes, which
would allow for better tube-to-tube
contacts. A conductivity as high
as 10 8 S
cm 1 is realized when the
composite has 1 wt.-% N-MWNT-PEI,
which is nearly three orders of magni-
tude greater than C-MWNT-PEI. For all
Figure 1. SEM images of freeze-fractured cross-sections of epoxy composites containing
1 wt.-% MWNT (a) and (b), 1 wt.-% N-MWNT-PEI (c) and (d), and 1 wt.-% C-MWNT-PEI MWNT concentrations, the composites
(e) and (f). These composites contain the MWNT that is stabilized by 8 wt.-% PEI. Arrows containing neat MWNT have the highest
indicate points of MWNT pullout. conductivity due to the aggregated
nanotube microstructure and lack of
functionalization dramatically improves the nanotube insulating PEI to interfere with intertubular junctions. In
dispersion. At low magnification it is difficult to find any the absence of PEI, the MWNT can efficiently transfer
large nanotube aggregates [Figure 1(e)]. Nanotubes are electrons to one another. When higher conductivity
also found to be better embedded into epoxy when MWNTs are used, with reduced functionality (6 wt.-%
covalently modified [Figure 1(f)], which is evidenced by the PEI), the conductivity differences between covalent and
lack of nanotube pullout from the matrix. At higher noncovalent are much more significant, as shown in
magnification, unfunctionalized [Figure 1(b)] systems Figure 2(b). In addition to having reduced PEI content,
show characteristic holes that are artifacts of MWNT these nanotubes have a greater maximum length than
pullout. Noncovalently functionalized nanotubes are those used in Figure 2(a) (200 vs. 30 mm). Greater length is
shown to have an intermediate level of dispersion [Figure known to enhance conductivity due to fewer junctions in a
1(c) and (d)]. Although some aggregation is apparent, given network.[44] For the two nanotube loadings exam-
many of the nanotubes are exfoliated into relatively small ined, the C-MWNT-PEI/epoxy samples exhibit lower
bundles or even individual nanotubes. Noncovalent conductivity relative to N-MWNT-PEI/epoxy and unfunc-
functionalization is expected to be less efficient due to tionalized composites. However, almost no conductivity
lack of strong bonds holding the PEI at the nanotube disparity is observed between MWNT/epoxy samples and
surface. Covalent functionalization guarantees that all PEI N-MWNT-PEI/epoxy samples, suggesting that when using
is used for stabilization and there is no free polymer mixed higher conductivity nanotubes with lower PEI function-
into the epoxy matrix, which may lead to poorer dispersion ality, the composite can maintain electrical conductivity
and possible plasticizing of the matrix. after noncovalent functionalization.
The changes in nanotube microstructure after functio- The dynamic mechanical properties of the composites
nalization have a dramatic influence on the electrical containing 1 wt.-% pristine nanotubes, C-MWNT-PEI, and

Macromol. Rapid Commun. 2009, 30, 627–632

ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.mrc-journal.de 629
 L. Liu, K. C. Etika, K.-S. Liao, L. A. Hess, D. E. Bergbreiter, J. C. Grunlan

Figure 3. Storage modulus as a function of temperature for

composites containing 1 wt.-% nanotubes. These MWNTs are
the low conductivity version with 8 wt.-% PEI from covalent
functionalization.

when all of the PEI molecules are covalently tethered to the

surface of the nanotubes.
Figure 4 shows the thermomechanical analysis of the
composites containing 1 wt.-% nanotubes, from which
coefficient of thermal expansion (CTE) can be derived. CTE
is taken as the slop of the curves shown in Figure 4, which
are normalized by the thickness of each sample prior to
heating. It can be seen that all composites show similar
glass transition temperature, near 110 8C, which is in
relatively good agreement with the DMA results (see
Figure 3). The CTE for the N-MWNT-PEI/epoxy composite
Figure 2. Electrical conductivity as a function of nanotube con- (before and after Tg) shows a slight increase as compared to
centration for composites containing MWNT, C-MWNT-PEI, and the MWNT/epoxy (unfunctionalized) sample. This is
N-MWNT-PEI, for low conductivity MWNTs with 8 wt.-% PEI
attachment (a) and higher conductivity MWNTs with 6 wt.-%
PEI attachment (b).

N-MWNT-PEI are shown in Figure 3. All the three samples

exhibit similar glass transition temperatures (96 8C). The
MWNT/epoxy composite is found to have nearly the same
room temperature storage modulus as the N-MWNT-PEI/
epoxy sample. Although better nanotube dispersion is
observed after noncovalent nanotube functionalization
(see Figure 1), the nanotube/polymer interface is likely not
as strong as the MWNT/epoxy sample due to the presence
of adsorbed PEI molecules on the surface of nanotubes. It is
possible that the contributions from better nanotube
dispersion and weakened nanotube/polymer interface
cancel one another and result in a comparable storage
modulus. The composite containing 1 wt.-% C-MWNT-PEI
shows an 8% improvement in storage modulus relative to Figure 4. Thermal expansion of epoxy composites containing
the other two samples. This improvement is expected due 1 wt.-% nanotubes. Stabilized nanotubes are associated with
to the greater nanotube/polymer interfacial interaction 8 wt.-% PEI.

Macromol. Rapid Commun. 2009, 30, 627–632

630 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/marc.200800778
Comparison of Covalently and Noncovalently Functionalized Carbon Nanotubes in Epoxy

believed to be due to the plasticizing effect of free PEI supported by the National Science Foundation (DBI 0116835), the
VP for Research Office, and TEES.
molecules. The C-MWNT-PEI/epoxy composite exhibits
significantly reduced CTE relative to the MWNT/ Received: December 12, 2008 Revised: January 24, 2009;
epoxy sample. The CTE values decreased from 71.6 mm/ Accepted: January 27, 2009; DOI: 10.1002/marc.200800778
(m 8C) to 64.3 mm/(m 8C) and from 191.2 mm/(m 8C) to Keywords: composites; conductivity; epoxy; nanocomposites;
177 mm/(m 8C) for the temperature ranges below and nanotubes
above Tg, respectively. The stronger interfacial interaction
between epoxy and C-MWNT-PEI prevents the composite
from expanding as rapidly over a given temperature range.
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Macromol. Rapid Commun. 2009, 30, 627–632

632 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/marc.200800778