Polymer 55 (2014) 5389e5395

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Polymer
journal homepage: www.elsevier.com/locate/polymer

Mechanical properties of polybutadiene reinforced with

octadecylamine modified graphene oxide
Yan Zhang a, James E. Mark a, *, Yanwu Zhu b, Rodney S. Ruoff c, Dale W. Schaefer d, **
a
Department of Chemistry, University of Cincinnati, Cincinnati, OH 45221-0172, USA
b
Department of Materials Science and Engineering and CAS Key Laboratory of Materials for Energy Conversion, University of Science and Technology of
China, Hefei, Anhui 230026, China
c
Department of Mechanical Engineering and The Texas Materials Institute, University of Texas at Austin, Austin, TX 78712-0292, USA
d
Department of Biomedical, Chemical and Environmental Engineering, College of Engineering and Applied Science, University of Cincinnati, Cincinnati, OH
45221-0012, USA

a r t i c l e i n f o a b s t r a c t

Article history: Octadecylamine-modified graphene-oxide (OMGO) polybutadiene nanocomposites with different OMGO
Received 26 June 2014 loadings were prepared by solution mixing. The dispersion of OMGO in chloroform is greatly improved
Received in revised form compared to GO. Toughness and elongation of PBDeOMGO nanocomposites increase by 332% and 191%
18 August 2014
respectively compared with pure PBD. However, Young's modulus of PBDeOMGO nanocomposite de-
Accepted 24 August 2014
Available online 3 September 2014
creases by 10% at 2-wt% loading. Graphene sheet crumpling accounts for the increased toughness, the
absence of modulus reinforcement and the absence of a Payne effect for PBDeOMGO. The oxidation
susceptibility of PBD is greatly reduced after the addition of OMGO, which is particularly desirable in the
Keywords:
Polybutadiene
tire industry.
Graphene oxide © 2014 Elsevier Ltd. All rights reserved.
Mechanical property

1. Introduction
Rubbers (elastomers) are an important class of commercial
polymers. Classic elastomers, such as polybutadiene and poly-
isoprene are used as general purpose rubbers in high volume
products such as tires, hoses, belting, and flexible automotive parts
[1]. Rubber materials have been extensively studied because of easy
processing, flexibility and excellent thermal properties [2e4].
However, rubber is commonly used in form of composites since
pure rubber lacks the required mechanical properties such as wear
resistance and strength.
Rubber nanocomposites are the class of filled rubbers in which
at least one dimension of the fillers is on the nanometer scale. Most
commonly used fillers are silica, carbon black, clay and carbon
nanotubes [5e7]. Increased modulus is achieved at relative high
filler loading such as 20e50 per hundred rubbers (phr), which can
reduce toughness due to defects caused by the fillers [8]. However,
the incorporation of small-size fillers in cross-linked elastomers
results in specific nonlinear mechanical behaviors including Payne
* Corresponding author. Tel.: þ1 513 556 9292; fax: þ1 513 556 9239.
** Corresponding author. Tel.: þ1 513 556 5431; fax: þ1 206 600 3191.
E-mail addresses: markje@ucmail.uc.edu (J.E. Mark), dale.schaefer@uc.edu,
schaefdw@ucmail.uc.edu (D.W. Schaefer).
effect and Mullins effect. The Payne effect is typically observed at
small strain. The dynamic storage modulus decreases strongly with
increasing strain amplitude [9]. Mullins et al. first reported that the
degree of softening increases with increasing stiffening ability of
the fillers [10]. Some Mullins softening is observed in carbon black
and silica filled rubber composites systems [11].
Polybutadiene (PBD), a synthetic rubber, has a higher resistance
to wear over styrene-butadiene rubber and natural rubber, which
are its main competitors in rubber-industry applications due to
their lower glass transition temperatures [12]. PBD is a low cost
rubber used for soles, gasket, seals and belts [13]. PBD is normally
formulated with fillers, such as silica or carbon black.
Graphene is an emerging filler candidate that has been widely
studied in thermoplastics, but not in elastomers. Graphene shows
high thermal conductivity (5000 W m
1 K
1) [14e16], highest
Young's modulus ever measured (1 TPa) [17] and large theoretical
surface area (2675 m2 g
1) [18]. High modulus and large surface
area promise dramatic improvement in mechanical properties,
which as yet has not been realized. Within the few published paper
on elastomers filed with graphene materials, Araby et al. [19] re-
ported that tensile strength of styrene butadiene rubber filled with
graphene increases by 230% using melt compounding. However, in
order to obtain such improvement, a large amount of graphene
(24%) was incorporated into rubber, which causes defects in
products and increases cost.

http://dx.doi.org/10.1016/j.polymer.2014.08.065
0032-3861/© 2014 Elsevier Ltd. All rights reserved.
5390 Y. Zhang et al. / Polymer 55 (2014) 5389e5395
An effective approach to achieve graphene-based polymer
composites is based on chemical transformation of graphite to
graphite-oxide (GO), which readily disperses in water and exfoli-
ates to form individual, single-layer graphene oxide sheets
[20e23]. Further modification of GO is necessary to achieve fully
dispersed GO in common organic solvents [24e28]. Here we
demonstrate a modification scheme based on octadecylamine
(ODA) modification of GO that greatly improves GO dispersion in
chloroform.
We report the synthesis of ODA-modified GO (OMGO) and
examine the mechanical properties of PBDeOMGO nano-
composites as a function of OMGO loading. The amino group in the
ODA modifier reacts with carboxylic acid groups in GO. In contrast
to the preponderance of graphene-based thermoplastic compos-
ites, we investigate the performance of thermosetting rubber ma-
terials. Toughness and elongation at break of PBDeOMGO improve
by 332% and 343% respectively at 2-wt% OMGO. However, Young's
modulus of PBDeOMGO decreases by 10% at OMGO loading 2 wt%.
2. Experimental section
2.1. Materials
GO, prepared by a modified Hummers method [20]. ODA and N,
N0 -diisopropylcarbodiimide (DIC) were purchased from Sigma-
eAldrich Co. Chloroform was purchased from Tedia Company Inc.
Anhydrous acetonitrile was purchased from Acros Organics. High
cis-1, 4-polybutadiene (c-PBD) was purchased from SigmaeAldrich
Co. Dibenzoyl peroxide (BPO) was purchased from Acros Organics.
All reagents were used as received.
2.2. Preparation of OMGO
ODA-modified GO (OMGO) was made using the reaction be-
tween carboxylic acid groups and epoxy groups from GO and amino
groups (using DIC to activate carboxylic groups), as shown in
Scheme 1. The selectivity of carboxylic acid groups and epoxy
groups remains an open question [29,30]. Briefly, the desired
amount of GO was dispersed in 40 ml anhydrous acetonitrile fol-
lowed by ultrasonication for 1 h. DIC was added into graphene
oxide dispersion followed by reaction for 4 h at 70  C to activate the
Scheme 1. Synthesis of OMGO with octadecylamine.
carboxylic acid groups. Then ODA was added into the mixture fol-
lowed by refluxing at 75  C overnight under nitrogen atmosphere.
After the reaction, the OMGO was purified by washing with
dimethyl formamide and acetone successively to remove residual
DIC and unreacted amines. Black, solid OMGO was obtained after
vacuum drying at 50  C overnight.
2.3. Preparation of the unfilled cis-PBD networks
The desired amounts of polymer were first dissolved in chlo-
roform. After a clear solution was obtained, 2-wt% BPO was added
[31]. The solution was stirred at room temperature for 2 h and then
transferred into Teflon™ dishes that were covered with aluminum
foil for overnight solvent evaporation. Films were pressed at
approximately 1.2  104 psi, 130  C for 2 h. The final samples were
approximately 1.0 mm thick.
2.4. Preparation of PBDeOMGO nanocomposites
The PBDeOMGO nanocomposites were prepared with various
loadings of OMGO. Firstly OMGO was dispersed in chloroform with
the aid of ultra-sonication for 1 h to yield a well-dispersed solution.
Secondly, the well-dispersed OMGO solution was mixed with c-PBD
with 0.50, 1.00 and 2.00 weight ratio for 2 h following the same
procedures as for unfilled c-PBD discussed above.
2.5. Characterization
Fourier transform infrared spectroscopy (FTIR) recorded on a
Nicolet 6700 (Thermo Scientific) spectrometer was used to char-
acterize the chemical structure of GO and OMGO. Samples were
measured under a mechanical force by pressing the un-exfoliated
sample's surface against a diamond window. FTIR spectra were
collected in the range 4000e450 cm
1.
Thermo-gravimetric analyses (TGA) were done on the GO and
OMGO powders using a TA Q500 instrument (TA Instruments)
under a nitrogen atmosphere with a heating rate of 5  C min
1.
Degradation temperatures of PBDeOMGO nanocomposites were
measured using NETZSCH STA 409 instrument under a purge flow
of 20 ml/min argon at heating rate of 20  C min
1 from 25 to 700  C.
Powder X-ray diffraction (XRD) measurements were carried out
using a PANalytical X'Pert Pro MPD diffractometer with Cu Ka ra-
diation (l ¼ 1.541 Å) at 45 kV and 40 mA. The diffraction angle was
increased from 5 to 35 with the scanning rate of 0.05 min
1.
Scanning electron microscopy (SEM) was conducted with an FEI
Phillips Electroscan XL30 ESEMeFEG microscope using an accel-
eration voltage of 15 kV. OMGO suspensions (0.03 mg ml
1) were
spin-coated onto a flat aluminum plate at 2000 r.p.m. for 30 s. Then
the OMGO-coated aluminum plate was mounted on a standard
specimen holder using a double-sided carbon conductive tape for
SEM imaging. A transmission electron microscopy (TEM) sample
was prepared by placing a few drops of dispersion onto a lacey
carbon film support on a Cu grid. Images were acquired in a JEOL
1230 transmission electron microscope operated at 80 kV.
Atomic force microscopy (AFM) images were obtained using a
Dimension 3100 AFM made by Veeco Instruments Inc., operated in
tapping mode using Veeco RTESP type silicon cantilevers with a
resonance of frequency of 360 kHz. The samples for AFM mea-
surements were prepared by ultrasonic treatment of OMGO in
chloroform for 1 h, followed by spin-coating OMGO suspensions in
chloroform (0.03 mg ml
1) on freshly cleaved mica surfaces at
2000 r.p.m. for 30 s and then drying under vacuum at room
temperature.
The tensile properties were measured using an ESM-301
(MARK-10) tensile tester. The experiments were carried out at
 Y. Zhang et al. / Polymer 55 (2014) 5389e5395 5391

room temperature at a crosshead speed of 50 mm/min using

dumbbell-shaped specimens with an original length of 40 mm.
Three dumbbell-shaped samples were measured and standard
deviation of three measurements is the error bar.
MettlereToledo DMA-861 was used to measure the viscoelastic
data in order to investigate the Payne effect of nanocomposites. The
tests were performed on rectangular samples in shear mode at 5 Hz
at different shear amplitude.

3. Results and discussions

FTIR data shows that ODA is linked to the GO by the reaction

with carboxylic acid group. Fig. 1 shows the FTIR spectra of GO and
OMGO. In the spectrum of GO, broad peak between 3550 and
2500 cm
1 (OeH stretching from COOH and OH groups), C]O
(1714 cm
1), and aromatic C]C (1595 cm
1) stretches were
observed. After modification with ODA, there is a peak between
3500 and 3000 cm
1, which is attributed to OeH stretching from
OH and two new peaks appear at around 2914 cm
1 and 2839 cm
1,
which are assigned to the CeH stretch in the methylene group from Fig. 2. TGA curves of GO and OMGO. GO shows 37% more weight loss compared to
ODA [32]. The peak at 1465 cm
1 is due to the asymmetrical OMGO between 100 and 280  C, indicating COOH groups have been converted after
bending vibration of methyl group from ODA. The reaction of car- ODA modification.

boxylic acid groups with amine groups in the ODA is confirmed by

the observed decrease in wavenumber for the peak of C]O stretch,
from 1714 to 1570 cm
1, which overlaps with C]C peak. Since the
intensity of peak is proportional to number of functional groups in
the system, the peak at 1570 cm
1 is relatively weak.
TGA was utilized to monitor the decomposition of functional
groups. Fig. 2 shows the typical TGA curves of GO and OMGO. In the
GO curve, relatively low thermal stability was observed. GO starts
losing mass below 100  C (about 7%), which is attributed to the
absorbed water. The 46% weight loss between 100  C and 280  C is
due to decomposition of the labile oxygen-containing functional
groups. Between 280  C and 600  C, no obvious weight loss was
observed indicating all of the oxygen functional groups have
decomposed below 280  C. The decrease in mass around 600  C is
due to the pyrolysis of the carbon skeleton of the GO. After modi-
fication with ODA, no weight loss is observed in OMGO below
100  C and the weight loss between 100 and 280  C is 9 wt% which
is 37 wt% lower than that of GO (46 wt%). The 37 wt% difference is
attributed to ODA modifier, which degrades above 280  C. We
conclude that 37 wt% of oxygen functional groups in GO have been
modified by ODA [33,34]. This value is consistent with the weight
loss (38 ± 2 wt%) between 280  C and 550  C, which is assigned to
the removal of alkyl chains. The consistency of these weight losses
confirms the mass loss between 100 and 280  C is due to ODA
modifier.
XRD was used to determine the morphology and the layer
spacing of dry GO and OMGO. Fig. 3 shows a diffraction peak at
2q ¼ 10.3 indicating an interlayer distance of 0.86 nm for GO. After
modifying GO with ODA, the 10.3 peak almost disappears. How-
ever, a broad peak appears with comparable intensity at 22 , which
is closer to the typical (002) diffraction peak of graphite (26.6 ),
corresponding to 0.40 nm of interlayer distance. The same 22 peak
is reported in the work of Dubin et al. [35] and Pei et al. [36]
Compared with diffraction peak of graphite, which is extremely

Fig. 1. FTeIR of GO and OMGO. The peaks at 2914 cm
1 and 2829 cm
1 appear after Fig. 3. XRD pattern of GO and OMGO. After modifying GO with ODA, the peak at 10.3
modification with ODA assigned to CeH stretch in the methylene group from ODA, disappears. The broad peak of OMGO between 15 and 30 indicates that OMGO sheets
which indicates ODA was attached to GO. are disordered stacks.
5392 Y. Zhang et al. / Polymer 55 (2014) 5389e5395

Fig. 4. (A): SEM image of OMGO indicating OMGO shows a layered structure; (B): TEM image of OMGO. Extremely thin layers were observed indicating that OMGO was fully
dispersed in chloroform.

Fig. 5. AFM images and height profiles of OMGO dispersed at a concentration of 0.03 mg ml
1 in chloroform. 5.0 mm  5.0 mm scan area was selected to measure the thickness of
OMGO, which is 0.9 nm.

sharp and intense, the broad peak of OMGO between 15 and 30
indicates that OMGO sheets are disordered stacking. Under soni-
cation OMGO sheets easily separate into single layers as shown in
Fig. 4B.
SEM and TEM measurements were performed to investigate the
morphology of OMGO. Fig. 4A shows the SEM of OMGO at 500 nm
scale indicating that OMGO displays a layered structure. The OMGO
observed with TEM (Fig. 4B) is in the form of flat sheet. In the darker
part on the right corner is carbon grid. Most of the area on the left is
light gray color, which is covered by very thin layer of dispersed
OMGO. Fully exfoliated OMGO sheets were achieved after ODA
modification. Some areas are darker, which indicates stacking of the
OMGO sheets.
AFM was used to determine the thickness of dispersed OMGO
(Fig. 5). The cross-sectional view of the AFM image of OMGO in-
dicates that the thickness of OMGO is 0.9 nm. The typical observed
monolayer GO sheet is 0.8 nm, which is larger than the theoretical
graphite sheet with van der Waals thickness of ca. 0.34 nm because
of the presence of oxygen functional group above and below the GO
plane. So our result indicates that the OMGO platelet is a single
layer, which can also be seen from TEM image.
TGA was employed to examine the degradation of PBDeOMGO
nanocomposites. Fig. 6 is a composite plot of the TGA mass loss
Fig. 6. TGA of PBDeOMGO nanocomposite with different filler loading. At 2 wt%
curves obtained from the 0, 0.5, 1 and 2 wt% OMGO filled systems. OMGO, the onset temperature of the PBDeOMGO composites is 5  C higher than pure
The introduction of OMGO into PBD increases the degradation PBD.
 Y. Zhang et al. / Polymer 55 (2014) 5389e5395 5393

Table 1
Degradation temperature of PBDeOMGO nanocomposites from Fig. 6.

PBDeOMGO nanocomposites

Loading Pure PBD 0.5 phr 1.0 phr 2.0 phr

Td ( C) 380 381 385 385

temperature (Fig. 6). The derivative of each mass loss curve defines
the degradation onset temperature as shown in Table 1. At 2 wt%
OMGO, the onset temperature of the PBDeOMGO composites is
5  C higher than pure PBD.
Different aspects of the mechanical properties of PBDeOMGO
nanocomposites were examined. Toughness greatly improves
while the Young's modulus of PBDeOMGO nanocomposites de-
creases slightly. Fig. 7A shows the stressestrain curves of
PBDeOMGO nanocomposites as a function of filler loading. The
areas under the curves are the toughnesses (Fig. 7B) and the
maximum extension reflects the elongation of composites (Fig. 7C).
The toughness and elongation increase 332% and 191% respectively
at filler loading of 2.0 wt%. The slope of the curves in the initial
small strain portion (Fig. 7D) is Young's modulus. The Young's
Fig. 8. Storage modulus (E0 ) aWs a function of shear amplitude at 5 Hz. The data show
modulus decreases, which indicates the stiffness of the materials almost no Payne effect (reduction of modulus with strain amplitude). These data
does not increase by adding OMGO as filler. The fact that Young's indicate that the crumpled OMGO has a lower modulus than the matrix.
modulus decreases and toughness increases by the introduction of
OMGO is due to single-sheet nature of OMGO, which adopts a reinforcement mechanism at large elongations, which improves
wrinkled morphology that imparts a measure of entropic, rubber- toughness and elongation at break.
like elasticity to the filler itself [37,38]. That is, because the The samples were tested using dynamic mechanical analysis
bending modulus of the sheets is so low, adding filler does not (DMA) to elucidate the cause of the low Young's modulus. A typical
enhance the modulus. In fact, the filler may interfere with cross- DMA result on PBDeOMGO nanocomposites deformed in shear
linking chemistry leading to decreased modulus. On the other mode is shown in Fig. 8. Pure PBD has a larger elastic modulus than
hand, stretching of the crumpled OMGO sheet adds an extra

Fig. 7. A. Stressestrain curves of PBDeOMGO composites with different filler loading. Fig. 7B. Toughness of PBDeOMGO naocomposites vs filler contents Fig. 7C. Elongation of
PBDeOMGO nanocomposites vs. filler loading. Fig. 7D. Young's modulus of PBDeOMGO composites vs. filler loading.
5394 Y. Zhang et al. / Polymer 55 (2014) 5389e5395
Fig. 9. Comparison of the Payne effect for PBDeOMGO and CNFePU. The storage modulus
for PBDeOMGO is calculated from shear modulus in Fig. 8 assuming a Poisson ration of 0.5.
CNF reinforces PU (and shows a Payne effect) even though PU matrix has a higher zero-
strain modulus than PBD. PBD shows neither reinforcement nor a Payne effect.
Fig. 10. (A) Cross-section SEM image of pure PBD at the fracture surface; (B) Cross-section SEM image of PBDeOMGO with 0.5 wt% OMGO at the fracture surface. No aggregation is
observed in the PBD matrix, which indicates that OMGO is fully exfoliated.
Fig. 11. (A): Pure PBD; (B): 0.5 wt% OMGO; (C): 1 wt% OMGO; (D): 2 wt% OMGO after 12 months.
PBDeOMGO. The modulus decreases as filler loading increases and
reaches minimum at 1.0 wt%, which matches the tensile result
(Fig. 7D). Within error, there is no observable Payne effect (decrease
of modulus with strain amplitude).
The Payne effect is necessarily absent in PBDeOMGO because
OMGO does not reinforce PBD. Fig. 9, compares the strain-
dependence of the storage modulus of PBDeOMGO with that of
carbon-nanofiber (CNF) reinforced polyurethane (PU) [38], which
does show a Payne effect. The latter reinforces PU at low strain, but
at strain amplitude of ~10%, the modulus of the matrix is recovered.
For OMGO the modulus of the matrix is already “recovered” at zero
strain so it cannot display a Payne effect.
The Payne effect is generally attributed to clustering of the filler
particles induced by van der Waals forces [39]. Clustering is dis-
rupted by strain, leading to reduced modulus enhancement and, at
high strain, no modulus enhancement (the Payne effect). Appar-
ently the crumpled morphology of OMGO precludes the formation
of deck-of-cards configurations required for strong van der Waals
attractions. In the case of CNFs, on the other hand, side-by-side
fiber configurations are present, at least over the persistence
length of the fibers [37,38], which leads to the clustering required
for both zero-strain modulus enhancement and the Payne effect.
After the tensile test, the fracture surfaces were examined by
SEM. Fig. 10A and B shows the cross-section SEM images at fracture
surface of pure PBD and PBDeOMGO with 0.5 wt% OMGO. No
 Y. Zhang et al. / Polymer 55 (2014) 5389e5395
aggregation is observed in the PBD matrix after the addition of
OMGO, which indicates that OMGO is fully exfoliated.
The degradation of PBDeOMGO nanocomposites was observed at
times up to 12 months after sample prepared. Fig. 11 compares pure
PBD with PBD filled with OMGO at three different percentages after 12
months. PBD has a double bond in the backbone, which is easily
oxidized by ozone when exposed to air [40]. After 12 month, pure PBD
becomes yellow, brittle and forms cracks. The addition of OMGO
greatly reduces oxidation. As the OMGO loading increases,
PBDeOMGO nanocomposites remain flexible. No cracking is observed
for 1 wt% and 2 wt% OMGO. The absence of oxidation in PBDeOMGO
nanocomposites might be due to the filler-polymer attraction. OMGO
has many C]C moities, which can form pep interactions with C]C in
PBD structure. This observation is very important to industry since
PBD is the most important rubber component in the tire industry.
4. Conclusions
GO was successfully modified by ODA. ODA attaches to surface
by reaction of surface carboxylic acid groups and epoxy groups on
GO with the amine group on ODA. The introduction of ODA onto GO
greatly improves exfoliation in chloroform and facilitates casting of
PBD composites. OMGO in the PBDeOMGO nanocomposites acts as
a spring, which stores energy leading to the 332% improvement in
toughness and 191% improvement in elongation. However, Young's
modulus of PBDeOMGO nanocomposites decreases, indicating the
crumpled sheets have a lower modulus than the rubber itself. Since
there is no modulus enhancement there is also no filler-induced the
Payne effect. The oxidation of PBD decreases after the addition of
OMGO.
Acknowledgments
This work was supported by the National Science Foundation
through Grant DMR-0803454 (Polymers Program, Division of Mate-
rials Research). We thank the Advanced Materials Characterizing
Center (AMCC) at University of Cincinnati for providing the in-
struments and Professor Vesselin Shanov's help on tensile
measurements.
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