Composites Science and Technology 71 (2011) 1397–1403

Contents lists available at ScienceDirect

Composites Science and Technology

journal homepage: www.elsevier.com/locate/compscitech

Fabrication of polypropylene/carbon nanotubes composites via a sequential

process of (rotating solid-state mixing)-plus-(melt extrusion)
Zhicheng Wang, Xi Fan, Ke Wang ⇑, Hua Deng, Feng Chen, Qiang Fu ⇑
Department of Polymer Science and Materials, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610065, PR China

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

Article history: In this study, a simple but effective method to realize excellent comprehensive performances in
Received 9 October 2010 polypropylene (PP)/multi-walled carbon nanotubes (MWNTs) was developed. Before melt extrusion,
Received in revised form 16 May 2011 solid-state iPP powders and MWNTs were pre-mixed upon high-speed rotating. By this way, the disper-
Accepted 20 May 2011
sion extent of nanotubes was significantly improved as comparing to the common one-step melt extru-
Available online 31 May 2011
sion strategy. As validated by scanning electron microscopy, most of MWNTs exist as a form of filament
bundles with size of hundreds nanometers; no obvious agglomerate was found even at high MWNTs con-
Keywords:
tent, 5%. The improvements of the major mechanical properties and electric conductivity were much effi-
A. Carbon nanotubes
A. Polymer–matrix composites (PMCs)
cient for the composites obtained via the two-step process of rotating solid-state mixing (RSSM)-plus-
B. Mechanical properties melt extrusion. The tensile strength, Young’s modulus and impact strength at 5% MWNTs content were
B. Electrical properties enhanced for 35%, 42% and 45%, respectively, indicating an excellent strength–rigidity–toughness bal-
B. Fracture toughness ance, which was hardly achieved in polyolefin/carbon nanotubes composite. It is believed that the
method developed in this study is so far the most effective and convenient for efficiently dispersing nano-
tubes into the nonpolar, intractable thermoplastics and resulting in good properties, among a variety of
fabrication method suggested in the previous researches. Importantly, the used RSSM equipment is a kind
of frequently used dispersion machine, thus it has tremendous potential to be applied in industrial pro-
ducing immediately.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction
Since carbon nanotubes (CNTs) were discovered in 1991, the ex-
tremely high modulus, strength, excellent electrical and thermal
conductivity enable them for a wide range of applications [1,2].
In particular, CNTs can act as an ideal modifier to enhance the
properties of polymer materials, frequently focused on mechanical
strength and electric conductivity [3]. However, the level of perfor-
mance enhancement is often limited, i.e., the addition of CNTs usu-
ally results in a mild increase of elastic modulus compared to
pristine polymer [4]. This is due to (1) CNTs tend to agglomerate
together because of van der Waals attraction and physical entan-
glement between adjacent nanotubes and (2) efficient stress trans-
fer from basal resin to nanotubes is absent. Therefore the good
dispersion of CNTs and strong interfacial adhesion are two domi-
nant issues for realizing superior performance enhancement in
polymer/CNTs nanocomposite.
Melt compounding is a facile approach to fabricate polymer/
CNTs composites, and has been most frequently adopted in the
previous literature. For polar thermoplastics with functional
⇑ Corresponding authors. Tel.: +86 28 85461795; fax: +86 28 85405402 (Q. Fu).
E-mail addresses: wkestar@scu.edu.cn (K. Wang), qiangfu@scu.edu.cn (Q. Fu).
groups, the high polarity similarity between basal resin and nano-
tubes [5] and/or the additional physical bonding arisen from a
combination of shear stress and thermal activation [6] could in-
duce relatively good dispersion of CNTs. Nevertheless, for non-
polar ones, such as polyolefin, there present more of a challenge
to achieve ideal CNTs-dispersion merely by melt compounding.
To optimize dispersion of CNTs and interfacial adhesion, tre-
mendous amount of methods have been developed. They can be
classified roughly into chemical (covalent) treatment [7–10] and
physical (noncovalent) treatment [11,12]. The first strategy in-
cludes the sidewall functionalization [13], the sidewall grafting
with polymer chains [14,15] and the in situ polymerization on
sidewall of CNTs [16]. By these covalent modifications, the chemi-
cal nature of CNTs was altered evidently, and the obvious incre-
ments in dispersion and interaction were desired [17,18]. The
cost of covalent treatment, however, does not justify the repay-
ment of property improvement. Their applications in industrial
fields are by far limited, especially for large-scale fabrication.
Therefore, the second strategy, noncovalent modification, has
attracted intensive attention [19,20]. Lu et al. [21] developed a
so-called latex technology that isotactic polypropylene (iPP) latex
was mixed into aqueous CNTs suspended solution containing
commercial surfactant likes sodium dodecyl sulfate (SDS), after

0266-3538/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2011.05.012
1398 Z. Wang et al. / Composites Science and Technology 71 (2011) 1397–1403
evaporation of liquid components a dispersion state of individual
CNT filament could be achieved. In a relatively simple procedures,
aqueous CNTs suspended solution was sprayed onto the surface of
PE granule [22], or the PE granules were immersed into such solu-
tion [23], after evaporation of solvent the CNT filaments adsorbed
on the surface of PE granule. The pre-dispersion state that PE gran-
ule was coated with CNTs, improved the dispersion of CNTs prom-
inently during the subsequential process of melt compounding.
Although the physical methods mentioned above can promote
the dispersion level of CNTs effectively, they still require a great
of liquid chemical solvent. To avoid this problem, some pre-disper
sion treatments have been implemented as solid-state upon the
shear fields. Masuda et al. [24] pre-dispersed MWNTs into PP resin
through a so-called solid-state shear pulverization (SSSP) technol-
ogy. The ultra-uniform dispersion of CNTs and the excellent com-
prehension properties were realized in the sequential melt
compounding. It may be due to the rigorous technological require-
ments that the SSSP cannot become a conventional processing
method at present. In an other similar research, Xia et al. [25]
pre-mixed iPP granules and CNTs together through a solid-state
mechanochemical pulverization process conducted on a pan mill-
ing. However, due to the severe decomposition of macromolecular
chains and scission of CNT filaments, the enhancements in
mechanical properties were retarded. So these solid-state premix-
ing methods mentioned are not suitable for fabrication of polymer/
CNTs composites in practical industrial fields though they result in
better dispersion of CNTs than simple melt compounding.
The major aim of this study is to explore the possibility that uti-
lizing a available and often used solid-state shear equipment,
rotating four-leaf oar mixer, to tailor the dispersion of CNTs in
PP. Our goal is to develop a simple but effective method for the
large-scale fabrication of polyolefin/CNTs composites with excel-
lent comprehension performances by only using some easily avail-
able processing equipments.
2. Experimental
2.1. Materials
Commercially available MWNTs (L-MWNT-1020, Shenzhen
Nano-Corporation, China), with purity: >98%, length: 5–15 lm,
outer mean diameter: 10–20 nm, surface area per unit mass: 40–
300 m2/g, synthesized by catalytic chemical vapor deposition, were
used in this study. The MWNTs are used as-received without any
chemical treatments. A powder-form isotactic polypropylene (iPP)
with melt flow index (MFI) of 5.0 g/10 min (2.16 kg loading,
190 °C), and a maleic anhydride-grafted polypropylene (PP-g-MA)
(trade-marked as E43, Westlake Chemical Corporation, USA), with
acid number: 40.0–55.0 mg-KOH, softening point: 153.0–162.0 °C,
viscosity at 190 °C: 150–700 CPS, were used as the basal polymers.
2.2. Preparation of composites
The compositions of iPP/PP-g-MA/MWNTs (90/10/x wt%, x = 0.5,
1, 3, 5) were firstly blended in a high-speed rotating mixer (DFY-600,
Linda Mechanical Co., Ltd. China) at 25,000 rpm for 3 min. In a strict
sense, the basal resin used in this study should be denoted as a blend
containing 90 wt% iPP and 10 wt% PP-g-MA, and this composition is
fixed during every processing step (RSSM and melt compounding)
and in every specimen (with or without MWNTs). Then the pre-dis-
persed iPP/PP-g-MA/MWNTs hybrid was melt-compounded in a
TSSJ-2S co-rotating twin-screw extruder. The temperatures of the
extruder were maintained at 170, 180, 190, 200, 200 and 195 °C from
hopper to die, and the screw speed was about 120 rpm. The resulted
nanocomposite is hereafter abbreviated as PP–MWNTx (x = 0, 0.5, 1,
3 and 5 wt%). After being pelletized and placed in a vacuum oven at
80 °C for 24 h, injection molding was conducted on a PS40E5ASE
injection machine (Japan) at 200 °C to obtain standard specimen
for mechanical property measurements. In addition, some extruded
pellets were compression-molded under 190 °C and 5 MPa to make
films with a thickness about 2.5 mm, and then cut into regular shape
for conductivity measurement. For comparison purpose, a series of
iPP/PP-g-MA/MWNTs (90/10/x wt%, x = 0.5, 1, 3, 5) composites de-
noted as PP-p-MWNTx were also prepared upon the same process-
ing conditions, but without experiencing the RSSM process.
2.3. Characterizations
2.3.1. Scanning electron microscopy (SEM)
The SEM experiments were performed using a Hitachi
S3400tEDX SEM instrument to inspect the dispersion of MWNTs
in nanocomposites. The samples were obtained by compression-
molding extruded pellets under 190 °C and 5 MPa to make batten,
then cryofractured, gold-coated and observed under an accelera-
tion voltage of 10 kV.
2.3.2. Differential scanning calorimetry (DSC)
The calorimetric analysis was implemented on a Perkin–Elmer
Pyris I differential scanning calorimeter with nitrogen as the purge
gas. The slice of testing sample, about 5 mg, was fast heated to
210 °C at a rate of 10 °C/min, hold for 5 min to erase any thermal
history and then cooled down to 50 °C at a rate of 1.5 °C/min.
2.3.3. Gel permeation chromatography analysis (GPC)
GPC was carried out on an HP1100 using two PL gel columns
(10 m 104 Å, 10 m 500 Å). Molecular weights are relative to mono-
disperse polystyrene standards. The mobile phase was trichloro-
benzene. Sample concentration was 1 g/l. The detector was RID
and the flow rate was 1 ml/min.
2.3.4. Mechanical properties measurements
Standard tensile tests were performed using an SANS universal
tensile testing machine controlled by a two-step program, accord-
ing to ASTM D638 standard. The notched izod impact strength of
the specimens was tested with a VJ-40 izod machine according
to ASTM D256 standard. All mechanical properties were measured
under room temperature (about 25 °C), and the average value was
obtained from over five specimens for each condition.
2.3.5. Dynamic mechanical analysis (DMA)
The dynamic mechanical property of as-prepared iPP/MWNTs
composites were measured using a dynamic mechanical analyzer
(DMA Q800, TA Instruments, Ltd. USA), and the 3-point blend
mode was adopted. The temperature range was from 60 to
160 °C under a heating rate of 3 °C/min, the frequency used was
1.0 Hz, and the size (length  width  thickness) of the test sam-
ples was 20  10.2  4.2 mm3.
2.3.6. Wide-angle X-ray diffraction (WAXD)
WAXD analysis was conducted on a DX-100 X-ray diffractome-
ter (radiation Cu Ka, k = 0.154 nm, reflection mode). The 2h range
was 10–30° with a scanning rate of 0.02 °/s.
2.3.7. Conductivity measurement
The electrical conductivity of the composites was measured in
accordance with ASTM D4496. Samples with the fixed cross-sec-
tional area and thickness were placed between two copper elec-
trodes, and the DC resistance was measured using a Fluke 87
multimeter. The surface area of the sample in contact with the
electrodes was coated with silver paint in order to reduce discrep-
ancies arising from micro-roughness. It was ensured that the
 Z. Wang et al. / Composites Science and Technology 71 (2011) 1397–1403 1399

surface area of the electrodes exceeded the cross-sectional area of
the discs.
3. Results and discussion
3.1. Rotating solid-state premixing (RSSM) process
Scheme 1 describes the transition of dispersion state between
iPP granules and MWNTs throughout a convective process of
high-speed rotating. Before the RSSM procedure, the MWNTs are
trended to aggregate together, and less area of iPP powder surface
was coated with nanotube filaments. The rotating four-leaf oar
mixer yielded tremendous disturbance effect and the collision
and friction occur intensively between iPP granules, MWNTs and
the stiff metal wall of mixer, resulting in a size decrease of pristine
iPP granule and compact adsorption of MWNTs on the surface of
iPP granule, as illustrated in Scheme 1. The topographic morphol-
ogy of iPP granule obtained after experiencing the RSSM has been
examined by SEM and also presented in Scheme 1. For every
individual iPP granule, the relative flat area is covered with
numerous MWNT filaments, while the crack region is filled with
mass MWNT coils. Obviously, the physical absorption of MWNTs
on the surface of iPP granule has been enhanced prominently via
the RSSM, which should be arisen from the following three items:
(1) static electric attraction yielded by frication between iPP gran-
ule and MWNTs; (2) the generation of new surface area because
the pristine iPP granule is broken up; (3) the appearance of crack,
which penetrates into the inner of iPP granule, attributed to the
crash effect. The occurrence that cracks filled with mass MWNTs
enables the dispersed level of MWNTs in iPP granule improved
remarkably.
3.2. Dispersion of MWNTs in composites
After experiencing the melt compounding step, the dispersion
status of MWNTs in composites has been ascertained by SEM, and
some typical micrographs are presented in Fig. 1. Since the remark-
able difference in electro-conductivity between CNTs and PP resin,
the CNT substance exhibits as light white, while the basal polymer
is commonly dark or gray, which offers high reliability for using

Scheme 1. Mechanism of dispersing MWNTs in PP powder during superhigh-speed shear blending and SEM images of (a) the surface morphology of the mixed powder, (b)
MWNTs absorbed on the surface of PP and (c) moderate and small MWNTs agglomerates inserted in the crack of PP granule.
1400 Z. Wang et al. / Composites Science and Technology 71 (2011) 1397–1403
Fig. 1. SEM micrographs for PP–MWNTx: x = 1 (a), 5 (b); the corresponding SEM micrographs for PP-p-MWNTx: x = 1 (c) and 5 (d).
SEM to identify the dispersion and/or distribution of CNTs in contin-
uous polymer matrix [24]. For the composites obtained via the two-
step procedure of RSSM-plus-melt compounding, numerous white
spots are found, which are the ends of MWNT filaments. It can be
concluded that most of MWNTs exist as a form of filament bundle
with size scale of hundreds nanometers, particularly for the high
MWCNT content, 5%. After carefully analyzing many SEM images,
we find the size scale of filament bundle of MWCNTs in PP–MWNT5
is in the range of 200–800 nm, and some typical examples are indi-
cated by arrows in Fig. 1b; nevertheless, the large aggregates of
MWNTs are seen in the composites prepared by direct melt com-
pounding. According to SEM images, the size of aggregation block
in PP-p-MWNT5 is ranged from several micrometers to ten microm-
eters, and this is indicated by arrows in Fig. 1d. By comparing the dis-
persion status between two-step procedure and single-step
procedure, it is concluded that the RSSM treatment can enhance
the dispersion level of MWNTs in iPP matrix remarkably.
3.3. Crystallization property of composites
CNTs can act as nucleating agent for semicrystalline polymer
likes polypropylene [26–28]. In the presence of CNTs, the crystalli-
zation temperature of iPP should be increased. The cooling crystal-
lization curves of PP–MWNTs and PP-p-MWNTs composites are
plotted in Fig. 2a. For PP–MWNTs systems, a sharp increment of
9 °C in Tc is found in PP–MWNT0.5 (122 °C), as compared with PP
(113 °C). With increasing the MWNTs content, Tc is further in-
creased and reached 127 °C in PP–MWNT5. This indicates strong
heterogeneous nucleation effect of MWNTs to facilitate the crystal-
lization of basal iPP. Comparing with the PP–MWNTs system, the
improvement magnitude of Tc is less in the composites of PP-p-
MWNTs. A maximum increment of Tc is only 7 °C from basal iPP
to PP-p-MWNT5. Obviously, the higher heterogeneous nucleating
efficiency in the composites of PP–MWNTs is due to the better dis-
persion of MWNTs induced by the RSSM treatment. At the same
content of CNTs, the extent of crystallization temperature increase
can be used as an indicator of CNTs dispersion. The higher the crys-
tallization temperature, the better the CNTs dispersion could be.
Actually, compared with the increase of crystallization tempera-
ture reported in literature [29,30], our result is the highest at the
same filler content. As to crystal type and crystallinity, the addition
of MWNTs has no impact on them, which is proved by WAXD
experiment (Fig. 2b). For the composites obtained via RSSM-plus-
melt compounding, only the diffraction characteristics for
 Z. Wang et al. / Composites Science and Technology 71 (2011) 1397–1403
(a)
Fig. 2. (a) Dependence of crystallization temperature (Tc) on MWNTs loading and (b) WAXD of PP–MWNTx: x = 0, 0.5, 1, 3, 5.
monoclinic iPP a-form are found, and the crystallinity is approxi-
mately constant (45%) for all MWNTs contents.
3.4. Enhancements of performance by the incorporation of MWNTs
The effect of RSSM treatment on the decomposition of macro-
molecule has been assessed by GPC experiment. Seeing Table 1,
the weight mean molecular weights (Mw) of basal iPP for the com-
posites obtained via RSSM-plus-melt compounding are comparable
to that of pure iPP prepared by single-step melt compounding. So
the decomposition of basal iPP does not occur during the RSSM
process. Meanwhile, the values of Mw in the composites are some-
what higher than that of pure iPP, and the polydispersity varies
irregularly with increasing the MWNTs content. The reason may
be due to less mass of insoluble species, MWNTs, is residual in
the testing solution, which disturbs the accuracy of GPC mildly.
Unlike to the solid-state pulverization process on a pan milling
[25], the RSSM process mainly offers a convective and disturbed ef-
fect and the shear stress intensity imposed is mild, therefore the
obvious scission of PP chains cannot occur. Since the RSSM treat-
ment has improve the dispersion extent of MWNTs as well as the
preserving of original physical property of basal iPP, superior per-
formance enhancements by the incorporation of MWNTs are
desirable.
The enhancements in mechanical performance by adding
MWNTs are illustrated in Fig. 3. The incorporation of MWNTs in-
duces a reinforcing effect in both two composite systems that the
tensile strength and Young’s modulus is improved continuously
as the MWNTs content increases (Fig. 3a). However, the improved
magnitude of mechanical properties in the PP–MWNTs system is
obviously higher than that in the PP-p-MWNTs one. Compared to
the basal iPP, the increments of 35% and 42% in tensile strength
and modulus, respectively, are achieved when the MWNTs content
is 5% for the composite obtained via RSSM-plus-melt compounding.
Table 1
The molecular weight characterizations of composites prepared by a two-step
procedure of RSSM-plus-melt extrusion.
Pure iPPa CNT 0.5% CNT 1% CNT 3%
Mw 53.5  104 57.4  104 54.1  104 57.6  104
Mw/Mn 5.6 5.4 7.4 6.5
a
It is indeed a blend system of iPP/PP-g-MA (90/10 wt%), and without experi-
encing the step of RSSM.
1401
(b)
In general, for polyolefin/CNTs composite, an excellent rein-
forced effect is easily obtained, but it is frequently accompanied
with a remarkable decrease in toughness. The impact strength of
the composites prepared by single-step melt compounding is re-
duced with increasing the MWNTs content, as shown in Fig. 3b.
However, the tendency of impact strength vs. MWNTs content
for the composites prepared by RSSM-plus-melt compounding is
totally different. Similar to the tensile properties, the impact
strength is improved monotonically with the increase of MWNTs
content, and an obvious increment for 45% is realized at the high-
est MWNTs content, 5%, indicating a simultaneously toughening
and strengthening effect induced by the two-step procedure of
RSSM-plus-melt compounding. As to the elongation at break,
which is also an indication for toughness, its dependence on
MWNT content differs to the impact strength. For both of PP–
MWNTs and PP-p-MWNTs systems, the elongation at break contin-
uously decreases with the increasing of CNT content. However, the
values for PP–MWNTs are significantly higher than that for PP-p-
MWNTs, particularly at high MWNT contents, indicating the duct-
ibility of PP–MWNTs is better than that of PP-p-MWNTs. The exact
toughening mechanism in the PP–MWNTs composites is not clear
at present. Yuan et al. [31] suggested that strong interfacial adhe-
sion are beneficial for higher toughening efficiency. In our present
study, we would rather to expect that the interfacial adhesion
could be reinforced, due to a possible transcrystallization region
formed around the sidewall of MWNTs, as visually validated by
Miltner et al. [32].
It should be noted that the strengthening effect of this study is
comparable to the best level reported in previous literature. In our
current study, the Young’s modulus is improved for 32% when 1%
MWNTs is incorporated. For the iPP/MWNTs composite synthe-
sized via in situ polymerization and molded by hot pressing, an
increment of 37% in Young’s modulus was achieved after adding
2.1% MWNTs [33]. For the PP/single-walled carbon nanotubes
(SWNTs) composite prepared in a melt internal mixer (Haake
Rhomix), the incorporation of 0.75% SWNTs resulted in a 39% in-
crease of Young’s modulus [30]. Masuda et al. [24] utilized a spe-
cific SSSP extrusion equipment to fabricate PP/MWNTs
composite, an obvious improvement of 57% in Young’s modulus
was achieved when the MWNTs content was 0.92%, which is by
CNT 5%
far the best strengthen effect for PP/MWNTs composite. However,
54.8  104 the excellent strength–rigid–toughness balance is rarely seen in
4.8
the polyolefin/CNTs composites, especially for the toughening ef-
fect [34]. It has been found only for the PE/PE-g-MWNTs compos-
ites prepared by chemical grafting of reactive extrusion with fine
1402 Z. Wang et al. / Composites Science and Technology 71 (2011) 1397–1403

(a) (b)

Fig. 3. Variation of (a) tension strength and Young’s modulus and (b) impact strength and elongation at break.

dispersion and strong interfacial adhesion [35]. Since the excellent

comprehensive mechanics are achieved, and importantly the used
RSSM equipment is a kind of frequently used dispersion machine,
which has tremendous potential to be applied in industrial produc-
ing immediately, the two-step procedure of RSSM-plus-melt com-
pounding is most effective and convenient for dispersing carbon
nanotubes into the nonpolar, intractable thermoplastics, among
variety of fabrication method suggested in the previous researches.
The mechanical reinforcement is also reflected on the dynamic
mechanical property. The storage modulus vs. temperature is plot-
ted in Fig. 4 for the PP–MWNTs composites. In general, within the
entire temperature range, the higher the MWNTs content the lar-
ger the storage modulus is, indicating the magnitude of reinforce-
ment is increased with the MWNTs content. The increase of G0 with
increasing MWNT content is obvious within the temperature re-
gime below Tg; but it becomes less when the testing temperature
is above Tg. For example, the G0 is increased from 3300 MPa for ba-
sal PP to 4050 MPa for PP–MWNT5 at 50 °C; while it is changed
from 2236 MPa to 2588 MPa at room temperature (20 °C). Fig. 5. The volume resistance of PP filled with various MWNT loadings.
Finally, the electronic conductivity is compared between the
PP–MWNTs system and the PP-p-MWNTs system. Seeing from
of percolation is attributed to better dispersion of MWNTs induced
Fig. 5, an abrupt decrease in volume resistivity occurs at 1%
by the RSSM treatment.
MWNTs content for the PP–MWNTs system, whereas it is at 3%
According to the current experimental evidences, it can be con-
MWNTs content for the PP-p-MWNTs system, indicating a lower
cluded at least that the two-step procedure of RSSM-plus-melt
threshold value for the formation of percolated conductive net-
compounding leads to a better dispersion of MWNTs than the sin-
work in the former system. Obviously, the lower threshold value
gle-step melt compounding, which is mainly responsible for excel-
lent comprehensive performances in the as-prepared composites.
As to the reason why the RSSM process can induce a better disper-
sion, it is due to an ideal pre-mixing status that PP granules are
physically coated by MWNTs is attained after experiencing this
treatment. However, it is argued that the enhanced dispersion
may be caused merely from the breaking up of MWNT aggregates.
To approve this assumption, the RSSM treatment was conducted
solely on MWNT powder, and then the breaking-up MWNTs were
compounded with iPP/PP-g-MA in the extruder. The resultant dis-
persion and mechanical properties obtained via such two-step pro-
cedure were almost same to that from the single-step melt
compounding. This result manifests the important role of the ideal
pre-mixing status that PP and MWNTs physically combined to-
gether on the realizing of better MWNT dispersion. On the other
hand, the RSSM process may also induce the scission of MWNTs.
We would like to believe that MWNTs partially occur scission
rather than seriously destroy because of (1) the shear intensity im-
posed by RSSM is not extremely strong; (2) a good strengthening
can be achieved by incorporation of RSSM-treated MWNTs; (3)
Fig. 4. Plots of storage modulus (G0 ) vs. temperature for PP–MWNTs. the shortening of MWNT length might explain why the toughness
 Z. Wang et al. / Composites Science and Technology 71 (2011) 1397–1403
improved moderately. In our current research, the powerful evi-
dence for the occurrence of MWNTs scission during RSSM is
unavailable, which will be implemented in our future work by,
such as, electro-microscopy observation, composite viscosity mea-
surement and Raman spectroscopy characterization on the pristine
MWNTs and RSSM-treated MWNTs.
4. Conclusions
A simple but effective methodology has been developed to fab-
ricate the iPP/MWNTs composites by using the easily available
processing equipments. The RSSM treatment can improve the dis-
persion extent of MWNTs and thus lead obvious enhancements in
variety of property. The tensile strength, Young’s modulus and im-
pact strength of composite prepared by the two-step procedure of
RSSM-plus-melt compounding is increased by 35%, 42% and 45%,
respectively, as the MWNTs is 5 wt%. Therefore, the simultaneously
toughening and strengthening effect has been induced by the
RSSM treatment, which is rarely seen in the polyolefin/CNTs com-
posites. Meanwhile, the critical MWNTs content for the formation
of percolated conductive network is 1% for the composite system
obtained via RSSM-plus-melt compounding, which is less than that
for the composites obtained via single-step procedure of melt com-
pounding. We believe that this methodology has tremendous po-
tential to be applied in practical industrial fields for fabricating
the polyolefin/CNTs composites with excellent comprehension
properties.
Acknowledgment
We would like to express our sincere thanks to the National
Natural Science Foundation of China for Financial Support
(50973065, 50873063, 20874064).
References
[1] Baughman RH, Zakhidov AA, de Heer WA. Science 2002;297:787.
[2] Cao J, Wang Q, Rolandi M, Dai H. Phys Rev Lett 2004;93:216.
1403
[3] McNally T, Potschke P, Halley P, Murphy M, Martin D. Polymer 2005;46:8222.
[4] Chazeau L, Gauthier C, Vigier G, Cavaillé JY. Relationships between
microstructural aspects and mechanical properties of polymer-based
nanocomposites. Handbook of organic–inorganic hybrid materials and
nanocomposites, vol. 2. American Scientific Publishers; 2003. p. 63–111.
[5] Zhang LY, Wan CY, Zhang Y. Compos Sci Technol 2009;69:2212.
[6] Zhang ZN, Zhang J, Chen P, Zhang BQ, He JS, Hu GH. Carbon 2006;44:692.
[7] Georgakilas V, Kordatos K, Prato M, Guldi DM, Holzinger M, Hirsch A. J Am
Chem Soc 2002;124:760.
[8] Dyke CA, Tour JM. J Phys Chem A 2004;108:11151.
[9] Blake R, Gun’ko YK, Coleman J, Cadek M, Fonseca A, Nagy JB, et al. J Am Chem
Soc 2004;126:10226.
[10] Tasis D, Tagmatarchis N, Bianco A, Prato M. Chem Rev 2006;106:1105.
[11] Chen RJ, Zhang Y, Wang D, Dai H. J Am Chem Soc 2001;123:3838.
[12] Chen J, Liu H, Weimer WA, Halls MD, Waldeck DH, Walker GC. J Am Chem Soc
2002;124:9034.
[13] Dyke CA, Tour JM. J Am Chem Soc 2003;125:1157.
[14] Hill DE, Lin Y, Rao AM, Allard LF, Sun YP. Macromolecules 2002;35:9466.
[15] Hong CY, You YZ, Pan CY. Polymer 2006;47:4300.
[16] Ginic-Markovic M, Matisons JG, Cervini R, Simon GP, Fredericks PM. Chem
Mater 2006;18:6258.
[17] Lee J, Yang SB, Jung HT. Macromolecules 2009;42:8328.
[18] Velasco-Santos C, Martinez-Hernandez M, Fisher FK, Ruoff R, Castario VM.
Chem Mater 2003;15:4470.
[19] O’Connel MJ, Boul P, Ericson LM, Huffman C, Wang Y, Haroz E, et al. Chem Phys
Lett 2001;342:265.
[20] Li X, Wong SY, Tjiu WC, Lyons BP, Oh SA, He CB. Carbon 2008;46:818.
[21] Lu K, Grossiord N, Koning CE, Miltner HE, Mele B, Loos J. Macromolecules
2008;41:8081.
[22] Zhang QH, Lippits DR, Rastogi S. Macromolecules 2006;39:658.
[23] Gao JF, Li ZM, Meng QJ, Yang Q. Mater Lett 2008;62:3530.
[24] Masuda J, Torkelson JM. Macromolecules 2008;41:5974.
[25] Xia H, Wang Q, Li K, Hu GH. J Appl Polym Sci 2004;93:378.
[26] Grady BP, Pompeo F, Shambaugh RL, Resasco DE. J Phys Chem B
2002;106:5852.
[27] Valentini L, Biagiotti J, Kenny JM, Lopez Manchado MA. J Appl Polym Sci
2003;89:2657.
[28] Leelapornpisist W, Ton-That MT, Perrin-Sarazin F, Cole KC, Denault J, Simard B.
J Polym Sci Part B 2005;43:2445.
[29] Bikiaris D, Vassiliou A, Chrissafis K, Paraskevopoulos KM. Polym Degrad Stab
2008;93:952.
[30] Manchado MAL, Valentini L, Biagiotti J, Kenny JM. Carbon 2005;43:1499.
[31] Yuan JM, Fan ZF, Chen XH, Chen XH, Wu ZJ, He LP. Polymer 2009;50:3285.
[32] Miltner HE, Grossiord N, Lu K, Loos J, Koning CE, Mele BV. Macromolecules
2008;41:5753.
[33] Koval’chuk AA, Shevchenko VG, Shchegolikhin AN, Nedorezova PM, Klyamkina
AN, Aladyshev AM. Macromolecules 2008;41:7536.
[34] Mahfuz H, Adnan A, Rangari VK, Jeelani S. Int J Nanosci 2005;4:55.
[35] Yang BX, Pramoda KP, Xu GQ, Goh SH. Adv Funct Mater 2007;17:2062.