Composites: Part A 41 (2010) 1797–1806

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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Influence of fiber-like nanofillers on the rheological, mechanical, thermal and

fire properties of polypropylene: An application to multifilament yarn
Andrés F. Vargas a,c,⇑, Víctor H. Orozco a,c, Francois Rault b,c, Stephane Giraud b,c, Eric Devaux b,c,
Betty L. López a
a
Grupo Ciencia de los Materiales, Universidad de Antioquia, Calle 62 52 59 Medellín, Antioquía 050010, Colombia
b
Univ Lille Nord de France, F-59000 Lille, France
c
Laboratoire de Génie et Matériaux Textiles (GEMTEX), UPRES EA 2461, Ecole Nationale Supérieure des Arts et Industries Textiles (ENSAIT), 2 Allée Louise et Victor Champier,
BP 30329, 59056 Roubaix Cedex 01, France

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

Article history: Polypropylene and polypropylene grafted maleic anhydride based composites with modified and non-
Received 18 February 2010 modified carbon nanotubes and sepiolite were prepared by melt extrusion. Their thermal, rheological,
Received in revised form 25 August 2010 and dynamic mechanical properties were evaluated. Multifilament yarns were obtained from the com-
Accepted 31 August 2010
posites by spin-drawing process and their mechanical properties were measured. Knitted fabrics from
the multifilament yarns were characterized by cone calorimetry. The best interaction was obtained for
polypropylene/carbon nanotubes and polypropylene/polypropylene grafted maleic anhydride/sepiolite
Keywords:
composites, as was confirmed by the increasing on the elastic modulus and thermal resistance. Nanofil-
A. Polymer-matrix composites (PMCs)
A. Nano-structures
lers changed the thermal decomposition profiles compared to bare polypropylene. Knitted structures
B. Thermal properties containing sepiolite decrease the maximum of heat release rate in comparison with unfilled samples.
Ó 2010 Published by Elsevier Ltd.

1. Introduction However, the enhancement of the mentioned properties de-

Polypropylene (PP) is a widely used polymer giving its balance
among strength, modulus and chemical resistance, it has fiber
forming capability, and its low density, low cost and easy process-
ability makes it suitable for applications in automobiles, packaging
and textile industry. However PP has to overcome some drawbacks
such as its maximum service temperature of 82 °C, high flammabil-
ity, thermal oxidation, and limited impact strength.
There are several ways to improve chemical, tribological,
mechanical, fire and thermal properties of polymer materials.
Incorporation of fillers into the polymer matrix has been exten-
sively used to improve the mentioned properties. Giraldo et al.
have improved the scratch resistance of polyamide 6 (PA6) by
incorporating carbon nanotubes (CNT) [1], silica particles have also
been used to improve the scratch and thermal resistance of poly-
mer films [2], Pérez et al. found out that nanometric mesoporous
silica particles enhanced the mechanical and thermal properties
of polystyrene, when styrene is polymerized in presence of silica
particles [3]. Manganese nanoparticles improved mechanical and
thermal properties of PP fibers [4].
⇑ Corresponding author at: Grupo Ciencia de los Materiales, Universidad de
Antioquia, Calle 62 52 59 Medellín, Antioquía 050010, Colombia. Tel.: +57 4
2196546; fax: +57 4 2196550.
E-mail address: andresfelipe.vargas@gmail.com (A.F. Vargas).
pends strongly on the interactions between filler and polymer.
Therefore, homogeneous dispersion of filler in polymer matrix
and good interfacial adhesion are crucial for the performance of
nanocomposites. Several approaches have been used to achieve
this goal, such as chemical functionalization of filler and/or matrix,
or by using compatibilization agents. Maleic anhydride (MA) mod-
ification has been widely employed to add polar moieties to the
polymer chains to improve the interface interactions. Impact resis-
tance of PP blends with ethylene propylene diene terpolymer
(EPDM) improved when both were grafted with MA [5]. Compos-
ites of clay and PP grafted MA (PPgMA) showed an enhancement
on their thermal stability, tensile and rheological properties [6].
Filler geometry plays an important role on the final properties
of the composite, for instance PA6 composites prepared with
different filler shape and sizes showed a rheological behavior
which depends on the aspect ratio of particles used [7,8]. CNT
are an especially attractive class (¿type no suena mejor?) of inclu-
sions because of their exceptional mechanical, thermal, electrical
properties, and its high aspect ratio and fiber-like shape. As a
result, they have been successfully used for preparation of compos-
ites [9–11]. Needle-like mineral clay sepiolite is also used to
prepare polymer nanocomposites, which have shown an improve-
ment of the mechanical properties in polymers [12–15]. Both sepi-
olite and CNT have fiber-like shape, for that reason they have
become very promising to prepare polymer nanocomposites for

1359-835X/$ - see front matter Ó 2010 Published by Elsevier Ltd.

doi:10.1016/j.compositesa.2010.08.018
1798 A.F. Vargas et al. / Composites: Part A 41 (2010) 1797–1806
the textile industry. Several works have been developed in fiber
based nanocomposites using different types of polymer matrices
and fillers [16–26].
Lee and Youn [27] found that tensile properties of nanocompos-
ite fibers got worse compared with those of bare PP fibers due to
aggregation of layered silicates, Rault et al. [28] reported that the
incorporation of more than 1 wt.% of clay causes difficulties for
the spinning. On the other hand, Bourbigot et al. [29] produced
multifilament yarns from PA6 clay nanocomposite, wherein the
heat release rate (HRR) of knitted structures of nanocomposite de-
creased about 40% respect to bare PA6. Joshi et al. [30] demon-
strated a significant improvement in the tensile properties of PP/
nanoclay composite filaments at very low clay loadings of 0.25–
0.5 wt.% A slight improvement on Young’s modulus was observed
for PP filaments filled with 1 wt.% of CloisiteÒ15A [28]. Clay
nanocomposites did not show an improvement on flame retardan-
cy respect to bare polymer, however the burning behavior of nano-
composites was affected by clay as showed elsewhere [31].
In this work two types of nanofillers, sepiolite and CNT, were
modified by ionic exchange and chemical oxidation respectively,
then nanocomposites with bare PP and/or PP/PPgMA blends were
prepared by extrusion using both functionalized and non function-
alized fillers. Thermal, rheological, and dynamic mechanical
properties of nanocomposites were evaluated and compared.
Multifilaments yarns obtained from the prepared blends were
characterized by mechanical tests and knitted structures by cone
calorimetry.
2. Experimental
2.1. Materials
A commercial grade of polypropylene (DOW H777-25R Polypro-
pylene Resin, MFI = 25 g/10 min, Dow Chemical) has been used as
the base polymer and a commercial PPgMA (Epolene G-3003, East-
man Mw 52.000) with 0.8 wt.% of MA has been chosen as compat-
ibilizer. CNT used was commercially obtained from nanocyl
(Belgium). It was produced by CVD and had a purity of 90%. The
diameter of MWNTs is about 10 nm and the length is between
0.1 and 10 lm. Micronized sepiolite is from Tolsa, Spain. Nitric acid
65 wt.% and cethyl trymethyl ammonium bromide (CTABr) are
from Sigma–Aldrich and were used as received.
2.2. Carbon nanotubes oxidation
CNT were dispersed in nitric acid (65 wt.%) in a 25:300 ratio
using an ultrasonic bath for 30 min at 80 °C. Then the dispersion
was put in a round bottom flask equipped with a condenser and
was refluxed at 80 °C for 48 h. The resulting dispersion was filtered
and oxidized carbon nanotubes (CNTO) were washed up to neutral
pH, and dried in vacuum at 40 °C overnight.
2.3. Sepiolite functionalization
1.10 g of CTABr were dissolved in 450 mL of water with mag-
netic stirring at 35 °C. Then 30 g of sepiolite were added to the
solution and stirred during 1 h. The slurry was left overnight, then
it was centrifuged and the functionalized sepiolite (SEPF) was dried
in vacuum at 40 °C overnight.
2.4. Fourier transform infrared spectroscopy (FTIR)
The FTIR spectra were recorded with a Perkin-Elmer spectrum
one spectrometer; powdered samples were dispersed in KBr and
thin disks were prepared and analyzed in transmission mode.
2.5. Preparation of the nanocomposites
The compositions of the ten blends are listed in Table 1. Prior to
compounding PP, PPgMA (pellets form) and sepiolite or carbon
nanotubes (powder form) were first hand mixed by shaking them
in a plastic container. All blends were then melt extruded using a
co-rotating, intermeshing twin screw extruder (Thermo Haake,
diameter of screw = 16 mm, L/D = 25). The temperature of the ex-
truder was maintained at 110, 170, 200, 200 and 200 °C in the dif-
ferent zones from hopper to the die and the screw speed was set at
100 rpm. The extrudate was then pelletized. A total of 1.5 kg was
processed for each sample.
2.6. Preparation of the nanocomposite multifilament yarns
Multifilaments yarns were made via melt spinning process
using the spinning device Spinboy I from Busschaert Engineering.
The pellets, previously prepared by extrusion, were first introduced
in the feeding zone of a single screw extruder and heated gradually
from 180 to 230 °C by using five heating zones. In order to obtain
continuous multifilament yarns, a volumetric pump with a flow
rate of 100 cm3/min was used. The molten polymer was pushed
through two 40-hole dies (D.I. 400 lm). The yarn was air cooled
and coated with a lubricating agent, and then it was hot-drawn
through two rolls, feeding and draw roll. The ratio between the
rotation speeds of the rolls mentioned above was 1.25. The tem-
perature of the first roll was 70 °C, and the temperature of the sec-
ond 80 °C.
2.7. Melt rheology
Sheets were made by means of compression molding, using a
temperature of 200 °C and a pressure of 60 bar. Rheological mea-
surements were carried out on the rheometer (AR2000 TA instru-
ments) equipped with a parallel plate geometry using 25 mm
diameter plates. The sheet samples in thickness of 2.0 mm were
first melted at 200 °C for 2 min in the parallel plate fixture to elim-
inate residual thermal history, and then dynamic strain sweep was
carried out to determine the linear viscoelastic region. At the strain
level of 1%, dynamic frequency sweep was carried out on all
samples.
2.8. Thermogravimetric analysis (TGA)
To study the thermal stability of composites, TGA were per-
formed using a TA Instruments Q500. Pellets of each sample were
used. Dynamic runs were carried out from 25 to 800 °C at the heat-
ing rate of 10 °C/min under nitrogen atmosphere.
2.9. Differential scanning calorimetry (DSC)
TA Instruments Q100 was used to determine glass transitions
Tg, melting points Tm, crystallization temperatures Tc and melting
enthalpies, DHm. The thermal history was erased during the first
run at a high heating rate up to 220 °C followed by a fast cooling
to 20 °C. Then temperature was increased at a heating rate of
10 °C/min to 220 °C.
2.10. Dynamic mechanical analysis (DMA)
Specimens of rectangular shape (length: 1.8 cm, width: 0.6 cm,
thickness: 0.2 cm) were analyzed in the dual cantilever mode at
1.0 Hz in dry nitrogen (20 mL/min) from 50 °C to 120 °C using
the heating rate of 3 °C/min in a TA Instruments DMA Q800
equipment.
 A.F. Vargas et al. / Composites: Part A 41 (2010) 1797–1806 1799

Table 1
Description of blends preparation.

Sample PP (%) PPMA (%) CNT (%) Sepiolite (%) CNTO (%) Sepiolite functionalization (%)
PP 100 0 0 0 0 0
PP/PPgMA 90 10 0 0 0 0
PPCNT 99.25 0 0.75 0 0 0
PP/PPgMACNT 89.25 10 0.75 0 0 0
PPSEP 99.25 0 0 0.75 0 0
PP/PPgMASEP 89.25 10 0 0.75 0 0
PPCNTO 99.25 0 0 0 0.75 0
PP/PPgMACNTO 89.25 10 0 0 0.75 0
PPSEPF 99.25 0 0 0 0 0.75
PP/PPgMASEPF 89.25 10 0 0 0 0.75

2.11. Scanning electron microscopy (SEM)
A FEI dual beam FESEM microscope was used to analyze the
morphology of the fillers. The samples were dispersed in ethanol,
and then a few drops were poured on the SEM holder and allowed
to dry. Finally the samples were gold-coated for the observation.
flux of 35 kW/m2. This flux corresponds to a typical heat flux in a
mild fire scenario. The mass loss calorimeter was used to deter-
mine time to ignition (tign), the total heat evolved (THE) and the
heat release rate (HRR). HRR measured at 35 kW/m2 was reproduc-
ible within ±10%. The data reported in this paper are the average of
three experiments.

2.12. Mechanical properties of multifilament yarn

3. Results and discussion

The linear density of multifilament yarns was calculated at

It is well known that PP is hydrophobic, which makes it suitable
standard atmosphere after determining the mass of 10 m of yarn.
to prepare blends with highly hydrophobic nanoparticles like
The measurement of the tensile properties of multifilament yarns
CNTs. We wanted to compare different compatibilization strategies
were carried out on an automatic tensile testing machine (STATI-
and their effect on the final properties of the composite. PP modi-
MAT M) manufactured by Textechno, located at the University of
fied with MA was used and polar moieties were introduced on CNT
Gent (Belgium). The gauge length was 100 mm, and the deforma-
surface by acidic oxidation, also sepiolite surface was modified by
tion rate was 5000 mm/min. The Young’s modulus was determined
ionic exchange to make it hydrophobic.
from the slope of the experimental curves. The tenacity was calcu-
lated by dividing the force at the top of the tensile curve by the lin-
ear density, and the elongation at break was determined from the 3.1. Carbon nanotubes oxidation
distance between the start and the point of break. All tensile prop-
erties were reported in terms of an average of 10 samples. Chemical treatment of nanotubes with nitric acid, sulfuric acid,
hydrogen peroxide and ammonium hydroxide has been used to
2.13. Knitted fabric of polypropylene nanocomposite multifilament introduce carboxylic groups on their surface, it is also important
yarns to highlight that this modification might cause shortening of CNT
by oxidative scission, introducing structural defects decreasing
Polypropylene and polypropylene nanocomposite multifila- their thermal resistance and lowering the mechanical properties.
ment yarns were knitted on flat machine gauge 8. The structure In contrast the polar moieties on the surface may enhance the
of the knitted fabric is represented on Fig. 1. interactions with hydrophilic blocks such as hydrogen bonding
and also chemical bonding with additional treatments [32–34].
2.14. Flame properties Fig. 2 shows the decomposition profile in air of CNT and CNTO.
The sample CNTO, as was expected, showed weight loss from room
Fire testing technology (FTT) mass loss calorimeter was used to
carry out measurements on samples following the procedure de-
fined in ASTM E 906. The equipment is identical to that used in
oxygen consumption cone calorimetry (ASTM E-1354-90), except
for a thermopile in the chimney, which is used to obtain the heat
release rate (HRR), instead of employing the oxygen consumption
principle. Knitted fabrics measuring 100 mm  100 mm  2 mm
arranged in horizontal position were exposed to an external heat

Fig. 1. Yarn path used for the fabrics. Fig. 2. TGA of oxidized and non oxidized CNT.
1800 A.F. Vargas et al. / Composites: Part A 41 (2010) 1797–1806
Fig. 3. FTIR spectra of sepiolite and functionalized sepiolite.
temperature to 150 °C due to the increase on their hydrophilicity.
There is a change of 150 °C in the maximum decomposition tem-
perature peak, this can be explained by the introduction of oxygen
atoms on the CNT surface which contributes to the oxidative reac-
tion, and besides the shortening and the increased amount of de-
fect density reduces the CNT thermal stability as was mentioned
before.
3.2. Sepiolite functionalization
Sepiolite is a 2:1 phyllosilicate, which is a hydrous magnesium
silicate with (Si12Mg8O30)(OH)4(OH2)48H2O as the theoretical unit
cell formula [35]. It is composed of two tetrahedral silica sheets
sandwiching a central sheet of magnesium oxide–hydroxide, dis-
continuities of the silica sheets gives rise to the presence of silanol
groups (Si–OH) at the edges of the tunnels. Silanol groups can pro-
mote the interaction of sepiolite with polar moieties, but to make it
compatible with hydrophobic polymers modification should be
carry out, for instance silane coupling agents [36] or cationic com-
patibilizer agents [37]. It has been shown that sepiolite can ex-
change its Mg+2 ions with positively charged amine groups [36],
therefore CTABr was used to enhance the compatibility of sepiolite
with PP through the aliphatic chains of cethyl group. FTIR spectra
of the non treated and treated sepiolite are shown in Fig. 3, bands
from 3430 to 3765 cm1 correspond to –OH groups from Mg3OH
and zeolitic water, band at 1664 is assigned to zeolitic water and
bound water. Both spectra showed the Si–O bands at 1213 and
1018 cm1 (not shown). After the cationic exchange treatment
two new bands appeared at 2926 and 2853 cm1, they are related
to the C–H stretching, which confirms the incorporation of CTABr
in the sepiolite.
Fig. 4. Variation of the elastic modulus vs. strain % at 1.0 Hz of (a) composites prepared with PP and (b) PP/PPgMA as polymer matrix.
3.3. Blends preparation
Samples prepared will be labeled according to Table 1, all of
them were successfully extruded and pelletized, and they were
also spin-drawn except the sample PP/PPgMACNTO, for the latter
it was not possible to obtain a continuous multifilament yarn,
due to an increment on the viscosity probably due to the high
interaction between carboxylic groups of CNTO and MA groups of
PPgMA as it will be shown further.
3.4. Melt rheology
In textile industry processing parameters are highly important,
because physical appearance and physical properties of polymer
and polymer composite depends on melt rheological behavior, it
also allows to design the suitable equipment and to optimize the
processing conditions in order to reduce the energy needed in
the whole process [38,39]. It is well known that nanofiller incorpo-
ration into a polymer matrix leads to a change in the viscoelastic
properties [40], therefore rheological measurements have to be
performed.
With the intention of finding the viscoelastic region, sweep
strain tests were carried out, from Fig. 4, it can be seen, that all
samples have a wide flat region from 0.01% to 30.00% where the
modulus does not change with increasing strain. On the other
hand, for samples prepared with CNTO, Fig. 4a, the elastic modulus
decreases after 1.00% strain, due to agglomeration–deagglomera-
tion process, called Payne effect, which is probably caused by poly-
mer–particle and particle–particle interactions, and it is highly
dependent on the filler surface [41]. Perhaps the oxidative process
on CNT surface improves the CNTO–CNTO interactions compared
to CNT–CNT interactions. The Payne effect for sample PP/
PPgMACNTO, Fig. 4b, is more pronounced than PPCNTO which ex-
plains why the former could not be spin-drawn. The samples
PPCNT and PP/PPgMASEP, presented in Fig. 4a and b, respectively,
showed the highest values of elastic modulus in the composites
whose matrices were PP and PP/PPgMA, respectively, due to the
formation of a filler network through the interaction polymer–filler
and filler–filler, the high aspect ratio of CNT also contributes to the
increase of modulus of PPCNT.
Previous studies have shown that slow changes in elastic mod-
ulus at low frequencies are related with a solid-like behavior [40]
due to structuration of filler into polymer matrix. Fig. 5 shows
the frequency dependency of elastic modulus for all samples, at
low frequencies there is an increase of elastic modulus for all sam-
ples respect to the bare polymer, except for the samples modified
with SEPF. Composites prepared with SEP do not change the visco-
 A.F. Vargas et al. / Composites: Part A 41 (2010) 1797–1806
Fig. 5. Variation of elastic modulus with frequency of (a) composites prepared with PP and (b) PP/PPgMA as polymer matrix.
elastic behavior contrary to the ones prepared with CNT and CNTO,
which present a structuration effect that is reflected on the first
stages of the plot, which confirms the Payne effect for these sam-
ples. At high frequency, which is related to polymer chains move-
ment at small time scale, there are no marked differences among
samples, therefore addition of nanofiller is not affecting chain
movement. The increase in the elastic modulus was greater than
the increase in the loss modulus (not shown), consequently the
structure of nanocomposites is more reflected on elastic modulus
than loss modulus.
Fig. 6 shows the complex viscosity (g) vs. frequency for PP and
PP/PPgMA, clearly g is higher for PP than PP/PPgMA, as rheology
behavior is very sensitive to molecular structure, PPgMA has pen-
dant groups in the backbone and also may have lower molecular
weight due to b scission suffered during the grafting process as
has been studied before [39].
It has been reported that viscosity increases when nanofillers
are added to polymer matrix [42], it can be seen in Fig. 7 that all
composite samples have a higher viscosity than bare polymer.
The high aspect ratio of the fillers explains the increase on the vis-
cosity. PP/PPgMACNTO showed the higher increase in viscosity,
this explains the problems to get multifilament yarns of this sam-
ple by spin-draw process as it was mentioned before.
Fig. 6. PP and PP/PPgMA absolute complex viscosity.
1801
3.5. TGA
Fig. 8 shows a typical TGA graph of PP nanocomposites, specif-
ically PPCNT is shown, only one weight loss is seen for all samples,
the extracted data from each TGA trial are summarized in Table 2.
Table 2 shows maximum decomposition temperature (Tmax)
and temperature at weight loss 10% (T10%) for all samples. First it
can be seen that addition of PPgMA to the polymer matrix
increases its thermal stability by 35 °C, this behavior has been al-
ready observed by Modesti et al. [43] when a nitrogen atmosphere
was used. This can be explained because during the pyrolisis reac-
tion, PPgMA can undergo decarboxylation followed by structural
rearrangement to form a char due to cleavage of MA. PPCNT sam-
ple shows an increase in thermal stability compared to bare PP, it
means that there is good compatibility between CNT and PP, this
behavior is not seen for CNT with PP/PPgMA. The effect of CNTO
in the thermal stability for PP is lower than CNT, however they
have a better interaction with the PP/PPgMA matrix, because there
is an increase of 25 °C in Tmax respect to PP/PPgMACNT.
The addition of sepiolite improves Tmax for all samples respect
to PP, even though Tmax for PPgMASEP is lower than PP/PPgMA,
thermal decomposition is higher for PP/PPgMASEP than PPSEP,
therefore sepiolite have a better interaction with PP/PPgMA than
with PP. When SEPF is used as filler, the increase in the Tmax is low-
er than SEP, then CTABr does not improve the thermal stability,
which could be due to the fact that it has a plasticizer effect or be-
cause the organic content increases.
The shifts on thermal stability are more marked for T10% than
Tmax, it probably means that the decomposition mechanism is
being influenced by the fillers, as it can be seen on Fig. 9, where
is possible to see that not only the maximum decomposition tem-
peratures is changing, but also the mechanism and reaction kinet-
ics are probably being affected by the fillers, because the shape of
the bands are being broadened or narrowed after adding the
nanoparticles.
3.6. DSC
The DSC technique has been described by Saiter and colleagues
[44]. Fig. 10 shows a typical DSC graph of PP nanocomposites, spe-
cifically PPCNT is shown, two thermal events are seen, crystalliza-
tion and melting, glass transition is not seen because the
crystallization rate is faster than the cooling rate of the equipment
used. The extracted data from each DSC trial are summarized in Ta-
ble 3.
1802 A.F. Vargas et al. / Composites: Part A 41 (2010) 1797–1806

Fig. 7. Absolute complex viscosity vs. frequency of (a) composites prepared with PP and (b) PP/PPgMA as polymer matrix.

The addition of nanofillers promotes the crystallization process,

which is reflected on DHmelt, except for sample PPSEPF, probably
SEPF prevents the arrangement of polymer chains.
DHcrys is higher for blends with CNT that those with CNTO,
hence there are more crystals when CNT is used, therefore the
interaction between CNT and polymer matrix is better. Samples
loaded with SEPF do not show a large change on DHcrys.

3.7. Dynamic mechanical analysis

The DMA technique has been already explained by Menard [45].

Fig. 11 shows a typical DMA graph for sample PPCNT, only the glass
transition (Tg) is observed. Tg was calculated from the loss modulus
and the elastic modulus was taken at 30 °C. Table 4 summarizes
the results.
From Table 4, it can be concluded that the addition of PPgMA
does not have an effect on chain mobility. For PPSEPF and PP/
PPgMASEPF, there is a marked reduction on chain mobility as it
is seen in the large increase on Tg compared with the other sam-
Fig. 8. Typical TGA plot. ples. The rest of the samples showed a slight decrease on Tg, which
is not a meaningful difference with the Tg for PP and PP/PPgMA,
perhaps the filler fraction was not high enough to induce a notice-
able change on Tg.
Table 2 There is a slight rise on elastic modulus at 30 °C for all samples
TGA summary results.
except PPSEP and PP/PPgMASEP, the highest value for E0 was ob-
Sample Tmax (°C) T10% (°C) tained for sample PPCNT, because CNT have a large effect on
PP 449.0 379.5 mechanical properties, as was expected.
PP/PPgMA 483.7 440.9
PPCNT 484.7 458.2 3.8. Mechanical properties of multifilament yarns
PP/PPgMACNT 442.8 380.7
PPSEP 469.9 432.5
PP/PPgMASEP 473.6 395.8 Tensile tests on the multifilament yarns were conducted to
PPCNTO 465.2 397.3 determine how mechanical properties were influenced by the
PP/PPgMACNTO 467.1 410.3 presence of PP grafted MA and incorporation of fillers. Young’s
PPSEPF 461.1 436.6
modulus, tenacity and elongation at break and linear density of
PP/PPgMASEPF 456.0 435.2
multifilament yarns of all samples are listed in Table 5. It can be
seen that the addition of 10 wt.% of PPgMA provides a decrease
of modulus and tenacity from approximately 24% and 54%, respec-
The addition of PPgMA to the PP increases Tcrys, DHcrys and tively. This decrease in mechanical properties can be attributed to
DHmelt, therefore PPgMA increased the crystalline fraction in the a reduction on molecular weight, as the PP b scission happens dur-
polymer matrix. The addition of CNT and CNTO have the same ef- ing the grafting reaction in order to obtain PPgMA [39].
fects on Tcrys for both PP and PP/PPgMA blends, they increase it, It can also be noticed that all PP multifilament yarns filled with
perhaps carbon nanotubes are behaving as nucleation sites for SEP or CNT reveal a high decrease of the Young’s modulus and
the polymer chains. There is not an obvious effect of SEP on Tcrys. tenacity. This reduction can be explained by debonding process
SEPF is slightly decreasing Tcrys. There is not any effect of the fillers and formation of voids in the matrix. Indeed, the absence of inter-
on Tmelt, as a result the crystalline phase is the same for all actions leads to a poor bonding between the particles and the PP
samples. matrix. When PP multifilament yarns filled with SEP or SEPF are
 A.F. Vargas et al. / Composites: Part A 41 (2010) 1797–1806 1803

Fig. 9. Derivative weight loss vs. temperature of (a) composites prepared with PP and (b) PP/PPgMA as polymer matrix.

Fig. 10. Typical DSC plot. Fig. 11. Typical DMA plot.

Table 3
DSC summary results. Table 4
a a
DMA summary results.
Sample Tcrys (°C) DHcrys (J/g) Tmelt (°C) DHmelt (J/g)
Sample Tg (°C) E0 (GPa)a
PP 111.7 94.1 160.1 92.9
PP/PPgMA 114.7 104.8 158.3 103.5 PP 1.7 1.53
PPCNT 119.8 108.1 161.3 108.0 PP/PPgMA 1.8 1.67
PP/PPgMACNT 119.7 107.0 161.0 106.3 PPCNT 1.3 2.06
PPSEP 112.3 97.9 161.2 99.1 PP/PPgMACNT 0.2 1.75
PP/PPgMASEP 113.1 105.6 160.9 107.6 PPSEP 0.8 1.56
PPCNTO 119.8 103.9 161.5 105.3 PP/PPgMASEP 0.5 1.55
PP/PPgMACNTO 119.2 102.4 161.3 100.6 PPCNTO 0.6 1.76
PPSEPF 109.2 99.6 164.1 90.8 PP/PPgMACNTO 0.3 1.85
PP/PPgMASEPF 109.5 99.0 160.8 101.2 PPSEPF 7.2 1.60
a
PP/PPgMASEPF 7.3 1.73
These values were corrected respect to the real amount of polymer in each
a
sample. All modulus measurement were taken at 30 °C.

compared, there is a slight increase of the modulus for the latest
one, since the functionalization of SEP increases the compatibility
of the filler with PP.
All yarns prepared with PP/PPgMA have similar modulus and
tenacity values, except sample PP/PPgMACNT. Due to needle-like
shape of SEP, its alignment with the fiber axis is easier than for
CNT, as it can be seen in Fig. 12, producing fibers with less voids,
therefore multifilament yarns filled with SEP had better mechani-
cal properties than those filled with CNT.
Elongation at break for sepiolite based composites was greatly
improved, because sepiolite can align itself with the fiber axis
whereas CNT forms very entangled bunches, as was shown in
Fig. 12. PPCNTO composite showed an improvement on elongation
at break, this fact is explained by the shortening of CNT as a result
of the oxidizing treatment, which makes them able to align with
the fiber axis.
Table 5 suggests that there was not a reinforcement effect of
fillers on the mechanical properties of multifilament yarns, but it
1804 A.F. Vargas et al. / Composites: Part A 41 (2010) 1797–1806

Table 5
Mechanical properties of multifilament yarns.

Sample Linear density (tex) Modulus (cN/tex) Tenacity (cN/tex) Elongation at break (%)
PP 219.4 200.7 ± 3.2 10.9 ± 0.2 237 ± 60
PP/PPgMA 367.4 153.4 ± 7.2 5.0 ± 0.1 446 ± 26
PPCNT 319.5 121.06 ± 6.3 4.1 ± 0.1 127 ± 24
PP/PPgMACNT 344.5 124.9 ± 8.6 3.2 ± 0.1 172 ± 29
PPSEP 324.6 124.0 ± 2.8 6.9 ± 0.3 488 ± 24
PP/PPgMASEP 371.8 155.4 ± 6.9 4.7 ± 0.1 505 ± 57
PPCNTO 354.3 134.4 ± 5.9 4.6 ± 0.1 356 ± 24
PP/PPgMACNTO ND ND ND ND
PPSEPF 366.8 133.1 ± 6.2 6.3 ± 0.3 494 ± 20
PP/PPgMASEPF 367.4 153.3 ± 7.0 5.2 ± 0.2 426 ± 35

Fig. 12. SEM micrographs of (a) CNT and (b) SEP.

is important to highlight that these properties are strongly depen-
dent of linear density of yarns and this is closely related to the
spin-drawing process.
3.9. Flame properties
The mass loss calorimeter is an efficient equipment to study the
reaction to fire of a material. It allows to determine several param-
eters, which can describe the fire behavior of a material, such as
the time to ignition (tign), the rate at which the heat is released
(HRR), and the total heat evolved (THE).
The HRR plots for knitted of all PP composites are shown in
Fig. 13a.
Fig. 13b shows the HRR plots for knitted fabrics of all PP/PPgMA
composites.
Fire properties of all samples are listed on Table 6. PP/PPgMA
blend behaves similarly to bare PP. From the curves, it comes out
that SEP and CNT have different impacts on tign. Certainly, the sam-
ples filled with SEP have a similar tign that unfilled samples. tign is
slightly higher for unfilled samples compared to CNT filled sam-
ples. The decrease on tign of PP knitted structure filled with CNT
has already been observed [28]. Furthermore Kashiwagi et al.
[46] suggested that the reduction of tign of the PP matrix in pres-
ence of low CNT content was due to an increase in the radiation
in-depth absorption coefficient induced by the addition of fillers.
The maximum peak of HRR (PHRR) of knitted structures based
on PP containing CNT clearly increases compared to the unfilled
samples. An increase of 19% and 25% on PHRR was observed with
the addition of 0.75 wt.% of CNTO and CNT, respectively. For PP/
PPgMA filled with CNTO the PHRR increases 8% respect to PP/

Fig. 13. Heat release rate profiles for knitted fabrics obtained from multifilament yarns of (a) composites prepared with PP and (b) PP/PPgMA as polymer matrix.
 A.F. Vargas et al. / Composites: Part A 41 (2010) 1797–1806 1805

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