The effect of the non-covalent functionalization of CNT by ionic liquid on electrical

conductivity and electromagnetic interference shielding effectiveness of semi-

biodegradable polypropylene/poly(lactic acid) composites.

Short Running title

CNT/ionic liquid in PP/PLA composites

Bluma Guenther Soaresa,b*, Elisangela Cordeiroa, Jorge Maiab, Elaine Cristina Lopes Pereiraa,b, Adriana
Anjos Silvac

a
Universidade Federal do Rio de Janeiro, PEMM-COPPE, 21941-972 Rio de Janeiro, Brazil
b
Universidade Federal do Rio de Janeiro, Instituto de Macromoléculas, 21941-598, Rio de Janeiro, Brazil.
c
Universidade Federal do Rio de Janeiro, Escola de Química, Rio de Janeiro, Brazil

Acknowledgements

This work was sponsored in part by Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brasil
(CAPES) – Finance code 001; Conselho Nacional de Desenvolvimento Científico e Tecnológico – CNPq
(Grant number 303457/2013-9), and Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro – FAPERJ
(Grant number E-26/201.183/2014).

B. G. Soares() e-mail: bluma@metalmat.ufrj.br

1
Abstract

Semi-biodegradable polypropylene/poly(lactic acid) (70:30 wt.%) blend with co-continuous structure was
used for the development of conducting composites. Multi-walled carbon nanotube (CNT) and the non-
covalently functionalized CNT with alkylphosphonium-based ionic liquid (IL-CNT) were used as conducting
fillers. Relative high AC electrical conductivity was achieved by using 1 wt.% of CNT (around 10 -3 S/m).
This property increased four orders of magnitude when IL-CNT was employed. The effect of the
functionalization with IL on the rheological, morphological and thermal properties was investigated. The DSC
analysis also suggested that the filler (CNT or IL-CNT) exerted strong influence on the cold crystallization of
the PLA phase and also on the melt crystallization of the PP phase. The effect of the IL on the dispersion of
CNT was also confirmed by rheological measurements and transmission electron microscopy. An increase of
the attenuation of the electromagnetic radiation, i.e., an improvement of the electromagnetic interference
shielding effectiveness (EMI SE) in the X-band microwave region (8 – 12 GHz) was achieved by using IL-
CNT, with an important influence of the absorption mechanism to this property.

Keywords: Biodegradable; conducting polymers; electron microscopy; nanocomposites; viscoelastic

properties.

2
INTRODUCTION

Conductive polymeric materials are of great interest in the field of materials science and engineering due
to their strategic applications as lightweight and flexible antistatic dissipating materials as well as
electromagnetic shields and/or absorbers and sensors. An important goal in the research is to find appropriate
systems able to provide good level of electrical conductivity with the lowest amount of filler as possible to
keep the mechanical performance and processability of the matrix and produce cost-effective composites. In
this sense, heterogeneous polymer blends are preferred due to the uneven distribution of the filler in one phase
of the polymer blend or even at the interface. By choosing a blend composition with co-continuous structure,
the conductive pathway can be formed with lower amount of filler. This morphological situation is known as
double percolation, where the phase containing the percolated filler is continuous [1].

Poly(lactic acid) (PLA) is a well-known bio-based polymer and has received great attention in the last
decades due to its biodegradability, sustainability and thermo-plasticity similar to conventional plastics [2-3].
However, it is brittle and presents low toughness, low heat stability and low melt strength [4]. Moreover, its
low moisture resistance and biodegradability, which is important from an ecological point of view, result in
shorter service time, thus limiting its use in some applications. Blending PLA with conventional polymers has
been recognized as a good strategy for minimizing these drawbacks. Besides reducing the biodegradation rate,
the appropriate choice of the polymer partner for PLA-based blends also reduces cost and improves some
physic-mechanical properties. The gradual decomposition of the PLA phase in the blend gives rise a
degradation process known as biodisintegration, where very small pieces of the non biodegradable component
can be obtained [5]. Among several available conventional polymers, polypropylene (PP) has been employed
on the development of PLA blends due to its low cost, recyclability, processability and good mechanical
properties. Some studies involving PP/PLA blends with different compositions have been reported in the
literature, with the aim of improving melt processability and toughness of PLA, increasing the crystallization
rate of PLA and combining low cost with biodegradability [6-9].

The addition of conductive filler in PLA/PP blends constitutes a promising approach for broadening the
field of applications of this semi-biodegradable composite as antistatic and microwave shielding/absorbing
materials. However, few reports in the literature have been devoted to this kind of composite. Lee and Jeong
used different amounts of CNT in PLA/maleic anhydride-grafted PP (50: 50 wt.%) blend and observed a
percolation threshold with about 1 wt.% of CNT, with a resistivity value corresponding to 10 5 .cm [10]. In
this system, CNT was preferentially localized in the PP-g-MA phase. On the other hand, Lee et al also
investigated the properties of PP/PLA (70:30 wt.%) loaded with 5 phr of CNT and found conductivity values
of around 10-2 S/cm and a preferential localization of CNT within the PLA phase [11]. Li et al also observed
the selective localization of CNT within the PLA phase and a resistivity of around 105 .cm, by using 1 wt.%
of CNT [12].

In spite of the high intrinsic conductivity of CNT and the high aspect ratio, low percolation threshold in
polymer blends prepared by melting process is not easily achieved due to the high tendency of CNT to
agglomerate because the attractive van der Waals forces. This problem can be minimized by choosing
appropriate processing conditions and surface treatment of the CNT. In this sense, ionic liquids have been

3
played a prominent role since they are able to physically interact with the surface of CNT through π-cation ,
thus favoring the debundling of the aggregates [13]. In addition, they can also interact with the polymer
matrix, thus promoting a good filler-matrix interaction. Some studies related to the use of ionic liquid-
functionalized CNT in thermoplastic –based composites were recently reported in the literature [14]. Most of
them employed imidazolium-based ionic liquids and observed an improvement of the CNT dispersion within
the thermoplastic matrix and an increase of the electrical conductivity of the corresponding composites in
several orders of magnitude with the functionalization [15-20]. Very recently, our group decided to
investigate the role of alkyl-phophonium-based ionic liquid in thermoplastic systems loaded with CNT [21-
23]. Polystyrene loaded with 0.66 wt.% of CNT displayed conductivity values around 10 -5 S/m [21]. The
functionalization of CNT with trihexyl (tetradecyl) phosphonium-bistriflimide resulted in a significant
improvement of the filler dispersion and an increase of the conductivity by four orders of magnitude, reaching
values of around 10-1 S/m [21]. An increase of the conductivity with the CNT/IL system was also observed for
systems involving heterogeneous polymer blends as the matrices as polystyrene/ ethylene-vinyl acetate
copolymer blend [23] and polypropylene/polyamide 12 [22].

Conductive polymer composites are well studied as electromagnetic shielding materials due to the ability
of the conductive particle dispersed within a polymer matrix in interacting with the electromagnetic radiation
[24]. These interactions result in an attenuation of the radiation by reflection and/or absorption of the
incoming radiation. The former is very common for materials with high conductivity and results from the
interaction between mobile charge carriers (electrons or holes) and the radiation. The attenuation by
absorption occurs through interactions between electric or magnetic dipoles. These properties are of vital
importance due to the increasing use of sophisticated electronic equipments and telecommunication devices.
The EM radiation emitted by these equipments interferes on the performance of other electronic devices,
affecting their reliability, durability and safety. Other important application of these materials includes the
stealth technology, for military application. For this application, the material must attenuate the radiation
mainly by absorption. Some reports in the literature showed that the modification of CNT with ionic liquid
improves the electrical conductivity and electromagnetic interference shielding effectiveness (EMI SE) of
some polymeric composites [ 16,21,25]. Thus, the development of materials with tunable absorbing properties
in microwave region is of great interest.

Based on the profitable results obtained with the treatment of CNT with phosphonium-based IL, the aim of
the present work was to investigate the efficiency of this approach in polypropylene / PLA (PP/PLA) blends.
Although the literature presents some few works related to conducting composites based on PP/PLA loaded
with CNT, to the best of our knowledge, this is the first time that the non-covalently functionalized CNT was
used in this system. The effect of this new conductive system on the rheological, electrical and
electromagnetic shielding properties of PP/PLA composites was investigated by using a PP/PLA composition
of 70:30 wt.%. The morphology of the blends was also investigated by scanning electron microscopy and
transmission electron microscopy to explain the electrical conductivity and electromagnetic interference
shielding effectiveness of the corresponding composites.

4
EXPERIMENTAL

Materials

Polypropylene (PP) (CP442XP) (melt flow index = 6 g/10 min, 230 C/2.16 Kg; density = 0.895g cm-3)
was purchased from Brasken S.A (Brazil). Poli(lactic acid) (PLA) (Ingeo 3251D), was fabricated by Nature
Works LCC, USA (Mn = 80,000 – 90,000 g.mol-1; D-isomer content = 4%; density = 1.24 g cm-1) and
commercialized by Oeko Bioplásticos (Santa Catarina, Brazil). Trihexyl(tetradecyl)-phosphonium
bistriflimide (Ph-TFSI) as the ionic liquid (density = 1.07 g cm-1) was kindly supplied by Cytec Inc. MWCNT
(NC7000) was kindly supplied by Nanocyl (average diameter = 9.5 nm; average length = 1.5 µm; carbon
purity = 90%; surface area = 250–300 m2/g; density = 1.67 g cm-1).

Composite preparation

CNT was first dispersed in ionic liquid (Ph-TFSI) in a mortar for about 20 min, obtaining a black paste.
For the neat blends, PP and PLA as pellets were previously dried overnight at 70 C and introduced into the
W50 EHT internal mixer of a Brabender Plastograph equipped with roller rotors. The blends were
compounded at 190 ºC for 8 min at 60 rpm. The CNT-based composites were prepared under the same
processing conditions, by adding the CNT or the IL-CNT paste after 3 min of PP/PLA blending. The mixing
was performed for more five minutes. After this step, the materials were milled and injection-molded at 190
ºC with a pressure of 450 bar in a Haake mini-injector (miniJet model, Duisburg, Germany). The samples for
conductivity and rheological measurements were compression-molded at 190 ºC and 6 MPa for 5 min and
immediately cooled at the same pressure.

Characterization

Rheological measurements were performed in oscillatory mode, on a Physica MRC 302 rheometer from
Anton Paar, using the following conditions: parallel plates with 25 mm diameter and a gap of 1.0 mm; 200
°C; frequency range from 0.1 to 100 Hz and amplitude of 0.1 %, which is within the linear viscoelastic region.

Scanning electron microscopy was performed on a TESCAN (Vega 3 model) at 15 kV. The samples were
cryogenically fractured and the surface was treated with dichloromethane to selectively extract the PLA
phase. Then it was coated with thin layer of gold before analysis.

Solartron SI 1260 gain phase analyzer equipped with a Solartron 1296 dielectric interface was employed
to determine the AC electrical conductivity (AC) of the composites, in a frequency range from 0.1 Hz to 10
MHz. The measurements were made at 25 ºC, using electrodes with 25 mm diameter and oscillating voltage
of 5 V. Samples of 1 mm thickness were employed.

Transmission electron microscopy was obtained from a Tecnai Spirit from Fei Company, operating at 120
kV, localized at the Centro Nacional de Bioimagens- CENABIO/UFRJ (Brazil). The samples were cryo-
ultramicrotomed with thickness of 60-90 nm in a Leica equipment.

5
 Electromagnetic interference shielding effectiveness (EMI SE) as well as absorption measurements were
evaluated in 8.2 – 12.4 GHz, using a network analyzer N530L PNA-L from Agilent, equipped with
rectangular waveguide. Samples of 2 mm thickness were used for these experiments.

RESULTS AND DISCUSSION

Assessing the co-continuous composition

Preliminary PP/PLA neat blends were prepared with different PLA content to establish the co-continuous
composition. A common and efficient technique for estimating the co-continuous structure in a heterogeneous
polymer blend is through the selective extraction of one phase. Thus, PLA was selectively extracted from
PP/PLA blends, using dichloromethane. The results are summarized in Table 1. From these results it was
possible to infer that the PP/PLA (70:30 wt.%) blend presented co-continuous structure, since all PLA phase
was extracted without affecting the dimensional stability of the specimen. Therefore, this composition was
chosen for the studies involving the corresponding CNT-based nanocomposites.

The effect of ionic liquid on the AC electrical conductivity of the composites

Figure 1 compares the AC electrical conductivity (σAC) versus frequency for PP/PLA composites loaded
with different amounts of pristine CNT (pCNT) or physically functionalized CNT with ionic liquid (IL-CNT).
The composite containing 0.5 wt.% of pCNT displayed the σAC value of around 10-8 S/m at lower frequencies.
Beyond a frequency of around 300 Hz, the σAC increased with frequency, characterizing an electrical
conduction through hopping process. Increasing the amount of the filler increased the σ AC values. Moreover,
the DC conductivity plateau shifted to increased frequency. Samples with 1 wt.% of CNT or higher displayed
conductivity values frequency independent in all frequency range studied, which is typical of conducting
materials. The composite loaded with 1 wt.% of pCNT displayed conductivity values of 1.5 x 10 -3 S/m, which
is similar to those reported in the literature for PP-g-MA/PLA (50:50 w.t%) [10] and PP/PLA (40:60 wt%)
blends [12].
The previous functionalization of CNT with IL (IL-CNT) resulted in significant increasing in
conductivity. Composite with 0.3 wt.% of CNT in IL-CNT displayed a slight DC conductivity plateau at
lower frequency with a conductivity value around 10 -9 S/m. Increasing the amount of IL-CNT to 0.4 wt.%, the
conductivity jumped several orders of magnitude, reaching values of around 4 x 10 -3 S/m. At this CNT
concentration, the conductivity was completely frequency independent, characterizing a conductive
composite. For the composites containing CNT lower than 1 wt.%, the IL/CNT ratio was established as 5:1,
because this proportion was reported in other studies as ideal to provide better response in terms of
conductivity [15]. For the composites containing higher amount of CNT (3 and 5 wt.%), the amount of IL was
fixed in 5 wt.%, to avoid excessive amount of IL, which should be deleterious for the physical-mechanical
properties, as modulus and stiffness, besides increasing cost. Even with lower IL/CNT ratio, the conductivity
was significantly higher than those corresponding to the composites containing pCNT. Although PP/PLA
blend containing 5 wt.% of IL also displayed some conductivity (around 10 -7 S/m), the improvement of the

6
conductivity in IL-CNT – based composites was significant and should be also attributed to the
disaggregation of the CNT bundles promoted by the IL at the CNT surface, thus favoring the formation of the
conducting pathway with lower amount of filler. Furthermore, IL presents ionic conductivity and may act as a
bridge between the CNTs, favoring the electrical conduction.
The effectiveness of the previous functionalization of CNT with IL on the conductivity of CNT-based
thermoplastic composites prepared by melt mixing has been also reported in other studies. Table 2
summarizes some of these results. The conductivity values reached in the present system was comparable or
even superior to those reported in the literature, probably due to the co-continuous structure of the
heterogeneous PP/PLA blend, the selective location of CNT in one phase, the chemical nature of the matrix
and the ability of phosphonium-based IL in promoting an efficient debundling of the nanotube, resulting in a
good filler dispersion within the matrix.
The outstanding electrical properties of the composites containing IL-CNT can be clearly observed by
plotting the variation of σAC (at 1 Hz) against the filler content, as illustrated in Figure 2. The amount of the
filler was expressed in volume fraction. The insulating-conducting transition for the nanocomposites
containing pCNT occurred in the range of 0.003 whereas for those containing IL-CNT this transition occurred
sharply between 6 x 10-4 and 2 x 10-3 volume fraction of filler with a jump of the electrical conductivity of
about six orders of magnitude, reaching values of around 4 x 10 -3 S/m. Moreover, conductivity value as high
as 10.9 S/m with a volume fraction of CNT of 0.006 was achieved with the previous functionalization with
IL. These results confirm the importance of the functionalization with IL in improving the disaggregation of
CNT and the formation of the conducting pathway at lower filler content.

Rheological properties

Rheology is a powerful tool for investigating the microstructure of a nanocomposite due to the great
influence that the filler dispersion state as well as the filler-matrix interactions exerts on the main viscoelastic
properties of the nanocomposites in the melt state. Figure 3 illustrates the complex viscosity of PP/PLA/pCNT
and PP/PLA/IL-CNT nanocomposites with different amounts of fillers, as a function of the frequency. The
neat PP/PLA blend exhibited a slight shear thinning behavior (i.e. decrease of complex viscosity with
increasing in frequency) mainly at higher frequencies, which is typical of pseudo-plastic polymeric materials.
By adding increased amount of pCNT, the viscosity increased, mainly in low frequency region, up to a pCNT
concentration corresponding to 3 wt.% (1.77 vol.%). The shear-thinning effect also increased as the amount of
pCNT increased, which can be related to the formation of a three-dimensional structure of pCNT [29]. The
nanocomposite loaded with 5 wt.% of pCNT presented lower viscosity than that filled with 3 wt.% of pCNT.
This behavior may be due to a reaggregation process of the filler in the melt promoted by the higher filler
concentration.

The nanocomposites loaded with IL-CNT presented different behaviors, depending on the amount of filler
in the system. Those nanocomposites loaded with low amount of IL-CNT (0.1 – 0.3 wt.%) displayed lower
viscosity than that found for the neat polymer blend. This behavior was also reported in other studies
involving IL-CNT in thermoplastic matrices, which was attributed to the plasticizing/lubricating effect of the

7
ionic liquid [15]. Composites containing 0.4 wt.% of IL-CNT or higher displayed higher viscosity values at
low frequency range and an increasing of the shear-thinning behavior. These phenomena became more
pronounced as the amount of IL-CNT increased, until a proportion corresponding to 3 wt.% of IL-CNT. A
great difference in viscosity was observed when the amount of IL-CNT increased from 0.5 to 1.0 wt.%,
indicating the formation of the three dimensional network structure. These * values were significantly higher
than those found for the PP/PLA/pCNT nanocomposites with similar filler content, suggesting that ionic
liquid exerted great influence on the debundling degree of the CNT due to specific interactions, thus
promoting the formation of the three dimensional conducting network, which was responsible for the
improvement of the electrical conductivity and the lower percolation threshold of these nanocomposites.

The dependence of the storage modulus, G’, with the frequency for the PP/PLA composites loaded with
different amount of pCNT or IL-CNT is illustrated in Figure 4. In both systems, G’ increased with increasing
the amount of filler up to 3 wt.% of filler, mainly in the low frequency region, which is typical of particle-
filled polymers. The composites containing 5 wt.% of filler presented lower G’ values as compared with those
loaded with 3 wt.% of filler, following the same tendency related to the * behavior. The addition of low
amount of IL-CNT (up to 0.3 wt.%) caused a decrease in G’ over the entire measured frequency range when
compared with the neat blend due to the plasticizing/lubricating effect of the ionic liquid, as discussed before.
Beyond this amount of filler, the G’ significantly increased with the amount of filler, whose values were
higher than those observed for the composites loaded with similar amount of pCNT. Moreover, the slope of
the G’ curves at low frequency related to the composites containing IL-CNT higher than 0.4 wt.%
substantially decreased as the amount of IL-CNT increased, confirming the formation of a percolated network
structure [30]. According to these G’ plots, one can suggest that the rheological percolation threshold for the
PP/PLA/pCNT and PP/PLA/IL-CNT composites occurred in between 1 - 3 wt.% (0.006 – 0.017 vol. fraction)
and 0.4-1.0 wt.% (0.0024 – 0.006 vol. fraction), respectively. It is important to point out that the composites
loaded with higher amount of IL-CNT also contain higher amount of IL. Therefore, the higher G’ values and
lower slope of the G’ curves at low frequencies for the IL-CNT – based composites imply that the higher
dispersion state and debundling degree of CNT promoted by the IL at the CNT surface overcome the
plasticizing action of the IL itself, regarding the rheological properties.

The comparison of storage modulus (G’) and loss modulus (G’’) plots against the frequency also provides
important informations about the formation of the percolated structure of the filler within a polymer matrix.
Figure 5 compares the G’ and G’’ profiles of neat PP/PLA blend and some of the composites containing 0.5,
1.0 and 3.0 wt.% of filler. In all samples, G’ and G’’ increased with the frequency. At low frequency, the neat
blend and those loaded with 0.5 wt.% of filler exhibited G’’>G’, which is characteristic of liquid-like
behavior. At a specific frequency (cross-over frequency) G’ and G’’ values are similar and after this
frequency G’>G’’, indicating the transition to solid-like behavior. This cross-over point (G’=G’’) shifted
towards lower frequencies as the amount of filler increased, confirming the formation of the three dimensional
network structure. The system containing 0.5 wt.% of IL-CNT presented the cross-over at lower frequency
than that loaded with similar amount of pCNT. Furthermore, the G’ values of the composites containing more
than 1 wt.% of IL-CNT were higher than the G’’ values for all frequency range studied, indicating solid-like
behavior. This rheological behavior suggests that the improvement of the electrical conductivity for the

8
composites loaded with IL-CNT is due to an improvement of the CNT dispersion and the formation of denser
networked structure rather than the intrinsic ionic conductivity of the IL itself.

Morphology

The effect of the CNT-based fillers on the morphology of PP/PLA composites was investigated by SEM
micrograph, whose images are shown in Figure 6. These images were taken from the criofractured surface
previously etched with dichloromethane to selectively extract the PLA phase. The neat PP/PLA blend
presented a co-continuous structure (Fig 6a), confirming the results obtained from the selective extraction
experiments, discussed before (Table 1). The co-continuous structure was also observed for the composite
loaded with pCNT (Figure 6b and 6c). Nevertheless, the PLA phase (corresponding to the holes) was smaller.
The changes in the morphology with the addition of pCNT were already reported in the literature [23], and
were attributed to the change in the viscosity ratio between the blend components, due to the uneven
distribution of the filler within the phases of the heterogeneous blend. The addition of 1 wt.% of IL-CNT (Fig.
6e) resulted in an additional refinement of the morphology, which looks like sea-island morphology with PLA
phase as smaller domains. This behavior suggests that the IL at the CNT surface also played the role of
compatibilizing agent. Indeed, the morphology of PP/PLA blend loaded with 5 wt.% of IL (Fig 6d) displayed
PLA domains with smaller size, well adhered to the PP matrix. The compatibilizing action of this (Ph-TFSI) -
based ionic liquid was also suggested for the PP/polyamide -6 blends [31].

The presence of CNT is better observed for the composites with higher amount of filler. Figure 7 presents
the SEM micrographs of the non-extracted samples of the composites containing 3 wt.% of pCNT and IL-
CNT. The very small white points in these images are assigned to the CNT. These pictures suggest that the
CNT are mainly localized in the PP phase. This observation is in agreement with the extraction experiments.
In fact, after selectively extracted the PLA phase from the loaded composites with dichloromethane for one
week, the solvent remained colorless, indicating that the carbon nanotube was in the other phase, i.e., in the
polypropylene phase. Similar features were also reported by Lee et al [10].

The effect of the noncovalent functionalization of CNT on the filler dispersion in the composites was
investigated by TEM microscopy. Figure 8 compares the TEM images of the composites loaded with 1 wt.%
of pCNT and IL-CNT. The composite loaded with pCNT (Fig 8a) presented some CNT as aggregates,
whereas that containing IL-CNT displayed the CNT better dispersed within the matrix, confirming the
effectiveness of the IL as dispersing agent for the CNT.

Thermal properties

The thermal properties of PP/PLA composites were investigated by DSC analysis. Figure 9 compares the
DSC thermograms (second heating and cooling) of PP, PLA and the neat PP/PLA blend with those
corresponding to the systems loaded with pCNT (1 wt.%), IL-CNT (1 wt.%) and IL (5 wt.%). The second
heating curve of PLA displayed an exothermic peak at 95 ºC and an endothermic peak at 166 ºC,
corresponding to the cold crystallization temperature (T cc) and melting temperature (T m), respectively. Pure

9
PP presented a broad Tm peak at around 164 ºC. As the Tm of PLA and PP appears in the same region, this
event related to each phase cannot be observed in the blend and composites. The neat PP/PLA blend presented
a small Tcc peak (at 93 ºC) related to the PLA phase. This peak appeared slightly shifted towards lower
temperature, suggesting that the PP phase enhanced the cold crystallization of the PLA phase. On the other
hand, the addition of 5 wt.% of IL in the blend resulted in an increasing of the T cc, indicating that the IL
interferes on the cold crystallization. This phenomenon suggests an improvement of the compatibility between
the two phases as previously observed by SEM micrograph. Similar feature was observed by Bas and Dong in
PP/PLA system compatibilized with maleic-anhydride-grafted PP [32].The presence of pCNT or IL-CNT
prevented the cold crystallization of the PLA phase. This process is due to the slow crystallization of the PLA.
Thus, the absence of this event for the composites means that the filler contributes for accelerating the
crystallization process of the PLA phase in the composite.

The DSC cooling curves are presented in Figure 9B. PLA did not present any crystallization peak (T c) due
to its slow crystallization rate. The Tc of the pure PP appeared at 110 ºC. The crystallization of PP in the
PP/PLA blend occurred at 112 ºC, suggesting that the PLA exerts a slight nucleating effect on the PP phase.
This behavior was more accentuated by the addition of the fillers. Indeed, the presence of 1 wt.% of pCNT or
IL-CNT shifted the Tc towards 115 and 118 ºC, respectively. These results imply that CNT accelerated the
overall crystallization rate of the PP due to the nucleating effect of CNT [33]. Similar behavior was also
observed by Lee and Jeong for the PP-g-MA/PLA blends loaded with CNT and attributed to the selective
localization of CNT in the continuous PP matrix [10].

EMI SE

Electromagnetic interference shielding effectiveness (EMI SE) of a material consists of an attenuation of

the incoming electromagnetic (EM) radiation after going through this material. The total EMI SE (SET) is
measured in terms of scattering parameters, S11 and S12 when using a vector network analyzer, which evaluate
the reflected and transmitted radiation respectively [34]. The absorbed radiation by the material located in the
waveguide can be estimated by the difference between the incident (I), transmitted (T) and reflected (R)
radiations (A = I-T-R). Figure 10 compares the SET of the PP/PLA composites loaded with different amounts
of pCNT or CNT-IL. The total attenuation of radiation increased as the amount of filler increased, due to the
increasing in the amount of charge carrier and also electrical dipole. The composites containing CNT-IL
displayed higher attenuation of the radiation (lower SE values), mainly those prepared with 3 and 5 wt.% of
CNT. This behavior is due to increase of the concentration of mobile charge carrier and free ions promoted by
the interaction between the IL and the CNT surface. Although the sample with 3 wt.% of CNT-IL presented
high conductivity level (around 10 S/m), the EMI SE stayed in the range of -13 dB. This result suggests that
the IL interfere on the attenuation of the EM radiation. The long alkyl chain in the phosphonium-based IL
used in the present work should decrease the interaction of the radiation with the mobile ionic and electronic
species.

10
 The contribution of the reflection and absorption mechanism towards the total shielding effectiveness is
summarized in Table 3 for the data taken at 10 GHz. The contribution for the absorption mechanism was
larger for the composites loaded with CNT-IL. Nevertheless, the reflection increased as the amount of the
filler increased, as expected, due to the increase of the amount of mobile charge carrier, whose interaction
with the M radiation is preferentially by reflection.

CONCLUSION

Pristine CNT was non-covalently functionalized with alkylphosphonium-based ionic liquid and used to
prepare semi-biodegradable PP/PLA conducting composites. PP/PLA blend composition of 70:30 wt.% was
used, which was identified as a co-continuous structure. From the results obtained in the present study, it was
possible to conclude that a good conductivity level, of around 10-3 S/m with only 1 wt.% or 0.60 vol.%, can be
achieved by using the PP/PLA blend with co-continuous morphology. Moreover, the non-covalent
functionalization of CNT with the IL resulted in outstanding electrical conductivity with an increase of four
orders of magnitude, related to the composite with pCNT. This phenomenon was attributed to an
improvement of the CNT dispersion, which promotes the formation of the conducting pathway in higher
extent. The formation of physical conducting network promoted by the use of IL-CNT was formed with CNT
content higher than 1 wt.%, as indicated by the higher melt viscosity value for the composites loaded with IL-
CNT, when compared with those with pCNT. In fact, composites loaded with 1 wt.% or higher of IL-CNT
presented accentuated shear-thinning effect and significantly higher G’ values at low frequency range. From
SEM micrographs it was possible to suggest that the ionic liquid acted as a compatibilizing agent for the
blend, and as dispersing agent for the CNT, as indicated by a more refined morphology of composites
containing ionic liquid or IL-CNT. The presence of IL-CNT also accelerates the crystallization process of
PLA and also the melt crystallization of PP phase. This behavior implies that the filler may be preferentially
located within the PP phase, as indicated by extraction experiments, but also in the PLA phase. This feature
was also suggested by TEM micrographs, where CNT may be detected in both white and gray phases. The
presence of the conducting filler in the PP/PLA blend resulted in material with good electromagnetic
interference shielding effectiveness in the X-band range (8 – 12 GHz). Higher efficiency was observed for the
composites loaded with IL-CNT in a proportion of 3 and 5 w.%. The contribution of the attenuation by
absorption was higher for composites prepared with IL-CNT, which is important for stealth technology.
Finally, the improvement of the conductivity and EMI SE by using low amount of CNT physically modified
with ionic liquid opens new possibilities and enlarges the field of applications as conducting packaging
polymeric materials with semi-biodegradability characteristic for antistatic and microwave
shielding/absorbing applications with increased service life.

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Table 1. Selective extraction of PLA in injection-molded PP/PLA blends
Blend components (wt.%) Amount of extracted PLA continuity
PLA PLA (%) (%)
PP
10 0 0
90
20 9 45
80
30 30 100
70
40 39 100
60

Table 2. Conductivity values of CNT-thermoplastic systems assisted by ionic liquids

Polymer matrix CNT Ionic liquid type Conductivity (S/m) Ref.
Without IL With IL

1 Ph-TFSI 10-4 0.1 [21]

PS
1 Aminopropyl imidazol 10-5 10-4 [26]
PC/PVDF
1 Amino terminated imidazol 10-3 10-2 [25]
PVDF/ABS
2 bmimPF6 10-10 1.0 [15]
PMMA
1 bmimPF6 10-10 10-1 [27]
PMMA
Veim.BF4 10-3 10-1 [28]
PVDF
1 Ph-TFSI 5 x 10-1 25 x 10-1 [23]
PS/EVA
1 Bmim.TFSI 3 x 10-7 2 x 10-4 [22]
PP/PA12
1 Ph-TFSI 2 x 10-3 10 This work
PP/PLA

14
Table 3. Effect of the pCNT and CNT-IL on the absorbed, reflected and transmitted radiation at 10 GHz,
through PP/PLA (70:30 wt.%) composite samples.

CNT SE A R T A/R
content
(dB) (%) (%) (%)
(wt.%)

pCNT CNT-IL pCNT CNT-IL pCNT CNT-IL pCNT CNT-IL pCNT CNT-IL

0.5 -1.8 -3.7 18 32 15 25 67 43 1.2 1.28

0.75 -2.6 - 23 22 55 1.04

1.0 -3.2 -3.7 24 30 28 28 48 42 0.85 1.07

3.0 -7.7 -12.9 31 42 51 53 18 5 0.61 0.79

5.0 -7.2 -12.5 35 34 46 60 19 6 0.76 0.57

A: absorption; R : reflection; T : transmission power

15
Figure legends

Figure 1. AC electrical conductivity (σAC) versus frequency for PP/PLA composites loaded with different
amounts of pCNT or IL-CNT.

Figure 2. AC electrical conductivity at 1 Hz of PP/PLA composites as a function of the filler content.

Figure 3.Complex viscosity versus frequency for PP/PLA/pCNT and PP/PLA/IL-CNT nanocomposites as a
function of the filler content.

Figure 4. Storage modulus versus frequency for PP/PLA/pCNT and PP/PLA/IL-CNT nanocomposites with
different amounts of fillers

Figure 5. G’ and G’’ profiles of PP/PLA composites containing 0.5, 1.0 and 3.0 wt.% of filler.

Figure 6. SEM micrographs of PP/PLA neat blend (a) and the composites containing CNT/IL = 1/0 (b); 3/0
(c); 0/5 (d); 1/5 (e); 3/5 (f).

Figure 7. SEM micrographs of non extracted PP/PLA blends containing 3% of CNT (a) and 3% of IL-CNT
(b).

Figure 8. TEM micrographs of P/PLA composites loaded with 1 wt% of pCNT (a) and IL-CNT (b).

Figure 9. DSC curves (cooling and second heating scan) for the PP, PLA and their blends and composites

Figure 10. EMI SE of the PP/PLA composites (A) with CNT and B with IL-CNT, as a function of the filler
content.

16