Applied Clay Science 53 (2011) 188–194

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Applied Clay Science

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c l a y

Research Paper

Polylactide and carbon nanotubes/smectite-clay nanocomposites: Preparation,

characterization, sorptive and electrical properties
Saveria Santangelo a,⁎, Giuliana Gorrasi b, Roberta Di Lieto b, Salvatore De Pasquale c, Giovanni Patimo c,
Elpida Piperopoulos d, Maurizio Lanza e, Giuliana Faggio a, Francesco Mauriello a,
Giacomo Messina a, Candida Milone d
a
Dept. of Mechanics and Materials, University “Mediterranea”, Loc. Feo di Vito, I-89122 Reggio Calabria, Italy
b
Dept. of Chemical and Food Engineering, University of Salerno, via Ponte don Melillo, I-84084 Fisciano (Salerno), Italy
c
Dept. of Physics, University of Salerno, via Ponte don Melillo, I-84084 Fisciano (Salerno), Italy
d
Dept. of Industrial Chemistry and Materials Engineering, University of Messina, Contrada di Dio, I-98166 Messina, Italy
e
CNR, Inst. for Chemical Physical Processes, Messina Section, Salita Sperone, Contrada Papardo, Faro Superiore I-98158 Messina, Italy

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

Article history: In order to prepare polylactide nanocomposites, hybrid fillers were synthesized by direct growth of carbon
Received 3 June 2010 nanotubes over as-purchased and Na+-exchanged clay catalysts with 15 wt.% iron load. The sorptive and
Received in revised form 7 December 2010 electrical behavior of nanocomposites obtained by the incorporation of 1–5 wt.% filler was investigated.
Accepted 7 December 2010
Results show that polylactide nanocomposites are endowed with increased sorption and outstandingly
Available online 15 December 2010
enhanced conductivity (up to 6 or even 9 orders of magnitude) with respect to the pristine polymer
Keywords:
(σ = 1 · 10−10 S/m). The origin of these changes is discussed, and the synergistic action between nanotubes
Clay catalysts and clay is evidenced.
CNT growth © 2010 Elsevier B.V. All rights reserved.
CNT-clay hybrids
Polymer fillers
Electrical properties
Sorptive properties

1. Introduction
Biodegradable polymers have attracted increasing interest in funda-
mental research as well as in technological applications, due to their
potential in addressing environmental concerns and biomedical needs.
Biodegradable polymers break down in physiological environments by
macromolecular chain scission into smaller fragments, and ultimately
into simple, stable end products. The degradation may be due to aerobic
or anaerobic microorganisms, biologically active processes (e.g., enzyme
reactions) or passive hydrolytic cleavage. The last two decades of polymer
technology have seen a sharp rise in the development and commercial
marketing of such new materials (Doi and Steinbüchel, 2002; Nair and
Laurencin, 2007). Aliphatic polyesters are amongst the most important
biocompatible and biodegradable materials that have received increasing
attention. Their applications in conventional fields, such as agriculture,
packaging and fiber, and biomedical fields, e.g., tissue engineering,
surgical suture, gene therapy and controlled drug delivery, have grown
significantly due to the availability of novel products with better
performance (Doi and Steinbüchel, 2002; Ikada and Tsuji, 2000; Im
⁎ Corresponding author. Tel.: + 39 0965 875305; fax: + 39 0965 875201.
E-mail address: saveria.santangelo@unirc.it (S. Santangelo).
et al., 2005; Iwata and Doi, 1999; Misra et al., 2006; Nair and Laurencin,
2007).
Polylactide, obtained from the polymerization of lactic acid (2-
hydroxypropionic acid, CH3–CH(OH)–COOH), is also known as poly
lactic acid, PLA. It has recently entered worldwide in the market for use
as a biodegradable plastic. Due to the comparable mechanical properties
with standard thermoplastics such as polyethylene terephthalate (PET)
and polyvinyl chloride (PVC), PLA could represent a good candidate for
the replacement of petrochemical thermoplastics.
In this scenario, our idea arose of exploring the preparation of
novel biodegradable PLLA nanocomposites by the use of carbon
nanotubes (CNT) and clay as filler, and of evaluating how their mass
and electrical transport properties change with respect to the unfilled
polymer.
In the recent years, great attention has been devoted to hybrid
organic–inorganic systems and, in particular, to those in which
layered silicates are dispersed at nanometric level in a polymeric
matrix (Giannelis, 1996). Such nanohybrid composites possess very
unusual properties, quite different from their microscale counter-
parts. They often show improved mechanical and oxidation stability,
barrier properties, decreased solvent uptake, self-extinguishing
behavior and, eventually, tunable biodegradability (Le Baron et al.,
1999).

0169-1317/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2010.12.013
 S. Santangelo et al. / Applied Clay Science 53 (2011) 188–194
The use of clay minerals (Zhang et al., 2010) as fillers for polymer-
based nanocomposite production is widely reported (Pavlidoua and
Papaspyridesb, 2008; Zhou, 2010; Zhou et al., 2010). Clay minerals are
typical layered structures (Jiang et al., 2010; Tong et al., 2010) with
about 1 nm thick unit layers and sizes ranging from several nanometers
to several micrometers. Each layer is formed by tetrahedrally-
coordinated silicon atoms fused into an edge-sharing octahedral plane
of either alumina or magnesia. All the families of lamellar solids share
these characteristics, but the smectite clays and related layered silicates
are the most often used for polymer nanocomposite design for two
principal reasons. Firstly, they exhibit a very rich intercalation
chemistry, which allows them to be chemically modified and made
compatible with organic polymers for dispersal on a nanometer length
scale. Secondly, they occur ubiquitously in nature and can be obtained in
mineralogically pure form at low cost.
CNT have also been considered as polymer fillers because of their
extremely high mechanical strength and high electrical and thermal
conductivity (Baughman et al., 2002; Bernholc et al., 2002; Biercuk
et al., 2002; Dalton et al., 2003; Sandler et al., 1999).
In the light of these considerations, it can be reasonably expected
that the combined CNT–clay action would provide outstanding
functionalities to the resulting composite materials, provided that a
homogeneous dispersion of the filler into the polymer matrix is
reached (Choi et al., 2004; Fornes et al., 2004; Gorrasi et al., 2007a,b;
Kojima et al., 1993; Mitchell et al., 2002; Paiva et al., 2004; Sarno et al.,
2004; Zhu et al., 2004).
An attractive strategy for the achievement of this goal is represented
by the use of a new class of hybrid nanomaterials, consisting in CNT–clay
systems prepared by direct catalytic chemical vapor deposition (CCVD)
growth of CNT on the clay (Milone et al., 2010; Tsoufis et al., 2008).
This work addresses the development of novel PLA-based
nanocomposites endowed with improved performance. This was
accomplished thanks to the incorporation of CNT–clay hybrids into
poly-L-lactide containing about 4.0 mol% of D-lactoyl units (PDLLA). In
particular, the paper reports on the preparation and characterization
of both filler and resulting composite. The synthesis of filler was
carried out by direct CCVD growth over as-purchased and iron-loaded
smectite-type clay (muscovite) catalysts. Isobutane (i-C4H10) was
used as a cheap, non-toxic and highly reactive carbon source in the
CNT synthesis (Donato et al., 2009).
Morphological properties and crystalline quality of the synthesized
CNT were evaluated by means of scanning electron microscopy (SEM),
transmission electron microscopy (TEM) and Raman spectroscopy (RS).
Nanofillers were incorporated into PDLLA via high-energy ball milling
(HEBM). Structural organization of the obtained nanocomposite films
was evaluated by X-ray diffraction (XRD) and their physical properties
(electrical and barrier properties to water vapor) were correlated to the
composition and morphology of the filler.
2. Experimental
2.1. Materials
PDLLA supplied (in pellet form) by NatureWorks® PLA Polymer
2002D contained about 4.0 mol% of D-lactoyl units. It was reduced in
powder form by dissolving the pellets in acetone at reflux, and
precipitating using methanol as coagulating agent. The powders were
filtered under vacuum and kept at 40 °C in vacuum oven for three days.
CNT–clay nanofillers were synthesized by direct growth of CNT on
iron-loaded muscovite and sodium exchanged muscovite catalysts by
CCVD. The iron content was 15 g per 100 g of clay. Iron catalysts,
prepared by wet impregnation of purchased clay (Aldrich) and Na+-
exchanged clay, were named Fe/clay and Fe/Na+-clay, respectively.
After slowly drying at 80 °C, the catalysts were calcined at 450 °C in air
and reduced for 2 h under (60 cc/min) hydrogen flow at 500 °C.
189
The CCVD syntheses were carried out, in the presence of i-C4H10–
H2, at 700 °C. For this purpose, 0.5 g of reduced catalyst were placed in
a quartz boat inside the quartz reactor, located in a horizontal electric
furnace, and preliminarily heated up to synthesis temperature under
120 cc/min 1:1 He–H2 flow. Helium was then replaced with i-C4H10
keeping a constant flow ratio and total flow rate. The reactions were
stopped after 2 h and the raw products were subsequently cooled
down to room temperature in He atmosphere.
The weight percentage of C deposited was calculated as C (wt.%)=
100⋅(m−m0R)/m, where m is the mass of all the materials (reaction
products+catalyst) after synthesis and m0R is the mass of the catalyst
after reduction.
The hybrid nanofillers obtained from growing CNT over Fe/clay and
Fe/Na+-clay catalysts were named CNT–Fe/clay and CNT–Fe/Na+-clay,
respectively.
2.2. Nanocomposite preparation
In order to prepare PDLLA based nanocomposites with hybrid filler
loads varying in the range 1.0–5.0 wt.%, PDLLA and appropriate
amounts of powders of the synthesized nanofillers were milled in the
solid state. This was accomplished by using a Retsch centrifugal ball
mill (model PM100). Samples were milled for 1 h in a 50 cm3
cylindrical steel jar with 5 steel balls of 10 mm in diameter at a
rotation speed of 650 rpm. An additional PDLLA sample, milled in the
absence of fillers, was taken as the reference. Besides, in order to
clarify the role played by each component of the dual filler,
composites were prepared with fixed contents of either solely CNT
or solely exchanged/as-purchased nanoclay.
The PDLLA based nanocomposites and milled PDLLA were molded
in a hot press (Carver Inc.) at 170 °C to form 0.0250 ± 0.0050 mm
thick films.
2.3. Material characterization
2.3.1. Nanofiller
The morphology, dimensions and crystalline structure of the CNT,
obtained by SEM and HRTEM, were investigated after dissolution of
the support and iron particles by refluxing the hybrids obtained in a
mixture of 12% HCl and 12% HF acids. Finally, C deposits were washed
thoroughly with distilled water and dried at 110 °C for 3 h.
SEM analyses were performed using a JEOL JSM 5600LV operating
at 20 kV. Purified samples were examined, recording at least 20
different images with diverse magnification factors per specimen, in
order to have a reliable picture of their bulk.
HRTEM analyses were performed utilizing a JEOL JEM 2010, operating
at 200 kV and equipped with a Gatan 794 Multi-Scan CCD camera.
The crystalline quality was evaluated by measuring Raman
scattering excited by the 514.5 nm line of an Ar+ laser (Coherent
Innova 70). The analysis was carried out, at room temperature, in the
800–3350 cm− 1 spectral range by using a double monochromator
(Jobin Yvon Ramanor U-1000) equipped with a microscope (Olympus
BX40, X50 objective) and a photomultiplier (Hamamatsu R943-02)
operating in photon-counting mode. The use of a low laser-power
(3 mW at the sample surface) prevented annealing effects. In order to
reliably describe the sample bulk, several different locations in each
specimen were sampled on account of the possible structural non-
homogeneity. A 30 s long acquisition time was used to improve the S/N
ratio. After normalization and averaging, background was subtracted
and Lorentzian bands were used to reproduce the spectra. The
integrated-intensity ratios were then calculated.
2.3.2. PDLLA based nanocomposites
XRD measurements were performed utilizing a Brucker diffractom-
eter (equipped with a continuous scan attachment and a proportional
counter) with Ni-filtered Cu Kα radiation (λ = 1.54050 Å).
190 S. Santangelo et al. / Applied Clay Science 53 (2011) 188–194
Mass transport experiments (diffusion and sorption of water
vapor) were performed using a conventional Mc Bain spring balance
system, consisting of a glass water-jacketed chamber serviced by a
high vacuum line for sample degassing and penetrant removal (Felder
and Huvard, 1980). Inside the chamber, samples were suspended
from a helical quartz spring supplied by Ruska Industries Inc. with a
spring constant of 1.892 cm/mg. The temperature was controlled to
30 ± 0.1 °C by a constant temperature water bath. Before beginning
the sorption experiments, the sample was exposed to vacuum for at
least 24 h in order to remove previously adsorbed air gases and water
vapor from the polymer. Liquid penetrant was subjected to several
freeze–thaw cycles to remove dissolved gases. Then, the sample was
exposed to the penetrant at fixed pressures, and the spring position
was recorded as a function of time using a cathetometer. The spring
position data were converted to mass uptake data using the spring
constant. Diffusion coefficients and equilibrium mass uptake were
extracted from these kinetic sorption data. Each of the data presented
is averaged on three samples having the same nominal filler content.
The electrical conductivity was measured with a Keithley 6517A
electrometer unit in a two-probe resistance measurement configura-
tion. Films were 0.0250 ± 0.0050 mm thick (as determined by a
micrometer), about 10 mm wide and at least 50 mm long. The
electrical conductivity was measured in the voltage range from −10 V
to 10 V.
3. Results and discussion
3.1. Synthesis, morphology and crystalline quality of CNT
CCVD of isobutane on Fe/clay and Fe/Na+-clay catalysts led to
hybrids containing 53.3 wt.% and 58.1 wt.% of deposited carbon,
respectively.
Fig. 1. Morphology of carbonaceous products, as monitored by SEM (left side) and TEM (right side). The micrographs shown refer to reaction products obtained over catalysts Fe/clay
(a, b) and Fe/Na+-clay (c, d). White arrows highlight graphite platelets in SEM image of deposits obtained over catalysts Fe/clay.
SEM analysis of carbonaceous products evidences that graphite
platelets (highlighted with pointing arrows in Fig. 1a) are co-
produced over Fe/clay catalyst with filamentous structures, while
the selectivity towards the formation of filaments considerably
improves over Fe/Na+-clay catalyst (Fig. 1c), in agreement with results
previously obtained on K10 montmorillonite (Milone et al., 2010). TEM
analysis (Fig. 1b and d) reveals the hollow nature of the filaments.
CNTs grown over Fe/clay are highly entangled in bundles (Fig. 1b),
conversely those formed over Fe/Na+-clay are disaggregated (Fig. 1d),
smooth and straight and less defective. Their length is greater than
1 μm, while the outer diameter ranges between 15 − 40 nm, regard-
less of the type of catalyst.
The average crystalline quality of CNT was evaluated by
measuring Raman scattering. Fig. 2 shows the evolution of the
shape of the main spectral features: the graphite-like in-plane
optical mode at 1580 cm− 1 (G-band); the band at 1350 cm− 1,
originating from lattice defects (vacancies, pentagons, heptagons…)
that break the basic graphene-layer symmetry (D-band) (Cseria
et al., 1995; Dresselhaus et al., 2005) and its overtone at 2700 cm− 1
(G’-band) that, conversely, is detected only in the presence of
graphitic long-range order, i.e. in nanotubes constituted by a
sequence of smooth graphene sheets (Kim et al., 2003).
For a fixed excitation energy, G/D intensity ratio (IG/ID) intensifies
with increasing in-plane correlation length (Ferrari and Robertson,
2001a,b), i.e. mean inter-defect distance (Ferrari and Robertson,
2001a, Thomsen and Reich, 2000). Thus, it monitors the average size
of domains with graphitic order (LC = 4.4·IG/ID) (Tuinstra and
Koening, 1970). Instead, the G’/G intensity ratio (IG’/IG) is usually
regarded as an indicator of long-range order (Di Leo et al., 2007; Kim
et al., 2003). Therefore, the G’/D intensity ratio (IG’/ID) pictorially
describes the overall crystalline quality, which improves with
increasing mean inter-defect distance and/or smooth tube-wall

G Fe/Na+-clay
IG' /ID=2.43
LC=8.5nm
Intensity (arb.un.)
D carbon, while all peaks for the clay disappear. The same is the case for
1000 1500 2000 2500
Raman shift (cm-1)
Fig. 2. Raman spectra of the CNT obtained over Fe/clay and Fe/Na+-clay catalysts. For an
easier comparison of the mean CNT crystalline quality, as depicted by the G’/D intensity
ratio (IG’/ID), the spectra are normalized to the D-band intensity. The average size of
graphitic domains (LC) is also reported.
number, i.e. with increasing IG/ID and/or IG’/IG, respectively (Di Leo
et al., 2007; Donato et al., 2009).
The results of spectra decomposition fully confirm the evidence
provided by electron microscopy analyses (Fig. 1). The crystalline
quality of CNT grown over the catalyst Fe/Na+-clay is largely higher
than that of CNT grown over Fe/clay: IG’/ID increased from 0.3 to 2.4
(Fig. 2). This is due to the remarkable smoothening of graphene sheets
(IG’/IG increased from 0.5 to 1.3) and to the sizable development of
graphitically ordered domains (LC increased from 2.9 nm to 8.5 nm).
Indeed, the overall degree of graphitization of the CNT synthesized
over Na+-exchanged clay is the highest ever reported for CNT grown
over similarly supported Fe-catalysts (Tsoufis et al., 2008). It largely
exceeds also than that of the CNT obtained over Fe-catalysts
supported on silica or alumina (Donato et al., 2009).
3.2. Structure of CNT-clay hybrids and PDLLA-nanocomposites
Fig. 3 displays the XRD spectra of the Fe/clay catalysts (Fig. 3a) and
CNT–Fe/clay hybrid (Fig. 3b). In the range of 2θ investigated Fe/clay
Intensity (a.u.)
5 10 15 20 25
2θ (deg.)
Fig. 3. XRD patterns of (a) fresh Fe/clay catalysts and (b) material discharged from the
reactor after CNT synthesis. Symbols: (●) muscovite; (♦) quartz; (★) carbon.
S. Santangelo et al. / Applied Clay Science 53 (2011) 188–194 191
sample shows several peaks at 8.9°, 17.8°, 19.5° and 26.5° (Fig. 3a)
Fe/clay
assigned to the 001 (10.1 Å), 002 (5.04 Å), 020 (4.49 Å) and 003
IG' /ID=0.30 (3.36 Å) reflections of muscovite, respectively. The presence of a peak
LC=2.9nm at 21° indicates the presence of quartz impurities in the mineral. The
diffraction pattern of the samples of Fe/Na+-clay (not shown for
brevity) does not significantly differ from that of un-exchanged clay.
G'
The XRD powder spectrum of the hybrid CNT-clay systems
(Fig. 3b) shows only a broad peak at 2θ = 24°, typical of graphitic
CNT-Fe/Na+-clay. Since the amount of clay in the hybrids is only
slightly lower with respect to the amount of CNT (46.7 wt.% and
41.9 wt.% for CNT–Fe/clay and CNT–Fe/Na+-clay, respectively), the
disappearance of the clay peaks might be due to its complete
exfoliation upon CNT growth, with consequent dramatic reduction
of the crystallite size.
3000 Fig. 4 shows the XRD spectra of films of pure PDLLA and of PDLLA
filled with 3.0 wt.% of CNT–Fe/clay and CNT–Fe/Na + -clay,
as representatives of all the PDLLA-nanocomposites. The non-
detection of the graphitic carbon peak might be due to there being
an insufficient amount for analytical purposes. The presence of
a broad XRD peak in all the spectra demonstrates that the polymer
has an amorphous structure, on which the incorporation of
nanofiller, regardless of its concentration, does not induce relevant
changes. As known, the optical isomer ratio (Levo/Dextro) of the
lactide monomers has a large impact on the PLA crystallization
properties. The presence of about 4.0 mol% of D-lactoyl units in the
investigated polymer significantly lowers its crystallization ability,
leading, under the processing-conditions considered (namely, a
high melt-cooling rate), to an amorphous structure, hardly changed
by the filler addition.
3.3. Physical properties of PDLLA-nanocomposites
3.3.1. Transport properties (sorption and diffusion) of water vapor
Composites are multiphase systems in which the coexistence of
phases with different permeabilities can cause complex transport
phenomena. When only one phase is permeable to the penetrant or
shows a much higher permeability than the other phases, one can
assume that transport only occurs in this phase. In semi-crystalline
polymers, the crystalline regions are considered to be impermeable to
the vapor molecules, whereas the amorphous phase (as the PDLLA
matrix) is supposed to have the same specific sorption capability,
irrespective of the extent of impermeable phases.
b
Intensity (a.u.)
b
a
a
30 35 40 5 10 15 20 25 30 35 40
2 θ (deg.)
Fig. 4. XRD patterns of (a) molded PDLLA, (b) PDLLA–CNT–Fe/clay and (c) and PDLLA–
CNT–Fe/Na+-clay. Filler loading of the nanocomposites is 3 wt.%.
192 S. Santangelo et al. / Applied Clay Science 53 (2011) 188–194
By measuring the relative increase of weight, undergone with time
by samples exposed to the water vapor at a given partial pressure, it is
possible to infer the equilibrium concentration of sorbed vapor, Ceq
(gs/100gp), where gs stands for grams of sorbed vapor and gp stands
for grams of polymeric sample. Fig. 5 displays the isotherms of water
vapor sorption as a function of vapor activity (awv = P/P0, P and P0
being respectively the vapor pressures of water and pure water at the
same temperature) for pure PDLLA, for PDLLA loaded with 3.0 wt.% of
CNT–Fe/clay (~ 1.3 wt.% Fe/clay) and CNT–Fe/Na+-clay (~1.3 wt.% Fe/
Na+-clay), and with 1.3 wt.% of Fe/clay and Fe/Na+-clay (no CNT). An
exponential increase is observed in the isotherms of all the samples
(Flory–Huggins behavior), indicating a preference for the formation of
penetrant–penetrant pairs.
Since XRD analysis demonstrates that filler addition does not
significantly alter the amorphousness of the polymeric host matrix,
the water vapor sorption capability of PDLLA nanocomposites should
be similar to that of unfilled polymer. Instead, at any vapor activity,
pure PDLLA exhibits smaller Ceq values than all the investigated PDLLA
nanocomposites. CNT being notoriously hydrophobic, this is thought
of to be the effect of the hydrophilic clay.
If the clay alone is utilized as a filler, the type of clay chosen is
unimportant, because the isotherms of PDLLA–Fe/clay and PDLLA–Fe/
Na+-clay are almost coincident. On the contrary, the comparison between
the isotherms of PDLLA–CNT–Fe/clay and PDLLA–CNT–Fe/Na+-clay
shows that when a hybrid CNT–clay filler is utilized, the type of clay
utilized becomes influential at higher activities (awv N 0.6), CNT–Fe/Na+-
clay favoring, while CNT–Fe/clay hampers the water sorption relative to
the corresponding sole-clay filler.
With no data concerning the distribution of the considered fillers
being presently available, we can only speculate that a different
dispersion of the hydrophilic component within the host matrix
might be the origin of the difference observed.
In the case of Fickian behavior, which is a linear dependence of
sorption on square root of time t (s), it is possible to derive the mean
diffusion coefficient, D (cm2/s). D is calculated
pffiffi from the linear part of
the reduced sorption curve, Ct/Ceq vs. t according to
rffiffiffiffiffiffi
Ct 4 Dt
= ;
Ceq τ π
where Ct is the instantaneous penetrant concentration and τ (cm) is
the thickness of the sample. For many polymer–solvent systems D
1,2 PDLLA
PDLLA-Fe/clay
1,0 PDLLA-CNT-Fe/clay
+
PDLLA-Fe/Na -clay
Ceq (gs/100gp)
+ 6
0,8 PDLLA-CNT-Fe/Na -clay
0,6
0,4
0,2
0,0
0,0 0,2 0,4 0,6 0,8
awv
Fig. 5. Isotherms of water vapor sorption for pristine polymer and nanocomposites
filled with 3.0 wt.% of CNT–Fe/clay (~1.3 wt.% Fe/clay) and CNT–Fe/Na+-clay (~1.3 wt.%
Fe/Na+-clay), and with 1.3 wt.% of Fe/clay and Fe/Na+-clay.
depends on concentration. This dependence can be generally
expressed through the empirical law (Vieth and Amini, 1974)
 
D = D0 exp γCeq ;
where D0 is the thermodynamic zero-concentration diffusion coeffi-
cient, relative to the condition Ceq = 0, and γ is the concentration
coefficient. Both these parameters are related to the fractional free
volume and hence to the mobility of the sorbing phase (Crank, 1956).
Therefore, they are useful, as widely demonstrated (Fujita, 1961;
Gorrasi et al., 2003, 2005; Vieth and Amini, 1974), in providing
information on the thermodynamic state of the permeable phase.
Since all the samples showed a Fickian behavior during the
sorption of water vapor at different activities, the average diffusion
coefficient was derived following Eq. (1). Fig. 6 displays the obtained
dependence of D on the concentration of sorbed water for pure PDLLA
and PDLLA loaded with 3.0 wt.% of CNT–Fe/clay (~1.3 wt.% Fe/clay)
and CNT–Fe/Na+-clay (~ 1.3 wt.% Fe/Na+-clay), and with 1.3 wt.% of
Fe/clay and Fe/Na+-clay (no CNT). Regardless of the kind of added
filler, pure PDLLA exhibits higher thermodynamic diffusion coeffi-
cients than PDLLA nanocomposites.
Since the filler addition does not substantially change the
amorphousness of the PDLLA matrix, the amount of permeable
phase and its thermodynamic state can be considered the same in all
the samples. Thus, the decrease can be attributed only to the reduced
mobility of polymer chains, thus to the decrease of fractional free
volume owing to the presence of filler.
The similarity between results obtained for PDLLA–Fe/clay and
PDLLA–Fe/Na+-clay indicates that the type of clay chosen is not
influential if the clay alone is utilized as filler. In contrast, lower D
values are obtained for PDLLA–CNT–Fe/Na+-clay than for PDLLA–
CNT–Fe/clay, revealing that the kind of clay utilized indirectly affects
the water diffusion. With the filler distribution being presently
unknown, we can only speculate that the difference observed in the
case of hybrids might be due to better dispersion and development of
a three-dimensional (3D) CNT–Fe/Na+-clay network, hampering, to a
ð1Þ greater extent than CNT–Fe/clay, the mass transport within the
permeable polymeric medium, particularly at smaller sorbed water
concentrations.
10
PDLLA
9 PDLLA-Fe/clay
PDLLA-CNT-Fe/clay
8 +
PDLLA-Fe/Na -clay
+
7 PDLLA-CNT-Fe/Na -clay
D (10-12 m2/s)
5
4
3
2
1
0,0 0,2 0,4 0,6 0,8 1,0 1,2
1,0 Ceq (gs/100gp)
Fig. 6. Diffusion coefficients (D), as a function of the equilibrium concentration for water
vapor sorption (Ceq), for pristine polymer and nanocomposites filled with 3.0 wt.% of CNT–
Fe/clay (~1.3 wt.% Fe/clay) and CNT–Fe/Na+-clay (~1.3 wt.% Fe/Na+-clay), and with
1.3 wt.% of Fe/clay and Fe/Na+-clay.
 S. Santangelo et al. / Applied Clay Science 53 (2011) 188–194 193

3.3.2. Electrical properties
Although electrical measurements evidence the non-linearity of the
I–V characteristics, especially at low applied voltages, Va (V), a straight
line reproduces the I–V curve well around Va = 10 V. Correspondingly, a
current Im (A) is measured. Such values were used to calculate the
conductivity, σ (S/m), of the nanocomposites loaded with CNT–Fe/clay
and CNT–Fe/Na+-clay by the use of the relationship
L 1 L Im
σ= = ;
Wτ R Wτ Va
where τ (m), W (m) and L (m) denote respectively thickness, width
and length of the specimens and R (Ω) = Va/Im is their resistance.
Fig. 7 displays the calculated σ values vs. the filler content. As can
be seen, both the fillers brought about outstanding changes in the
electric properties. Upon addition of CNT-clay hybrids, the insulating
(σ = 1·10−10 S/m) polymer matrix assumes conductivity values close
to semi-conductive materials. Contrarily, upon addition of the sole
iron-loaded clay (not shown), PDLLA maintains its insulating
properties. Since iron-loaded clay, alone, does not modify the
electrical behavior of the polymer, it is argued that CNTs are fully
responsible for the sizable conductivity enhancement observed in
nanocomposites, as expected.
The data shown in Fig. 7 prove that the nature and amount of the
filler strongly influence the electrical behavior of nanocomposites.
PDLLA–CNT–Fe/Na+-clay nanocomposites show a semiconductive
behavior already for filler loading higher than 1 wt.%, while a higher
loading (N2.5 wt.%) is required when CNT–Fe/clay is added to PDLLA. At
the highest filler content (5 wt.%), the use of CNT–Fe/clay leads to a
conductivity enhancement of 6 orders of magnitude (σ = 6·10−4 S/m),
while an increase of about 9 orders of magnitude is achieved with CNT–
Fe/Na+-clay (σ = 2·10−1 S/m).
According to the traditional percolation theory (Deutsher, 1984),
the electrical conductivity of electronic composites can be analytically
described by the equation
 β
σc = σ0 x–xp ; for x N xp
where β is the critical exponent generally reflecting the dimension-
ality of the system, x (wt.%) is the weight fraction of conductive filler,
xp (wt.%) is the percolation threshold (i.e. the minimum weight
fraction of conductive filler that effectively modifies the conductivity)
and σ0 (S/m) is a parameter that basically depends on the electrical
conductivity of the filler.
1
+ Differing from each other substantially for the presence of
0,1 PDLLA-CNT-Fe/Na -clay
0,01 σ =4.4 10 ( -1.35)
-3 3.0
1E-3
1E-4
σ (S/m)
By fitting experimental conductivity data to the function (2) we
obtained the values of xp, σ0 and β reported in Fig. 7. The remarkably
higher degree of graphitization of CNT grown on sodium-exchanged
clay (IG’/ID = 2.4 against IG’/ID = 0.3 for CNT synthesized on un-
exchanged clay) explains their higher conductive character. In turn,
this accounts for the enhancement by almost 2 orders of magnitude in
σ0 (from 9.6 · 10−5 S/m to 4.4 · 10−3 S/m).
As for the difference in exponent β, the value of 3 obtained for
PDLLA–CNT–Fe/Na+-clay is likely to reflect the availability of a
continuous 3D network (as proposed in sub-sect. 3.3.1) for electric
transport. Instead, the value obtained for PDLLA–CNT–Fe/clay (1.3)
closely reflects the one-dimensional character of CNT, thus suggesting
that conduction is limited by tunneling through potential barriers
between conductive regions (Deng et al., 2009a,b).
A larger CNT content of the filler (58.1 wt.% against 53.3 wt.%) and,
principally, better CNT conductive properties (and the likely existence
of a continuous conducting network) account for the lower percola-
tion threshold of PDLLA–CNT–Fe/Na+-clay (1.35 wt.%) with respect to
PDLLA–CNT–Fe/clay (2.80 wt.%).
3.3.3. Influence of clay on the electrical properties and advantages in
using hybrid fillers
From the above discussion it comes out that the incorporation of
hybrid clay-based filler upgrades the electric properties of the
insulating pristine polymer, rendering PDLLA semiconductive. How-
ever, the extent of improvement obtainable depends on the type of
clay chosen. In fact, graphitization level and morphology of the CNT
grown, which, affecting conductivity and possibly dispersion degree
of the filler, are critical parameters for the electric properties of
PDLLA-based composites, vary sizably with the choice of clay.
In order to shed further light on the role of clay, a further aspect has
to be considered. Provided that the addition of clay has no direct
influence on the electric behavior of the polymer-based nanocomposite,
a question arises spontaneously: is the presence of clay really essential?
In principle, one can envisage using the clay exclusively during the step
of CNT growth – choosing the type of clay to allow obtaining well-
crystallized (highly conductive), straight and disaggregated (easy to
ð2Þ
disperse) CNT – and to subsequently remove it, so as to finally
incorporate the sole conductive component of the filler (CNT). If it
were so, a marked simplification to the process might derive from the
use of high quality commercial CNT. In order to answer the above
question, two PDLLA composites were considered containing the same
amount of CNT synthesized through the same reaction: PDLLA–CNT–Fe/
Na+-clay with 3.0 wt.% of CNT–clay (~1.7 wt.% CNT), obtained by
incorporation of as-grown CNT–Fe/Na+-clay hybrid, and PDLLA loaded
with 1.7 wt.% of CNT that, after synthesis, have been detached from the
Fe/Na+-clay catalyst by treatment with HCl/HF mixture.
(electrically inactive) clay, the two composites should have comparable
conductivities. Instead, the measured σ values were 1.62·10−1 S/m and
9.00·10−5 S/m for PDLLA–CNT–Fe/Na+-clay and PDLLA–CNT, respec-
tively. With the same CNT having been used, the remarkable diminish-
ing of conductivity observed can be understood only as the result of the

1E-5 poorer dispersion into PDLLA of the CNT separated from the clay
1E-6 PDLLA-CNT-Fe/clay catalyst-support. This finding proves that clay and CNT exert a
synergistic action in upgrading the polymer electric properties. Although
σ =9.6 10 ( -2.80)
1E-7 -5 1.3
indirect, the influence that the clay has on the composite conductivity
1E-8 renders its presence in the filler as essential. This justifies the complexity
1E-9 of the process followed for the preparation of nanocomposites based on
CNT/clay hybrids.
1E-10
The smaller changes in electric properties obtained by simpler
0 1 2 3 4 5 processes further reinforce this conclusion. For instance, in P3OT-SWCNT
composites (Kymakys et al., 2002), prepared by dispersing powders of
Filler loading (wt.%)
commercial single-walled carbon nanotubes and commercial poly(3-
Fig. 7. Electrical conductivity (σ) of PDLLA nanocomposites as a function of the filler octylthiophene) in chloroform or toluene, an increase of conductivity is
loading. The functions fitting the experimental data are also reported. achieved of 5 orders of magnitude with respect to the pure P3OT
194 S. Santangelo et al. / Applied Clay Science 53 (2011) 188–194
(σ= 1·10−8 S/m). Note that, although conductivity of the pristine P3OT
is 2 orders of magnitude higher than that of pure PDLLA, such variation is
smaller than that presently obtained by using the (less performing) CNT–
Fe/clay filler. In addition, the content of SWCNT needed to produce the
change is largely greater – 35 wt.% against ~3 wt.% of MWCNT (contained
in 5 wt.%-loaded nanocomposites) – than that able to produce variations
of 6 or even 9 orders of magnitude here.
4. Conclusion
Nanocomposites, based on biodegradable PDLLA, were prepared
by HEBM incorporation of hybrid CNT–Fe/clay and CNT–Fe/Na+-clay
fillers, synthesized by direct CCVD growth of CNT over clay-based
catalysts, and their sorptive and electrical behavior was investigated.
Results show that PDLLA-composites are endowed with improved
properties with respect to the pristine polymer. The increase of water
vapor sorption capability in PDLLA-composites is primarily due to the
hydrophilic component (clay) of the filler, whereas the conductive
component (CNT) is chiefly responsible for the sizable conductivity
enhancement (6–9 orders of magnitude) with respect to the insulating
PDLLA (σ = 1·10−10 S/m). Nonetheless, the results obtained suggest
that clay and CNT exert a synergistic action in improving the polymer
properties.
PDLLA–CNT–Fe/Na+-clay exhibited better performance than
PDLLA–CNT–Fe/clay. On the basis of indications emerging from the
systematic investigation of hybrids by SEM, TEM, XRD and RS, such a
difference is understood as the effect of the larger degree of
graphitization and the minor level of bundling of the CNT formed
over Fe/Na+-clay. The latter factor might be responsible for a different
degree of dispersion of the CNT–Fe/Na+-clay filler within the PDLLA
matrix. Further analyses are however needed to test this hypothesis.
References
Baughman, R.H., Zakhidov, A.A., de Heer, W.A., 2002. Carbon nanotubes—the route
toward applications. Science 297, 787–792.
Bernholc, J., Brenner, D., Nardelli, M.B., Meunier, V., Roland, C., 2002. Mechanical and
electrical properties of nanotubes Ann. Rev. Mater. Res. 32, 347–375.
Biercuk, M.J., Llaguno, C., Radosavljevic, J.K., Yun, A., Johnson, T., Fischer, J.E., 2002. Carbon
nanotube composites for thermal management. Appl. Phys. Lett. 80, 2767–2769.
Choi, Y.S., Ham, H.T., Chung, I.J., 2004. Effect of monomers on the basal spacing of
sodium montmorillonite and the structures of polymer-clay nanocomposites.
Chem. Mater. 16, 2522–2529.
Crank, J., 1956. The mathematics of diffusion, ed. Oxford University, London.
Cseria, T., Békássy, S., Figueras, F., Cseke, E., de Menorval, L.C., Dutartre, R., 1995.
Characterization of clay-based K catalysts and their application in Friedel–Crafts
alkylation of aromatics. Appl. Cat. A. 132, 141–155.
Dalton, A.B., Collins, S., Muñoz, E., Razal, J.M., Ebron, V.H., Ferraris, J.P., Coleman, J.N.,
Kim, B.G., Baughman, R.H., 2003. Super-tough carbon-nanotube fibers. Nature 423,
703.
Deng, H., Skipa, T., Zhang, R., Lellinger, D., Bilotti, E., Alig, I., Peijs, T., 2009a. Effect of
melting and crystallization on the conductive network in conductive polymer
composites. Polymer 50, 3747–3754.
Deng, H., Zhang, R., Bilotti, E., Loos, J., Peijs, T., 2009b. Conductive polymer tape
containing highly oriented carbon nanofillers. J. Appl. Polym. Sci. 113, 742–751.
Deutsher, G., 1984. Percolation and Superconductivity. Plenum, New York.
Di Leo, R., Landi, B.J., Raffaelle, R.P., 2007. Purity assessment of multiwalled carbon
nanotubes by Raman spectroscopy. J. Appl. Phys. 101, 64307–64311.
Doi, Y., Steinbüchel, A., 2002. Polyester III. Applications and Commercial Products.
Wiley-VCH, Weinheim.
Donato, M.G., Galvagno, S., Lanza, M., Messina, G., Milone, C., Piperopoulos, E., Pistone,
A., Santangelo, S., 2009. Influence of carbon source and Fe-catalyst support on the
growth of multi-walled nanotubes. J. Nanosci. Nanotechnol. 9, 3815–3823.
Dresselhaus, M.S., Dresselhaus, G., Saito, R., Jorio, A., 2005. Raman spectroscopy of
carbon nanotubes. Phys. Rep. 409, 47–99.
Felder, R.M., Huvard, G.S., 1980. Methods of Experimental Physics. Academic Press, New York.
Ferrari, A.C., Robertson, J., 2001a. Interpretation of Raman spectra of disordered and
amorphous carbon. Phys. Rev. B. Condens. Matter. Mater. Phys. 61, 14095–14107.
Ferrari, A.C., Robertson, J., 2001b. Resonant Raman spectroscopy of disordered,
amorphous, and diamond like carbon. Phys. Rev. B Condens. Matter. Mater. Phys.
64, 75414–75426.
Fornes, T.D., Hunter, D.L., Paul, D.R., 2004. Nylon-6 nanocomposites from alkylammo-
nium-modified clay: the role of alkyl tails on exfoliation. Macromolecules 37,
1793–1798.
Fujita, H., 1961. Diffusion in polymer–diluent systems. Adv. Polym. Sci. 3, 1–47.
Giannelis, E.P., 1996. Polymer layered silicate nanocomposites. Adv. Mater. 8, 29–35.
Gorrasi, G., Tortora, M., Vittoria, V., Pollet, E., Lepoittevin, B., Alexandre, M., Dubois, P.,
2003. Vapor barrier properties of polycaprolactone montmorillonite nanocompo-
sites: effect of clay dispersion. Polymer 44, 2271–2279.
Gorrasi, G., Tortora, M., Vittoria, V., 2005. Synthesis and physical properties of layered
silicates/polyurethane nanocomposites. J. Polym. Sci. B Polym. Phys. 43, 2454–2467.
Gorrasi, G., Sarno, M., Di Bartolomeo, A., Sannino, D., Ciambelli, P., Vittoria, V., 2007a.
Incorporation of carbon nanotubes into polyethylene by high energy ball milling:
morphology and physical properties. J Polym. Sci B Polym. Phys. 45, 597–606.
Gorrasi, G., Romeo, V., Sannino, D., Sarno, M., Ciambelli, P., Vittoria, V., De Vivo, B., Tucci,
V., 2007b. Carbon nanotube induced structural and physical property transitions of
syndiotactic polypropylene. Nanotechnology 18, 275703–275714.
Ikada, Y., Tsuji, H., 2000. Biodegradable polyesters for medical and ecological
applications. Macromol. Rapid Commun. 21, 117–132.
Im, S.S., Kim, Y.H., Yoon, J.S., Chin, I.J., 2005. Bio-based Polymers: Recent Progress.
Wiley-VCH, New York.
Iwata, T., Doi, Y., 1999. Crystal structure and biodegradation of aliphatic polyester
crystals. Macromol. Chem. Phys. 200, 2429–2442.
Jiang, G.F., Zhou, C.H., Xia, X., Yang, F.Q., Tong, D.S., Yu, W.H., Liu, S.M., 2010. Controllable
preparation of graphitic carbon nitride nanosheets via confined interlayer nano-
space of layered clays. Mater. Lett. 64, 2718–2721.
Kim, Y.A., Hayashi, T., Osawa, K., Dresselhaus, M.S., Endo, M., 2003. Annealing effect on
highly disordered multi-wall carbon nanotubes. Chem. Phys. Lett. 380, 319–324.
Kojima, Y., Usuki, A., Kawasumi, M., Okada, A., Fukushima, Y., Kurauchi, T., Kamigaito, O.,
1993. Mechanical properties of nylon 6-clay hybrid. J. Mater. Res. 8, 1185–1189.
Kymakys, E., Alexandrou, I., Amaratunga, G.A.J., 2002. Single-walled carbon nanotube-
polymer composites: electrical, optical and structural investigation. Synth. Met.
127, 59–62.
Le Baron, P.C., Wang, Z., Pinnavaia, T., 1999. Polymer layered silicate nanocomposites:
an overview. Appl. Clay Sci. 15, 11–29.
Milone, C., Manikandan, D., Santangelo, S., Lanza, M., Galvagno, S., Messina, G., 2010.
K10 montmorillonite based catalysts for the growth of multiwalled carbon
nanotubes through catalytic chemical vapor deposition. Ind. Eng. Chem. Res. 49,
3242–3249.
Misra, S.K., Valappil, S.P., Roy, I., Beccaccini, A.R., 2006. Polyhydroxyalkanoate (PHA)/
inorganic phase composites for tissue engineering applications. Biomacromolecules 7,
2249–2258.
Mitchell, C.A., Bahr, J.L., Arepalli, S., Tour, J.M., Krishnamoorti, R., 2002. Dispersion of
functionalized carbon nanotubes in polystyrene. Macromolecules 35, 8825–8830.
Nair, L.S., Laurencin, C.T., 2007. Biodegradable polymers as biomaterials. Prog. Polym.
Sci. 32, 762–798.
Paiva, M.C., Zhou, B., Fernando, K.A.S., Lin, Y., Kennedy, J.M., Sun, Y.P., 2004. Mechanical
and morphological characterization of polymer–carbon nanocomposites from
functionalized carbon nanotubes. Carbon 42, 2849–2854.
Pavlidoua, S., Papaspyridesb, C.D., 2008. A review on polymer-layered silicate
nanocomposites. Prog. Polym. Sci. 33, 1119–1198.
Sandler, J.P., Shaffer, M.S., Prasse, T., Bauhofer, W., Schulte, K., Windle, A.H., 1999.
Development of a dispersion process for carbon nanotubes in an epoxy matrix and
the resulting electrical properties. Polymer 40, 5967–5971.
Sarno, M., Gorrasi, G., Sannino, D., Sorrentino, A., Ciambelli, P., Vittoria, V., 2004.
Polymorphism and thermal behavior of syndiotactic poly(propylene)/carbon
nanotube composites. Macromol. Rapid Comm. 25, 1963–1967.
Thomsen, C., Reich, S., 2000. Double resonant Raman scattering in graphite. Phys. Rev.
Lett. 85, 5214–5217.
Tong, D.S., Zhou, C.H., Ming Yan Li, M.Y., Yu, W.H., Beltramini, J., Lin, C.X., Xu, Z.P., 2010.
Structure and catalytic properties of Sn-containing layered double hydroxides
synthesized in the presence of dodecylsulfate and dodecylamine. Appl. Clay Sci. 48,
569–574.
Tsoufis, T., Jankovic, L., Gournis, D., Trikalitis, P.N., Bakas, T., 2008. Evaluation of first-
row transition metal oxides supported on clay minerals for catalytic growth of
carbon nanostructures. Mater. Sci. Eng. B. 152, 44–49.
Tuinstra, F., Koening, J.L., 1970. Raman spectrum of graphite. J. Chem. Phys. 53, 1126–1130.
Vieth, W.R., Amini, M.A., 1974. Permeability of plastic films and coatings. In:
Hopfenberg, H.B. (Ed.), Permeability of Plastic Films and Coatings to Gases, Vapors,
and Liquids : Proceedings of the Borden Award Symposium of the Division of
Organic Coatings and Plastics Chemistry of the American Chemical Society,
Honoring Professor Vivian T. Stannett, Plenum Press, London, pp. 49–61.
Zhang, D., Zhou, C.H., Lin, C.X., Tong, D.S., Yu, W.H., 2010. Synthesis of clay minerals.
Appl. Clay Sci. 50, 1–11.
Zhou, C.H., 2010. Emerging trends and challenges in synthetic clay-based materials and
layered double hydroxides. Appl. Clay Sci. 48, 1–4.
Zhou, C.H., Xia, H., Jiang, G., Tong, D., Yu, W., 2010. Natural and synthetic clay minerals
for tailoring preparation of nanostructured functional materials. Abstracts ACMS21,
21st Conference of Australian Clay Minerals Society—Brisbane, August 7–8.
Zhu, J., Peng, H., Rodriguez-Macias, F., Margrave, J.L., Khabashesku, V.N., Imam, A.M.,
Lozano, K., Barrera, E.V., 2004. Reinforcing epoxy polymer composites through
covalent integration of functionalized nanotubes. Adv. Funct. Mater. 14, 643–648.