J Polym Environ (2006) 14:393–401

DOI 10.1007/s10924-006-0033-4

ORIGINAL PAPER

Aromatic Copolyester-based Nano-biocomposites: Elaboration,

Structural Characterization and Properties
Frédéric Chivrac Æ Zuzana Kadlecová Æ
Eric Pollet Æ Luc Avérous

Published online: 15 August 2006

Springer Science+Business Media, Inc. 2006

Abstract Biodegradable polymers are one of the most This situation is not entirely adequate because most of
promising ways to replace non-degradable polymers. these long-lasting polymers produced from petro-
But, to be a real alternative to classical synthetic chemicals are not biodegradable and are a significant
polymers and find applications, biopolymer (biode- source of environmental pollution. Thus, reaching the
gradable polymer) properties have to be enhanced. conditions of conventional plastic replacements by
Nano-biocomposites, which are obtained by incorpo- degradable polymers is of major interest for different
ration of nanofillers into a biomatrix, are an interesting actors of the socio-economical life. However till now,
way to achieve these improvements. Modified and biopolymers (biodegradable polymers) have not found
unmodified montmorillonites have been introduced extensive applications [1]. To be more attractive, some
into a biodegradable aromatic copolyester, poly(butyl- properties OF biopolymers have to be enhanced.
ene adipate-co-terephthalate) (PBAT). Structural Preparations of blends or conventional composites
characterization, thermal and mechanical tests have are among the possible routes to improve polymers
been carried out to understand better the relations properties [2]. A new area of composites called nano-
between the nanofillers structuring and the final nano- composites, in which the reinforcing material has
biocomposite properties. Main results show that clay nanometric scale, has emerged and seems to be very
incorporation and the obtained intercalated structures promising. For instance, at low level of nanofillers
improve PBAT properties (enhanced thermal stability, incorporation (less than 5 wt%) [3–4], the reinforce-
increased stiffness) and thus may increase the attrac- ment efficiency of nanocomposites can match that of
tiveness of this biopolymer. conventional composites with 40–50 wt% of loading
with classical fillers. This improvement is due to the
Keywords Nano-biocomposites Æ Biodegradable dispersion of nanoscale fillers into the matrix, which
polymer Æ Poly(butylene adipate-co-terephthalate) Æ results in a high surface area with high interactions
Layered silicates Æ Montmorillonite between nanofillers and the polymer matrix.
The addition of nanofillers into a biodegradable
polymer matrix leads to the creation of a novel class of
Introduction materials, called nano-biocomposites which combine
nano-materials with an environmental approach.
Nowadays, most of the short-term application materi- Recent studies have been previously reported for the
als (e.g., packaging) are based on synthetic polymers. elaboration and characterization of these nano-mate-
rials, based on polylactide [5–7], poly(3-hydroxybuty-
rate)[8] and corresponding copolymers [9], plasticized
F. Chivrac Æ Z. Kadlecová Æ E. Pollet Æ L. Avérous (&) starch [10–12], poly(butylene succinate) [13] or poly(e-
ECPM-LIPHT (UMR CNRS 7165), University Louis
caprolactone) [14–18].
Pasteur, 25 rue Becquerel, F-67087 Strasbourg, Cedex 2,
France Various nano-reinforcements are currently under
e-mail: [email protected] investigation. The most intensive researches concern

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layered silicates as the reinforcing phase due to Experimental Part

their availability, versatility and respectability towards
the environment [19]. Enhanced thermal stability, Materials
improved gas barrier properties, increased stiffness or
low melt viscosity are among the properties that can be The matrix is a biodegradable aromatic copolyester
achieved by these multiphase systems [20]. Montmo- PBAT, which has been kindly supplied by Eastman
rillonite (MMT) is a layered silicate commonly used in (EASTAR BIO Ultra Copolyester 14766). Figure 1
polymer nanocomposite preparation. It is a crystalline shows PBAT chemical structure. Figure 2 shows the
1
2:1 layered clay mineral with a central alumina H NMR spectrum of PBAT, dissolved in CDCl3. The
octahedral sheet sandwiched between two silica tetra- ratio between each monomer unit has been determined
hedral sheets [20]. These nanofillers have a hydrophilic by 1H NMR. The integration of the peaks of the adi-
character due to the presence of inorganic cations (Na+, pate unit (BA) and the terephthalate unit (BT),
Ca2+...) in the inter-layer spacing [21]. An ion-exchange respectively at 2.33 ppm and 8.1 ppm, gives PBAT
reaction of intergallery inorganic cations with, for in- composition: 57% of BA and 43% of BT. Determined
stance, alkyl ammonium cations can be carried out to by size exclusion chromatography (SEC), average
promote the polymer–silicate compatibility. molecular weight (Mw) and polydispersity index (I) are
Three main techniques can be used to prepare 48,000 g mol–1 and 2.4, respectively. Melt flow index
polymer/clay nanocomposites: melt intercalation, sol- (MFI) is 13 g/10 min at 190 C/2.16 kg. Density is
vent intercalation and in situ polymerization [4]. In the 1.27 g/cm3 at 23 C.
first two techniques, the preformed polymer is mixed The clay minerals studied were kindly supplied by
with the clay either in the molten state or in solution. Southern Clay Products, Inc. (Cloisite 20A), Laviosa
In the third approach, clay is dispersed into the Chimica Mineraria S.p.A. (Dellite LVF, Dellite
monomer solution which is further polymerised. The 43B) and Süd-Chemie (Nanofil 804). The unmodified
nanoparticles dispersed into the polymer matrix can be montmorillonite is Dellite LVF (MMT-Na). The
intercalated by macromolecules and/or exfoliated. three organo-modified montmorillonites are Cloisite
Intercalated structures show regularly alternating lay- 20A (OMMT-Alk) which is organo-modified by
ered silicates and polymer chains compared to exfoli- dimethyl dihydrogenated tallow ammonium, Dellite
ated structures in which the individual clay layers are 43B (OMMT-Bz) which is organo-modified with ben-
individually delaminated and fully dispersed in the zyl dimethyl hydrogenated tallow ammonium and
polymer matrix. Best performances (mechanical and Nanofil 804 (OMMT-(OH)2) which is organo-modi-
physical properties) are commonly observed with the fied by dihydroxyethyl methyl tallow ammonium. As
exfoliated structures. determined by thermogravimetric analysis (TGA),
Recently, Someha et al. [22] have published on the organic contents are 31.0 wt%, 8.0 wt% and 30.5 wt%
analysis of nano-biocomposites based on poly(butylene for OMMT-Alk, OMMT-Bz and OMMT-(OH)2,
adipate-co-terephthalate) (PBAT) and layered silicates respectively. Organo-modifiers chemical structures are
they have themselves organomodified. PBAT is a given in Fig. 3.
synthetic copolyester obtained from fossil resources
and known to be biodegradable. The degradation Nano-biocomposites Elaboration
mechanism of this biopolymer has been investigated by
both the study of the hydrolytic and the enzymatic Before processing, PBAT and clays were dried over-
degradation [23, 24]. These studies have demonstrated night at 80 C under reduced pressure. To obtain nano-
that the biodegradation rate mainly depend on the biocomposites, from 3 wt% to 9 wt% of MMT have
adipate content of this bio-copolyester. The present been added into PBAT matrix according to two syn-
article completes and expands the Someha’s work. It is thetic routes: solvent or melt intercalation.
focussed on the elaboration and characterization of
PBAT nano-biocomposites prepared by both solvent Solvent Intercalation
and melt intercalation with different kind of commer-
cial organo-modified montmorillonites. Structural, The nano-biocomposites were prepared by solvent
thermal and mechanical properties have been studied intercalation in chloroform. About 700 mg of PBAT
as a function of the preparation method as well as the are introduced into 35 mL of CHCl3 at 50 C and
content and nature of clay to understand better the sonicated until solubilisation. Then, the adequate
relations between the nanofillers structuring and the amount of MMT is introduced into the mixture and
final nano-biocomposite properties. sonicated at 50 C for 4 h. Finally, the solution is

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J Polym Environ (2006) 14:393–401 395

Fig. 1 Chemical structure of O

poly(butylene adipate-co- O O O
O
terephthalate) * CH 2 *
4 4
x y
O O O

Fig. 2 1H NMR spectrum of BT

PBAT C6H4 (8,1 ppm)

COCH2CH2

OCH2CH2

OCH2

BA
COCH2
(2,33 ppm)

CHCl3
Integral

1.0000

1.0105
1.3361

1.3502

3.7856
10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
(ppm)

poured into a petri dish and nano-biocomposites films Characterization

are obtained by solvent casting under atmospheric
conditions, at ambient temperature for 24 h. SEC and 1H NMR Measurements

Melt Intercalation SEC measurements were performed in THF (HPLC

grade), with PS standards for the calibration, on a
The nano-biocomposites were prepared by mechanical Shimadzu LC-10AD liquid chromatograph (Japan)
kneading with an internal batch mixer, a counter- equipped with a Shimadzu RID-10A refractive index
rotating mixer Rheocord 9000 (Haake-USA), at detector and a Shimadzu SPP-M10A diode array UV
160 C for 15 min with a rotor speed of 50 rpm fol- detector. 1H NMR spectra were recorded in CDCl3 on
lowed by another step at 120 C for 20 min with a rotor a Bruker 300 UltrashieldTM 300 MHz (Germany).
speed of 100 rpm. After melt processing, the molten
materials were compression-molded to obtain films XRD Characterization
with a hot press at 160 C applying 20 MPa pressure
for 10 min. The molded specimens were quenched The X-Ray Diffraction (XRD) morphological analyses
between two steel plates for 3 min to allow the speci- were performed on a powder diffractometer Siemens D
mens to be fully crystallized before testing. 5000 (Germany) using Cu (Ka) radiation (wavelength:

Fig. 3 Chemical structures of CH3 CH3 CH2CH2OH

the organo-modifiers + + H 3C N
+
T
H3C N HT H3C N CH2

HT CH2CH2OH
HT

OMMT-Alk OMMT-Bz OMMT-(OH)2

T = Tallow (~65% C18; ~30% C16; ~5% C14)
HT = Hydrogenated Tallow

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1.5406 Å) at room temperature in the range of 2h = 1.5 TGA Characterization

to 30 by step of 0.03 of 1s, each.
All thermogravimetric analyses (TGA) were per-
formed on 5–15 mg samples, at a heating rate of 20 C/
TEM Analysis
min from 25 to 600 C on a Hi-Res TGA 2950 appa-
ratus from TA Instruments (USA). For all PBAT/clay
For TEM observation, the samples were microtomed
nano-biocomposites, the analyses were carried out
at low temperature (–55 C) using a Leica Ultracut S
under ‘‘synthetic air,’’ which is a mixture of 75% N2
cryo-microtome (Japan) equipped with a diamond
and 25% O2. The clay content in inorganics (in wt%)
knife. The ultra thin sections (ca. 40 nm, prepared from
of each composite was assessed by TGA as the com-
3 mm thick plates) were examined using a Philips CM
bustion residue left at 600 C. The organic content (in
12 (Netherland) transmission electron microscope
wt%) of the organo-modified clay was determined by
using an acceleration voltage of 120 kV.
the weight loss recorded between 150 C and 450 C,
corresponding to the ammonium cations thermal deg-
DSC Characterization radation. The degradation temperature is determined
from the peak temperature of the derivative weight
The thermal behaviours of PBAT and its nano-bio- loss curve.
composites were analyzed by Differential Scanning
Calorimetry (DSC) using a DSC 2910 apparatus from Mechanical Tests
TA Instrument (USA). The analyses were performed
on 5–10 mg samples, at a heating rate of 10 C/min Tensile tests were carried out with an Instron tensile
from –70 C to 200 C. The reported values were testing machine (model 4204, USA), at 25 C with a
recorded during the second heating scan. The glass constant deformation rate of 10 mm/min, according to
temperature (Tg) is measured at the maximum of the the ASTM D882-91 norm. Samples were dumbbell-
derivative of the heat flow signal when the DCp gap shaped specimens prepared by injection molding
occurs. The melting temperature (Tm) is measured (160 C, 100 Mpa) with a Minijet from ThermoHaake
from the maximum of the endothermic peak. The (USA). Ten samples for each formulation were tested.
melting enthalpy (DHm) is measured from the area of The non-linear mechanical behaviour of the different
the endothermic peak and has been corrected from a samples was determined through different parameters.
dilution effect using the Eq. (1), where x is the per- The true strain is given by Eq. (3). In this equation, L
centage of organic content, DHm0 is the initial melt- and L0 are the length during the test and at zero time.
ing enthalpy and DHm the corrected melting Two different strains were calculated; strain at the
enthalpy. yield point (ey) and at break (eb).

100 L
DHm ¼ DHm0
ð1Þ e ¼ lnð Þ ð3Þ
x L0

The degree of crystallinity (v) is estimated from Eq. The nominal stress was determined by Eq. (4),
2, where DHm is the corrected enthalpy of nano-bio- where F is the applied load and S0 is the initial cross-
composites based on PBAT and DHm100 is the theo- sectional area. The true stress was given by Eq. (5),
retical enthalpy of 100% crystalline PBAT. where F is the applied load and S is the cross-sectional
area. S was estimated assuming that the total volume of
DHm the sample remained constant, according to Eq. (6).
v¼
100 ð2Þ
DHm100 The estimation of S is strictly valid before striction and
has no physical meaning after. Both, stress at the yield
DHm100 has been determined following the approach point (ry) and at break (rb) are determined. ry is
presented by Herrera et al. [23] DHm100 is calculated by estimated with the true stress value and rb is deter-
the contribution of the different chain groups. The mined with the nominal stress value (because of the
contributions of ester, methylene and p-phenylene striction).
groups are –2.5 kJ/mol, 4.0 kJ/mol and 5.0 kJ/mol,
respectively. The calculated values ( DHm100 ) is equal to F
\r[ ¼ ð4Þ
22.3 kJ/mol, i.e. 114 J/g. From this value, the degree of S0
crystallinity of PBAT has been determined.

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J Polym Environ (2006) 14:393–401 397

F Table 1 Inter-layer spacing values for the pristine MMT and

r¼ ð5Þ their respective PBAT nano-biocomposites
S
Samples D001 (Å)
L0
S ¼ S0
ð6Þ Nanofillers MMT-Na 12.1
L
OMMT-Alk 21.8
Young’s modulus (E) was measured from the slope of OMMT-Bz 32.7
OMMT-(OH)2 18.5
the low strain region in the vicinity of 0 (r = e = 0). Solvent intercalation PBAT/OMMT-Alk 3 wt% 38.5
PBAT/OMMT-Alk 6 wt% 36.3
PBAT/OMMT-Alk 9 wt% 35.7
Results and Discussion PBAT/OMMT-Bz 3 wt% 37.4
PBAT/OMMT-Bz 6 wt% 36.8
PBAT/OMMT-Bz 9 wt% 36.6
Structural Characterization Melt intercalation PBAT/MMT-Na 3 wt% 25.1
PBAT/MMT-Na 6 wt% 24.7
XRD Characterization PBAT/MMT-Na 9 wt% 23.9
PBAT/OMMT-Alk 3 wt% 29.8
PBAT/OMMT-Alk 6 wt% 28.8
Figure 4 shows typical XRD patterns recorded for PBAT/OMMT-Alk 9 wt% 26.4
pristine PBAT, OMMT-Alk organoclay and PBAT/ PBAT/OMMT-Bz 3 wt% 28.5
OMMT-Alk nano-biocomposites. Five diffraction PBAT/OMMT-Bz 6 wt% 28.5
PBAT/OMMT-Bz 9 wt% 26.7
peaks of the PBAT crystal structure are observed at 2h PBAT/OMMT-(OH)2 3 wt% 29.1
angle 16.4, 17.4, 20.6, 22.8 and 24.7, respectively. PBAT/OMMT-(OH)2 6 wt% 28.3
These five characteristic peaks are also observed at the PBAT/OMMT-(OH)2 9 wt% 27.9
same values for all PBAT nano-biocomposites. Con-
sequently, these results suggest that there are no
important transcrystallinity at the nanofillers/PBAT OMMT-(OH)2 obtained by solvent and melt interca-
interface and thus, few or no change in the PBAT lation. It was impossible to obtain nano-biocomposites
crystal structure induced by nanofillers incorporation. from solvent intercalation with MMT-Na and OMMT-
A decrease of the intensity of these diffraction peaks is (OH)2, because these two nanofillers sediment in
observed when clay loading increases, indicating a drop chloroform.
in the PBAT crystallinity. Thus, it seems that the For all the PBAT nano-biocomposites samples, an
nanofillers likely hinder the crystal growth of PBAT intense d001 diffraction peak is observed meaning that
crystallite. these materials are mostly intercalated and not fully
The OMMT-Alk diffraction pattern displays two exfoliated. Table 1 shows that samples prepared from
diffraction peaks at low 2h angles (4.1 and 7.9) corre- solvent intercalation present an increase of the inter-
sponding to the d001 and d002 values, respectively. The layer spacing, thus suggesting an effective intercalation
clay inter-layer spacing is calculated from the d001 peak of PBAT chains. Inter-layer spacing values observed
using the Bragg’s law. Table 1 summarizes the inter- for nano-biocomposites prepared with OMMT-Alk
layer spacing results for different nano-biocomposites and OMMT-Bz are equivalent, which probably means
prepared with MMT-Na, OMMT-Alk, OMMT-Bz and that these two nanofillers have an equivalent affinity
with PBAT.
12000
Except for the PBAT/OMMT-Bz samples, results
obtained from melt intercalation show an increase of
10000
the inter-layer spacing. This means that there is inter-
Intensity [A.U.]

9 wt %
8000 calation of PBAT chains into montmorillonite inter-
6 wt % layer spacing. However, we can notice lower polymer
6000
intercalations compared to those obtained by solvent
3 wt %
4000 intercalation. An interesting point is the increase of
2000
OMMT-Alk
intergallery spacing observed for nano-biocomposites
PBAT prepared with MMT-Na. This result demonstrates that
0
0 5 10 15 20 25 30 35 intercalated nanocomposites can be obtained with
2 theta (°) PBAT even without organo-modifying the nanofillers.
Fig. 4 Typical XRD patterns of PBAT/OMMT-Alk nano- Equivalent results had been obtained on plasticized
biocomposites starch [10–12]. But, non-modified montmorillonite

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melt-blended with polyesters usually leads to micro- Thermal Properties

composites [3].
DSC
TEM
Table 2 summarizes the results obtained by DSC
Figure 5 shows typical TEM micrographs of the measurements. According to these measurements,
PBAT/OMMT nano-biocomposites stemmed from PBAT glass temperature (Tg) is –38 C, PBAT melting
melt intercalation containing 3 wt% of OMMT-Alk. temperature (Tm) is 110 C and crystallinity degree (v)
Since silicate layers are composed of heavier elements is around 10.8%. On one hand, the nano-biocompos-
(Al, Si, Mg) than surrounding matrix (C, H, N and O), ites glass temperature (Tg) values seem to indicate that
they appear darker in the bright-field images. The nanofillers have no effect on glass transition. Similarly,
micrographs show that the montmorillonite layers are the nano-biocomposite melting temperatures (Tm) are
not homogeneously dispersed. TEM results confirm closed to neat PBAT melting temperature. These re-
that PBAT-based nano-biocomposites mainly display sults agree with XRD analyses indicating that nano-
an intercalated structure on agreement with XRD filler addition does not change PBAT crystal
analyses. Evaluated from the micrographs, the average organization. On the other hand, the melting enthalpy
distance between clay layers is found to be around (DHm) and therefore the crystallinity (v) are affected
30 Å which is in good agreement with the inter-layer by clay addition. Compared to neat PBAT, the varia-
spacing results obtained from XRD analyses. tions observed at 3 wt% are not significant, but drops
of v are observed when clay content increases towards
9 wt%. This result also agrees with XRD analyses, and
seems to indicate that nanofillers hinder the PBAT
crystallite growth.

TGA

The thermal stability is assessed by thermogravimetric

analysis (TGA). Figure 6 shows typical TGA thermo-
grams obtained for neat PBAT and the corresponding
nano-biocomposites proceed from melt intercalation.
Table 3 presents the nano-biocomposite degradation
temperatures. PBAT degradation temperature is
395 C. The nano-biocomposite degradation tempera-
tures are higher or at least equal to PBAT one. The
highest improvements are observed for nano-biocom-
posites filled with 3 wt% of montmorillonite and a
decrease of the degradation temperature is observed
for higher clay contents, both with melt and solvent
intercalations. This behaviour is in agreement with
published results obtained on polyester/montmoril-
lonite nanocomposites [20]. The highest degradation
temperatures are observed for PBAT/MMT-Na nano-
biocomposites.
It is widely accepted [3, 25–28] that layered silicates
enhance the thermal stability of the polymer matrix
because they act as a heat barrier, which enhances the
overall thermal stability of the system, as well as assists
in the formation of char during thermal decomposition.
Nevertheless, only a slight improvement is observed
for PBAT nano-biocomposites. To explain this rather
Fig. 5 TEM picture of a PBAT/OMMT-Alk 3 wt% nano- low thermal stability improvement with some nano-
biocomposite obtained by melt intercalation composite systems, Sinha Ray and Okamato [20] have

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J Polym Environ (2006) 14:393–401 399

Table 2 Thermal properties

Preparation method Samples Tg (C) Tm (C) DHm (J/g) v (%)
of PBAT nano-biocomposites
measured by DSC – PBAT – 38 110 12.3 10.8
Solvent intercalation PBAT/OMMT-Alk 3 wt% – 38 111 12.6 11.1
PBAT/OMMT-Alk 6 wt% – 38 111 12.5 11.0
PBAT/OMMT-Alk 9 wt% – 38 111 12.1 10.6
PBAT/OMMT-Bz 3 wt% – 37 111 11.4 10.0
PBAT/OMMT-Bz 6 wt% – 37 111 11.2 9.8
PBAT/OMMT-Bz 9 wt% – 37 111 10.9 9.6
Melt intercalation PBAT/MMT-Na 3 wt% – 37 111 13.2 11.6
PBAT/MMT-Na 6 wt% – 37 111 11.0 9.6
PBAT/MMT-Na 9 wt% – 38 112 11.4 10.0
PBAT/OMMT-Alk 3 wt% – 37 110 10.2 8.9
PBAT/OMMT-Alk 6 wt% – 37 111 10.3 9.0
PBAT/OMMT-Alk 9 wt% – 37 111 10.0 8.8
PBAT/OMMT-Bz 3 wt% – 37 111 11.6 10.2
PBAT/OMMT-Bz 6 wt% – 37 112 10.6 9.3
PBAT/OMMT-Bz 9 wt% – 36 113 10.4 9.1
PBAT/OMMT-(OH)2 3 wt% – 38 111 12.0 10.5
PBAT/OMMT-(OH)2 6 wt% – 38 111 10.2 8.9
PBAT/OMMT-(OH)2 9 wt% – 38 111 9.3 8.2

Fig. 6 Typical thermograms

(weight loss vs. temperature)
obtained under ‘‘synthetic
air’’ flow for PBAT, PBAT/
MMT-Na 3 wt%, PBAT/
OMMT-Alk 3 wt%, PBAT/
OMMT-(OH)2 3 wt% and
PBAT/OMMT-Bz 3 wt%
stemmed from melt
intercalation

recently assumed that in the early stages of thermal Table 3 Degradation temperatures of PBAT and its nano-
decomposition, the clay would shift the decomposi- biocomposites
tion to higher temperature. But in a second step, Preparation Samples Degradation
the clay layers could accumulate heat and then be method temperature (C)
transformed as a heat source and promote an
acceleration of the decomposition process in combi- – PBAT 395
Solvent PBAT/OMMT-Alk 3 wt% 405
nation with the heat flow supplied by the outside heat intercalation PBAT/OMMT-Alk 6 wt% 403
source. That could explain why in our case there is only PBAT/OMMT-Alk 9 wt% 395
a slight improvement of the thermal degradation Melt PBAT/MMT-Na 3 wt% 410
temperatures. intercalation PBAT/MMT-Na 6 wt% 408
PBAT/MMT-Na 9 wt% 405
PBAT/OMMT-Alk 3 wt% 406
Mechanical Properties PBAT/OMMT-Alk 6 wt% 395
PBAT/OMMT-Alk 9 wt% 394
Tensile tests have been carried out on nano-biocom- PBAT/OMMT-Bz 3 wt% 411
PBAT/OMMT-(OH)2 3 wt% 407
posite samples prepared from melt intercalation.

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10 PBAT sion. The addition of nanofillers does not really change

9 PBAT/OMMT-Alk 3 wt% PBAT
PBAT/OMMT-Alk 6 wt% 3 wt% the stress at yield, except for PBAT/MMT-Na 9 wt%.
Nominal Stress (MPa)

8 PBAT/OMMT-Alk 9 wt%
6 wt%
This poor value is probably induced by the lower
7
6
9 wt% affinity of PBAT for MMT-Na.
5
4
3 Conclusions
2
1
The aim of this study was the elaboration of nano-
0
0 50 100 150 200 250 biocomposites by two methods: solvent and melt
True Strain (%) intercalation. Structural, thermal and mechanical
Fig. 7 Typical tensile curves obtained for neat PBAT and characterizations were performed to understand bet-
PBAT/OMMT-Alk 3, 6 & 9 wt% ter the relations between the preparation routes,
nanofillers structuring and the final nano-biocom-
posites properties. For both elaboration techniques,
Figure 7 presents the typical tensile curves obtained intercalated nano-biocomposites were obtained. This
for PBAT/OMMT-Alk 3, 6 and 9 wt%. Table 4 sum- nanostructure was pointed out by both XRD analy-
marizes the Young’s modulus (E) and other mechani- ses and TEM observations. Higher intercalation lev-
cal properties of PBAT and nano-biocomposites. els have been obtained for samples prepared from
According to these mechanical tests, PBAT Young’s solvent intercalation compared to those obtained by
modulus (E) is 57 MPa, strain at yield (ey) is 28%, melt intercalation. No significant change induced by
strain at break (eb) is 188%, stress at yield (ry) is the nanofillers incorporation has been observed by
8.1 MPa and stress at break (rb) is 55 MPa. The XRD on the PBAT crystal structure. Both XRD and
addition of nanofillers leads to substantial improve- DSC analyses have evidenced a decrease in the
ment in stiffness correlated to the increase in clay PBAT crystallinity induced by the clay incorporation,
loading, even if there is a decrease of the PBAT crys- probably because nanofillers hinder crystallite
tallinity observed by both DSC and XRD. Conse- growth. The DSC results have shown that the
quently, the observed increase in rigidity is induced by nanofillers have no significant influence on the bio-
the nanofiller incorporation into the matrix and stem polymer Tg and Tm. An improvement of PBAT
from strong interactions between nanofillers and thermal stability has been noticed by TGA, mainly at
PBAT chains. However, there are notable differences low clay content (3 wt%). Tensile tests have shown
in the level of improvement between PBAT/MMT-Na that the nano-biocomposites stiffness increases con-
and PBAT/OMMT-Alk. The stronger affinity of org- tinuously with clay content. Nevertheless, a decrease
ano-modified montmorillonites with PBAT leads to a in the strain at yield (ey) and at break (eb) has been
better dispersion and stronger interactions resulting in observed.
a higher Young’s modulus. The addition of clay leads Therefore, all results presented here clearly dem-
to a decrease in the strain at yield (ey) and at break (eb) onstrate that the appropriate incorporation of mont-
values. These drops are correlated with the clay con- morillonite as a nanofiller can improve PBAT
tent and are more pronounced for unmodified mont- properties and thus increase the attractiveness of this
morillonite. The decrease of stress at break (rb) biodegradable polymer. Indeed, these nano-biocom-
observed for all nano-biocomposites samples when clay posites materials are on agreement with the emergent
loading increases is likely linked to nanofillers disper- concept of sustainable development.

Table 4 Mechanical properties (calculated from the stress-strain curves) of PBAT nano-biocomposites prepared by melt-intercalation
Samples E (MPa) ey (%) eb (%) ry (MPa) rb (MPa)

PBAT 57 ± 3 28 ± 1 188 ± 15 8.1 ± 0.4 55 ± 11

PBAT/MMT-Na 3 wt% 66 ± 4 26 ± 3 128 ± 22 8.4 ± 0.3 26 ± 6
PBAT/MMT-Na 6 wt% 81 ± 4 20 ± 1 120 ± 15 8.3 ± 0.4 23 ± 4
PBAT/MMT-Na 9 wt% 88 ± 4 15 ± 4 59 ± 8 6.7 ± 1.5 11 ± 1
PBAT/OMMT-Alk 3 wt% 72 ± 2 26 ± 2 172 ± 7 8.1 ± 0.3 42 ± 4
PBAT/OMMT-Alk 6 wt% 84 ± 4 23 ± 2 163 ± 7 8.5 ± 0.3 36 ± 4
PBAT/OMMT-Alk 9 wt% 111 ± 3 21 ± 2 144 ± 8 8.6 ± 0.5 27 ± 2

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J Polym Environ (2006) 14:393–401 401

Acknowledgments The authors thank the IPCMS (Institut de 12. Park HM, Li X, Jin CZ, Park CY, Cho WJ, Ha CK (2002)
Physique et Chimie des Matériaux et du Solide) and the ICS Macromol Mater Eng 287:553
(Institut Charles Sadron) in Strasbourg (France) for their tech- 13. Ray SS, Okamoto K, Maiti P, Okamoto M (2002) J Nanosci
nical support. Thanks are also extended to Dr. Christian Chau- Nanotechnol 2:171
mont and Perrine Bordes (ECPM-Strasbourg) for their technical 14. Pantoustier N, Alexandre M, Degee P, Calberg C, Jerome R,
insight. Henrist C (2001) e-Polymer 9:1
15. Pantoustier N, Lepoittevin B, Alexandre M, Kubies D,
Calberg C, Jerome R (2002) Polym Eng Sci 42:1928
References 16. Lepoittevin B, Devalckenaere M, Pantoustier N, Alexandre
M, Kubies D, Calberg C (2002) Polymer 43:4017
17. Viville P, Lazzaroni R, Pollet E, Alexandre M, Dubois P,
1. Avérous L (2004) J Macromol Sci Pt C-Polym Rev C44:231 Borcia G, Pireaux JJ (2003) Langmuir 19:9425
2. Le Digabel F, Boquillon N, Dole P, Monties B, Avérous L 18. Gain O, Espuche E, Pollet E, Alexandre M, Dubois P (2005)
(2004) J Appl Polym Sci 93:428 J Polym Sci Pt B-Polym Phys 43:205
3. Alexandre M, Dubois P (2000) Mater Sci Eng R 28:1 19. Okamoto M (2004) J Ind Eng Chem 10:1156
4. Pinnavaia TJ, Beall GW (2000) Polymer–clay nanocompos- 20. Ray SS, Okamoto M (2003) Prog Polym Sci 28:1539
ites. Wiley, New-York 21. Grim RE (1953) Clay mineralogy. McGraw-Hill, New York
5. Ogata N, Jimenez G, Kawai H, Ogihara T (1997) J Polym Sci 22. Someya Y, Sugahara Y, Shibata M (2005) J Appl Polym Sci
Pt B-Polym Phys 35:389 95:386
6. Bandyopadhyay S, Chen R, Giannelis EP (1999) Polym 23. Herrera R, Franco L, Rodriguez-Galan A, Puiggali J (2002)
Mater Sci Eng 81:159 J Polym Sci: Pt A: Polym Chem 40:4141
7. Ray SS, Yamada K, Okamoto M, Ueda K (2002) Nano Lett 24. Tsutsumi C, Hayase N, Nakagawa K, Tanaka S, Miyahara Y
2:1093 (2003) Macromol Symp 197:431
8. Maiti P, Batt CA, Giannelis EP (2003) Polym Mater Sci Eng 25. Blumstein A (1965) J Polym Sci: Pt A: Polym Chem 3:2665
88:58 26. Biswas M, Ray SS (2001) Adv Polym Sci 155:167
9. Chen GX, Hao GJ, Guo TY, Song MD, Zhang BH (2004) J 27. Giannelis EP (1998) Appl Organomet Chem 12:675
Appl Polym Sci 93:655 28. Gilman JW (1999) Appl Clay Sci 15:31
10. de-Carvalho AJF, Curvelo AAS, Agnelli JAM (2001) Car-
bohydr Polym 45:189
11. Park HM, Lee WK, Park CY, Cho WJ, Ha CS (2003) J
Mater Sci 38:909

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