ISSN 0965-545X, Polymer Science, Series A, 2022, Vol. 64, No. 5, pp. 519–531. © Pleiades Publishing, Ltd., 2022.

ISSN 0965-545X, Polymer Science, Series A, 2022. © Pleiades Publishing, Ltd., 2022.

COMPOSITES

Addition of Organo-Modified Nanoclay for Tuning

the Microstructure, Thermal Stability, and Biodegradability
of Poly(lactic acid)/Polycarbonate Immiscible Blends
Nadjat Chelghouma, Imane Mayoufa,*, Ali Larousa, Melia Guessouma,
Magali Foisb, and Nacerddine Haddaouia
aLaboratoire de Physico-Chimie des Hauts Polymères (LPCHP), Département de Génie des Procédés,
Faculté de Technologie, Université Ferhat ABBAS Sétif-1, 19000 Sétif (Algérie)
b
Centre d’Etudes et de Recherche en Thermique, Environnement et Système (CERTES EA-3481),
Université Paris Est Créteil, Créteil, France
*e-mail: imen_myo@yahoo.fr
Received October 8, 2021; revised May 11, 2022; accepted June 6, 2022

Abstract—Poly(lactic acid) (PLA)/polycarbonate (PC) blends and composites were compared to investigate
the effects of matrix composition and nanoclay content on the materials properties. The composites were pre-
pared by incorporating 1, 3, and 5 wt % of organo-modified montmorillonite (MMT) and varying the PC
content from 10 to 30 and 50%. The formulations were melt blended then subjected to many investigations
such as thermal, structural and morphological analyses and to biodegradation. Microstructure observation
revealed a significant morphology refinement of the mixtures forming the composites matrices and pointed
out an optimal dispersion of PC domains into the PLA phase. This could be assigned to the fact that the inter-
actions evolved between PC chains and MMT tactoids contribute in creating a barrier against PC domains
coalescence, thus reducing their size and refining the morphology. As a result, the thermal and thermo-
mechanical analyses of PLA/PC/MMT composites unveiled notable variations on the crystallization and vis-
coelastic properties depending on the matrix composition and MMT content. Also, TGA and biodegradabil-
ity assessment by soil burial method emphasized the crucial contribution of MMT in increasing the compos-
ites thermal stability and promoting their biodegradation.

DOI: 10.1134/S0965545X22700225

INTRODUCTION the neat polymer. Chang et al. [11] compared the

Fillers are usually added to polymers and polymer
blends to improve their thermal, mechanical and other
important properties [1‒6]. Also, nanoscale spherical
particles, nanotubes, and layered clays are incorpo-
rated because of their high specific areas and out-
standing properties [7]. In this sense, several attempts
have been conducted in order to enhance poly(lactic
acid) (PLA) properties via adding inorganic fillers [8].
Pluta et al. [9] studied PLA/montmorillonite (MMT)
nanocomposites prepared in presence of modified and
unmodified MMT. Morphological analysis pointed
out the achievement of an intercalated structure due to
the good affinity between the organo-modified nano-
clay and PLA, which thermal stability has been nota-
bly improved. Also, Ray et al. [10] investigated PLA
performances after incorporating MMT modified
with trimethyloctadecylammonium cations. All the
nanocomposites exhibited important improvements in
several properties such as storage modulus, flexural
modulus and strength, heat distortion temperature,
gas barrier property and biodegradability relatively to
properties of PLA nanocomposites prepared by add-
ing MMT and fluorinated-mica both modified with
hexadecylamine. The higher tensile strength and
modulus were obtained for the clay and mica contents
of 4 and 8 wt %, respectively. Besides, Chang et al. [12]
studied the properties of PLA in presence of MMT
modified with alkylammonium salts and showed that
the clay nanolayers were uniformly dispersed into the
matrix, thus contributing in decreasing the PLA oxy-
gen permeability by the half for MMT loadings up to
10 wt %.
The improvement of blends nanocomposites prop-
erties could also be owed to the crucial role of nano-
clays in morphology refinement and matrix compati-
bilization, resulting from the selective affinity of the
nanofiller for one of the blend’s components. Accord-
ingly, Hong et al. [13] focused on compatibilizing
polybutylene terephthalate (PBT) and polyethylene
(PE) immiscible blend using an organoclay and con-
cluded that the clay layers are first positioned at the
interface and then they are dispersed selectively in the

519
520 NADJAT CHELGHOUM et al.
PBT phase for which the nanofiller presents the higher
affinity. Additionally, the valuable refinement of the
dispersed phase droplets was reported to derive from
the decrease in the surface tension and prevention of
coalescence resulting from the interfacial localization
of the organoclay, thus acting as an the effective com-
patibilizer. Similarly, Salehiyanet al. [14] investigated
the microstructure of PLA/polycaprolactone
(PCL)/MMT nanocomposites and noticed, through
morphological observations, that modified MMT
reduced significantly the size of the dispersed phase
nodules. Also, Singh et al. [15] reported the role of an
organically modified nanoclay as an efficient compat-
ibilizer for polycarbonate (PC)/poly(methyl methac-
rylate) (PMMA) matrix through observing a single
glass transition temperature Tg, a decrease in opacity
and a transition from a biphasic morphology for neat
blends to more homogeneous morphology in presence
of the nanofiller. Likewise, Xi et al. [16] stated that the
addition of nanoparticles refines the morphology of
PMMA/PC blends to a lesser extent and improves
noticeably the thermal and mechanical properties.
In a previous paper [17], we studied the properties
of PLA/PC blends and tried to remedy the problem of
their incompatibility by promoting transesterification
reactions catalyzed with samarium acetylacetonate.
Many other researchers worked on the compatibiliza-
tion of this system through catalyzed interchange reac-
tions using many other catalysts [18] or by adding
compatibilizers [19]. The main goal of the present
paper is to study the properties of PLA/PC blends pre-
senting different compositions namely 90/10, 70/30,
and 50/50 after incorporating 1, 3, and 5% of a com-
mercial organoclay consisting of montmorillonite
modified with bis(2-hydroxyethyl) methyl tallow
ammonium. The work is particularly focused on sub-
stantiating the efficiency of the organoclay in promot-
ing compatibility and improving the dispersion of PC
into the PLA matrix via the study of the thermo-
mechanical properties and morphology as a function
of PC and organoclay contents.
EXPERIMENTAL
Materials
PLA is manufactured by Nature Plastunder the
name PLI 005 (melt flow index (MFI) at 190°C and
under 2.16 kg: 10‒30 g/10 min, melting temperature:
155‒160°C). PC is Makrolon 2858 supplied by Bayer
(MFI at 190°C: 10 g/10 min, density 1.20 g/cm3). The
organophilic nanoclay is nanomer 1.34TCN of Nano-
cor, and it consists of a montmorillonite modified
with bis(2-hydroxyethyl) methyl tallow alkyl ammo-
nium.
POLYMER SCIENCE, SERIES A
Processing
PC, PLA, and MMT were placed in an oven at
60°C for 24 h to dry before melt blending. Then,
(90/10), (70/30), and (50/50) PLA/PC blends were
melt mixed without MMT then in presence of 1, 3,
and 5% of the nanoclay to get PLA/PC/MMT com-
posites. The materials were prepared in a 60 cm3 Bra-
benderchamber for 15 min at 220°C and 30 rpm rotat-
ing speed.
Differential Scanning Calorimetry (DSC)
DSC measurements were performed on samples of
approximately 10 mg using a Perkin-Elmer instrument
under inert atmosphere. The samples were first heated
from 25 to 250°C, maintained at this temperature for
two minutes, then cooled to 25°C, and finally they
were reheated to 250°C. The heating and cooling rates
were 10 K/min.
Dynamic Mechanical Analysis (DMA)
Dynamic mechanical analysis was carried out on a
TA instrument under inert atmosphere on specimens
having the dimensions 50 × 10 × 1 mm3. The samples
were analyzed in shearing mode, with a dynamic strain
of 0.05%, at a frequency of 1 Hz, and from 25 to 180°C
varying at a heating rate of 3 K/min.
Scanning Electron Microscopy (SEM)
Morphology was studied by scanning electron
microscopy using a JSM-6301F microscope. Obser-
vations were performed on gold coated surfaces pro-
duced on fracturing at liquid nitrogen temperature.
X-ray Diffraction (XRD)
A Bruker D8 Advance diffractometer, equipped
with a CuKα generator operating at a wavelength of
0.15406 nm was used to perform X-ray diffraction
analysis.
Thermogravimetric Analysis (TGA)
Thermogravimetric analysis was carried out using a
Perkin Elmer TGA 4000 and by heating the samples
from 25 to 700°C at a heating rate of 10 K/min under
a flow of nitrogen gas.
Biodegradation
To monitor weight loss for a period of one year, soil
burial method was carried out on 20 × 20 mm2 sam-
ples. Samples of an initial mass m0 were buried at a dis-
tance of 10 cm underground irrigated periodically by
activated sludge collected from a municipal wastewa-
ter treatment plant. The samples were periodically
Vol. 64 No. 5 2022
 ADDITION OF ORGANO-MODIFIED NANOCLAY 521

Heat flow, mW Heat flow, mW

(a) (b)
2
2
endo up

endo up
6
6
5
5
4
4
3
3

1 1

40 80 120 160 200 240 40 80 120 160 200 240

Temperature, °C Temperature, °C

Heat flow, mW
(c)
2
endo up

5
4
3

40 80 120 160 200 240

Temperature, °C

Fig. 1. DSC thermograms of (1) PLA, (2) PC and PLA/PC matrix compositions: (a) (90/10), (b) (70/30), and (c) (50/50) with
different MMT contents: (3) 0, (4) 1, (5) 3, (6) 5%.

recovered and weighed to get their mass mt and calcu-
late the variations of the weight residual percentage Rw
versus burying time according to the following equa-
tion [20]:
 m − mt 
Rw (%) =  0  × 100.
 m0 
RESULTS AND DISCUSSION
Thermal Properties of PLA/PC/MMT Composites
The DSC curves corresponding to the second heat-
ing cycles of PC, PLA, PLA/PC blends and their
counterparts filled with 1, 3, and 5% of MMT are
shown in Figs. 1a–1c, respectively. The PC and PLA
thermograms reveal that the glass transition tempera-
tures of the two polymers are situated at about 145 and
59°C, respectively. Also, PLA exhibits a crystallization
peak which maximum refers to a crystallization tem-
perature Tc around 107°C and its area to a crystalliza-
tion enthalpy ΔHc of 33.6 J/g. Furthermore, the melt-
ing behavior of neat PLA is indicated by a double peak
with melting temperatures Tm1 and Tm2 of about 155
and 162°C and a total area corresponding to a melting
enthalpy ΔHm of the order of 36 J/g. The bimodal
(1)
melting behavior results from the presence of pseudo-
orthorhombic disordered and orthorhombic ordered
PLA crystalline phases.
The DSC thermograms of neat PLA/PC blends
show that the PLA phase glass transition is unchanged
after melt blending with PC, which delineates clearly
the total immiscibility of the two polymers for all the
studied compositions. The PC phase Tg is not observ-
able because it situated in the temperature interval
wherein PLA melting occurs. Also, the blends ther-
mograms reveal that the crystallization temperature of
PLA increases with the PC concentration; the lower
the PLA contribution into the matrix, the higher are

POLYMER SCIENCE, SERIES A Vol. 64 No. 5 2022

522 NADJAT CHELGHOUM et al.
Table 1. Analysis of DSC thermograms for PLA homopolymer and PLA phase into PLA/PC blends and composites
PLA/PC Tc, °C
MMT, % 0 1 3 5 0 1
100/0 99 – – – 33
90/10 101 110 109 110 31
70/30 102 110 112 112 25
50/50 102 111 114 109 18
its crystallization temperature and the contribution of
the pseudo-orthorhombic crystalline population in
the melting process. These results have already been
reported by Chelghoum et al. [17] who explained that
despite the total immiscibility of the blend, the PC
glassy phase exerts a notable inhibitory effect causing
restrictions to PLA chains mobility thus delaying its
crystallization process.
The composites thermograms reveal trivial varia-
tions on Tg and Tm of PLA phase with the addition of
MMT, contrary to the crystallization temperature
which displaces to higher values as MMT content
increases. This suggests that in presence of clay nano-
layers, the PLA crystallization is disturbed and so it
occurs at higher temperatures. The highest values of Tc
are reported for the composites with 3% of MMT,
probably due to the better dispersion of the nanoclay,
which imposes more restrictions to the PLA chains
motions, thus retarding their crystallization. Addi-
tionally, it has been observed that as MMT concentra-
tion increases, the melting peaks owing to PLA ort-
horhombic and pseudo-orthorombic crystalline pop-
ulations illustrate evident changes in their amplitude,
thus substantiating variations in their proportions into
the composites, as compared to neat PLA and
PLA/PC blends. The concomitant increase in the first
peak intensity and decrease in that of the second one
affirms that due to MMT, more disordered crystalline
populations are formed (Table 1).
Viscoelastic Properties of PLA/PC/MMT Composites
Figures 2, 3, and 4 display the variations of the con-
servation modulus G' and the damping factor tanδ as
a function of temperature for neat PLA/PC blends and
their counterparts filled with 1, 3, and 5% of MMT.
Below Tg, PLA storage modulus appears like a plateau
and presents a value around 1141 MPa. As the glass
transition occurs at approximately 63°C, the storage
modulus decreases drastically due to the loss of PLA
stiffness. An increase in the modulus is again regis-
tered resulting from the cold crystallization process,
which increases the polymer stiffness [17]. Glassy PC
presents a storage modulus of about 1048 MPa, which
decreases abruptly around 150°C due to the glass tran-
POLYMER SCIENCE, SERIES A
ΔHc, J/g ΔHm, J/g
3 5 0 1 3 5
– – – 36 – – –
34 34 32 32 31 26 29
29 27 24 26 25 23 23
20 19 18 19 18 17 16
sition. Below PLA’s Tg, the PLA/PC blends exhibit
intermediate storage moduli which experience two
drops as PLA and PC glass transitions occur (Figs. 2a,
3a, and 4a).
As it is represented in Figs. 2b, 3b, and 4b giving the
variations of tanδ versus temperature, the maxima of
the peaks identifying the PLA and PC Tg values are
slightly changed, thus corroborating the blend immis-
cibility as depicted from the DSC results. These minor
variations could be due to several factors including
interactions of both polymers with MMT functional
groups, the eventual plasticizing effect induced by the
nanoclay modifier, which creates extra volume at the
interface between the filler and the matrix [21] and the
rubbery PLA, which prompts PC chains mobility after
the PLA glass transition.
In the temperature range comprised between the
PLA phase Tg and cold crystallization, it is noticed
that the storage modulus increases proportionally with
the PC content into the matrix. The composites based
on (70/30) and (50/50) PLA/PC matrices exhibit rel-
atively higher storage moduli than that of pristine
PLA, thus confirming the effective reinforcing effect
induced by the PC phase. For the composites based on
(90/10) PLA/PC blend, it was noted that the increase
in storage modulus is detected only for 5% of MMT
due to the great enhancement in the composite stiff-
ness. However, the composites with 1 and 3% of MMT
experienced a sharp decrease suggesting that the filler
altered the structural cohesion of the PLA matrix due
to the disruption of inter-chains interactions into the
polymer. Also, it is observed that beyond the PLA cold
crystallization temperature, the storage modulus
increases significantly due to MMT, but without
showing a consistent trend with the nanoclay content.
Additionally, the positive effect of MMT on the
thermo-mechanical properties seems more prominent
for higher PC content. These outcomes suggest that as
MMT is dispersed into the composites, its localization
around the PC phase bring more reinforcement than
when it is restrictively confined into PLA matrix.
The study of tanδ variations is a powerful tool to
reveal interactions between polymers and fillers in
composite materials. Also, it might bring supplemen-
tary information regarding the selective affinity of the
nanofiller for a certain phase forming the matrix. As it
Vol. 64 No. 5 2022
 ADDITION OF ORGANO-MODIFIED NANOCLAY 523

G ', Pa
(a) 1
1010 2
3
4
5
6
109

108

107

40 80 120 160
Temperature, °C
(b)
tan
1.6 1
2
3
4
5
1.2 6

0.8

0.4

0
40 80 120 160
Temperature, °C

Fig. 2. Variations of (a) the storage modulus and (b) tanδ versus temperature for (1) PLA, (2) PC and (90/10) PLA/PC blend
filled with different MMT contents: (3) 0, (4) 1, (5) 3, (6) 5%.

is well known for composite materials, the intensity of
tanδ peak is inversely proportional to the interfacial
tension [22, 23]. From a structural point of view,
MMT could present affinity for PLA as well as PC
because both polymers have similar functional groups
that are susceptible to interact with the hydroxyls of
the nanoclay. However, it appears that its affinity for
the PC phase is higher because it is observed that the
height of tanδ peak owing to the PC phase decreases
noticeably in presence of MMT, especially for the
concentration of 3%, for which a stronger interface is
probably produced. This could be due to the more
favorable interactions between the PC phase func-
tional groups and the MMT modifier.
Microstructure Analysis of PLA/PC/MMT Composites
Figure 5 compares the evolution of morphology for
PLA/PC blends before and after the incorporation of
3% of MMT. Figures 5a and 5c illustrating, respec-
tively, the morphologies of (90/10) and (70/30)
PLA/PC blends are typical of an immiscible polymer

POLYMER SCIENCE, SERIES A Vol. 64 No. 5 2022

524 NADJAT CHELGHOUM et al.

G ', Pa
(a) 1
1010 2
3
4
5
6
109

108

107

40 80 120 160
Temperature, °C
(b)
tan
1
1.6 2
3
4
5
6
1.2

0.8

0.4

0
40 80 120 160
Temperature, °C

Fig. 3. Variations of (a) the storage modulus and (b) tan δ versus temperature for (1) PLA, (2) PC and (70/30) PLA/PC blend
filled with different MMT contents: (3) 0, (4) 1, (5) 3, (6) 5%.

mixture, or a two-phase morphology in which PC reg-
ular spherical domains are dispersed within the PLA
continuous phase. The micrographs show full PC
nodules presenting different sizes ranging between 13
and 2 μm and between 40 and 2 μm for (90/10) and
(70/30) blends, respectively, and hollows due to delo-
calization by impact load. The PC phase nodules
reveal smooth contours with no evident deformation
confirming thus that the PC particles have not with-
stand the applied load as the same time as the PLA
matrix. This underlines the absence of effective stress
transfer caused by the high interfacial tension and the
poor adhesion.
The Fig. 5b, presenting the (90/10/3)
(PLA/PC/MMT) composite, shows a finer morphol-
ogy compared to its unfilled counterpart. The PC
spherical nodules exhibit an obvious decrement in
their size, which attains values between 1.5 and 5 μm.
Similarly, the (70/30/3) (PLA/PC/MMT) compos-
ite, exemplified in Fig. 5d, reveals a much more finer
morphology featured by further decrease in PC nod-

POLYMER SCIENCE, SERIES A Vol. 64 No. 5 2022

 ADDITION OF ORGANO-MODIFIED NANOCLAY 525

G ', Pa
1
1010 (a) 2
3
4
5
6
109

108

107

40 80 120 160
Temperature, °C
tan (b)
1
1.6 2
3
4
5
6
1.2

0.8

0.4

0
40 80 120 160
Temperature, °C

Fig. 4. Variations of (a) the storage modulus and (b) tan δ versus temperature for (1) PLA, (2) PC and (50/50) PLA/PC blend
filled with different MMT contents: (3) 0, (4) 1, (5) 3, (6) 5%.

ules size which ranges between 3 and 0.5 μm. This sug-
gests that MMT reduces significantly the interfacial
tension and decreases the tendency of PC domains to
agglomeration by preventing their coalescence. It is
thought that the morphology refinement could result
from the contribution of both shear forces that help in
the cleavage of the PC phase into finer nodules and
the interactions linking these domains to the MMT
layers. All these effects reduce the interfacial energy
and stabilize the morphology by suppressing nodules
interconnecting.
The (50/50) PLA/PC blend (Fig. 5e) reveals a co-
continuous morphology due to the equivalent propor-
tions of the two phases into the mixture. The blend
shows a coarse morphology with large fracture paths
resulting from the rapid growth of microcracks to pro-
duce the rupture of the composite. However, the
Fig. 5f of (50/50/3) PLA/PC/MMT composite shows
a less coarse co-continuous morphology due the per-
sistence of PC micro-domains. The localization of
MMT tactoids around PC nodules delays their coales-
cence and prevents the formation of a co-continuous

POLYMER SCIENCE, SERIES A Vol. 64 No. 5 2022

526 NADJAT CHELGHOUM et al.

(а) 100 μm (b) 25 μm

(c) 100 μm (d) 25 μm

(e) 100 μm (f) 25 μm

Fig. 5. SEM micrographs of PLA/PC blends and PLA/PC/MMT composites: (a) (90/10), (b) (90/10/3), (c) (70/30),
(d) (70/30/3), (e) (50/50), and (f) (50/50/3).

microstructure similar to that showed by the neat
blend. As result, somewhat droplet-matrix morphol-
ogy, consisting of regular dispersed domains, with
dimensions between 7 and 1.8 μm, is still observed.
The microstructure shows also smaller fracture lines
denoting the contribution of the matrix in the transi-
tion to a more energy consuming mechanism in pres-
ence of MMT.
Recently, several studies reported that clays can
effectively reduce the size of polymer domains in mix-
tures and play the role of compatibilizers in many
immiscible polymer blends [24]. In this context,
As’habi et al. [25, 26] concluded a noticeable refine-
ment of the dispersed phase domains induced by
organo modified nanoclay incorporated into
PLA/linear low density polyethylene (LLDPE)
matrix. They proposed that the clay nanolayers could
form a solid barrier around the nodules of the LLDPE
dispersed phase, thus inhibiting coalescence. Simi-
larly, it is reported that such interfacial localization of
clay layers enhances adhesion and refines the dis-
persed phase nodules in immiscible blends [26]. Like-
wise, Lipatov et al. [27] suggested that the addition of
inorganic particles into polymer blends is an efficient
method for stabilizing morphology through the
adsorption of the two polymers on the surface of the
filler particles.
The XRD patterns of MMT, PLA and the (50/50)
PLA/PC blend and its counterpart with 3% of MMT
are demonstrated in Fig. 6. XRD pattern of MMT dis-
plays a principal diffraction peak at 2θ of 4.7° owing to
the basal reflection (001), and accounting for 1.86 nm
interlayer spacing.
The diffractogram of the (50/50/3)
PLA/PC/MMT composite reveals also the character-
istic diffraction peak of MMT but at 5.64°, which cor-
responds to ad-spacing of 0.78 nm. However, this did
not exclude that may be an intercalated structure
could be detected for lower 2θ values. Salehiyan et al.
[28] observed an intercalated structure even though
the trivial change in MMT d-spacing and suggested
that some platelets disperse in matrix phases whereas

POLYMER SCIENCE, SERIES A Vol. 64 No. 5 2022

 ADDITION OF ORGANO-MODIFIED NANOCLAY
Intensity, a.u.
4 5 6 7
Fig. 6. XRD patterns of (1) MMT, (2) PLA, (3) (50/50) PLA/PC blend, and (4) its composite with 3% of MMT.
the other fraction of the nanofiller is immobilized at
the interphase. Conclusively, this supposes the dispo-
sition of the nanoclay tactoids at the interface between
PC and PLA phases. The preferential localization of
MMT around the PC domains forms a solid barrier
disabling their aggregation and hindering the coales-
cence originated from the blend immiscibility.
Accordingly, it was found that hydrophobic nanopar-
ticles trapped in the interfacial region of (80/20) poly-
propylene (PP)/polystyrene (PS) blend induces a
finer morphology, while relatively hydrophilic
nanoparticles did not yield morphological improve-
ments [29, 30].
Thermal Stability of PLA/PC/MMT Composites
TG and DTG thermograms of PLA, PC, (50/50)
(PC/PLA) blend and their composites containing 3%
of MMT are displayed in Figs. 7a, 7b. PLA decompo-
sition occurs in one step that begins around 295°C and
finishes by 388°C, whereas PC presents a relatively
higher thermal stability and decomposes between 410
and 627°C. Pristine (50/50) (PLA/PC) blend exhibits
an intermediate thermal stability and its thermogram
shows essentially two degradation steps due to the
decomposition of PLA and PC phases into the mix-
ture. The decomposition temperature of the PC phase
into the blend is lower than that of the PC homopoly-
mer due to the residues of the degraded PLA phase,
which accelerate the PC decomposition [31]. In addi-
tion, the DTG thermogram of (50/50) (PLA/PC)
blend exhibits an evident shoulder observed between
the PLA and PC degradation steps, resulting probably
POLYMER SCIENCE, SERIES A Vol. 64 No. 5
527
4
3
8 9 10
2θ, deg
from interchange reactions between the two polymers
even in absence of catalyst [18].
The TG and DTG thermograms of homopolymers
composites point out that Td0 values registered an evi-
dent decrease compared to corresponding neat poly-
mers. The acceleration effect of the clay on the ther-
mal degradation of both PLA and PC is believed to be
associated to the surfactant agent inserted into the clay
layers [32]. But, contrary to PLA composite, the PC
composite exhibits a higher stability thanks to the good
interactions relating the PC chains and the clay
nanoparticles, which seem to form a more thermally
stable char around the PC domains, thus delaying
their degradation.
The (50/50/3) PLA/PC/MMT composite shows a
significantly better thermal stability than that of the
corresponding mixture and decomposes essentially in
two stages. The thermal degradation of the composite
starts with a minor initial weight loss due to the
decomposition of the MMT modifier. Afterwards, the
PLA and PC phases decompose and show notable
increments on the degradation temperatures, thus
stating for a higher thermal stability of the whole com-
posite. This might be on account of the differences in
morphologies between the blend and its composite.
Actually, SEM micrographs pointed out that the
(50/50) PLA/PC blend forming the matrix composite
preserved a somewhat droplet-matrix morphology
allowing the better dispersion of the MMT-stabilized
PC droplets within the PLA matrix. This seems to
confer a higher thermal resistance relatively to the co-
continuous morphology where the PC and PLA
2022
528 NADJAT CHELGHOUM et al.

Weight, %
(a)
100

80

60

40 1
2
3
20 4
5
6
0
200 300 400 500 600
Temperature, °C
dm/dt, %/min
(b)
0

−10

−20
1
2
3
−30 4
5
6

−40
200 300 400 500 600
Temperature, °C

Fig. 7. (a) TG and (b) DTG thermograms of homopolymers (1) PLA, (2) PC, (3) PLA/MTT (3), (4) (50/50) PLA/PC blend,
(5) PC/MTT (3), (6) (50/50/3) PLA/PC/MMT composite.

phases are almost totally separated and behave like
their respective homopolymers. Furthermore, MMT
tactoids contribute in retarding the degradation by
forming a more stable char, which acts as a barrier
against the degrading medium.
Biodegradation of PLA/PC Blends and Their
Composites
Figure 8 shows that neat PLA film undergoes bio-
degradation directly after a relatively short induction
time and reveals a high weight loss. The degradation
process initiates by the sample fragmentation to extend
the contact area of the polymer with the external
medium. Afterwards, the microorganisms attack the
ester bonds, which are the most vulnerable sites of the
PLA skeleton, by excretion of enzymes that allow the
decrease in the polymer molecular weight then its
assimilation and mineralization [33, 34].
PLA/PC blends show longer induction times and
lower biodegradation ability which depends on their
PLA content; the more important the PLA content

POLYMER SCIENCE, SERIES A Vol. 64 No. 5 2022

 ADDITION OF ORGANO-MODIFIED NANOCLAY 529

Rw, %

100

90

80

70
1
2
3
60 4

0 2 4 6 8 10 12
Time, month

Fig. 8. Time-dependence of weight residual percentage for (1) PLA, PLA/PC blends: (2) (90/10), (3) (70/30), (4) (50/50).

Rw, %

100

80

60

1
2
40
3
4
5
20

0 2 4 6 8 10 12
Time, month

Fig. 9. Time-dependence of weight residual percentage for (1) PLA and PLA/PC/MMT composites at 3% of MMT:
(2) PLA/MMT, (3) PLA/PC/MMT (90/10/3), (4) PLA/PC/MMT (70/30/3), (5) PLA/PC/MMT (50/50/3).

and the higher the tendency of the blend to biodegra-
dation. This could be attributed to the too slow rate of
biodegradation in presence of the non-degradable PC
phase dispersed throughout the PLA matrix. Further-
more, the incompatibility of the mixture is a promoter
factor that accelerates both the fragmentation of the
sample and its biodegradation due to the easy access of
microorganisms to the polymer chains through the
free volume forming the interface between the two
polymers [35].
Biodegradation results for (90/10/3), (70/30/3),
and (50/50/3) PLA/PC/MMT composites are dis-

POLYMER SCIENCE, SERIES A Vol. 64 No. 5 2022

530 NADJAT CHELGHOUM et al.
played in Fig. 9. PLA/MMT and PLA/PC/MMT
composites present a more pronounced aptitude to
decomposition relatively to the neat materials. Indeed,
the blends composites depict more important rates of
decomposition and relatively short induction times.
This is due to the promoter role of the nanoclay, which
accelerates biodegradation via polymer/clay interface
and the increased aptitude to water absorption due to
the nanofiller hydrophilicity. Therefore, the access of
microorganisms brought by the activated sludge to the
cleavable groups of the PLA phase is facilitated and
fastened, which declines the induction time and accel-
erates the PLA phase hydrolysis [26, 36].
The (70/30/3) PLA/PC/MMT composite experi-
enced the more important weight loss due to the nota-
ble morphology refinement resulting in a better dis-
persion of the PC domains, thereby increasing the
contact area of the PLA phase with the degrading
medium via the interface. This is further accentuated
by the nanoclay localization at the interfacial region
between PLA and PC, thus promoting a more homo-
geneous hydrolysis process through the PLA matrix.
As a result, a much finer fragmentation of the compos-
ites is produced and induces a faster assimilation of the
sample.
CONCLUSIONS
DSC analysis of the composites revealed that the
crystallization enthalpy and temperature were affected
by the clay particles and the PC domains, which seem
to disturb seriously the PLA aptitude to crystallization.
The viscoelastic properties of the composites were also
closely related to the MMT content and the matrix vis-
cosity that is determined by the polymers contribu-
tions. Indeed, it has been concluded that the
(70/30/3) PLA/PC/MMT composite exhibited the
highest conservation modulus, beyond the PLA glass
transition temperature, due to the contribution of
MMT in ensuring a better dispersion of PC nodules
into the matrix. Also, tanδ variations supported the
fact that MMT presents a higher affinity for the PC
phase, which improved its dispersion into the PLA
matrix. In addition, SEM observation of (70/30/3)
PLA/PC/MMT composite showed great changes in
the matrix microstructure, from a coarse morphology
to a notably refined droplet/matrix microstructure.
This was assigned to the involvement of PC chains into
interactions with MMT particles, which stabilized its
morphology and prevented coalescence. Finally, the
presence of MMT and PC phase finer dispersion
prompted the composites biodegradation.
CONFLICT OF INTEREST
The authors declare that they have no conflicts of interest.
POLYMER SCIENCE, SERIES A
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