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Polymer Degradation and Stability 93 (2008) 707e713

www.elsevier.com/locate/polydegstab

Ageing of polylactide and polylactide nanocomposite laments

Samuel Solarski, Manuela Ferreira*, Eric Devaux
Laboratoire de Genie et Materiaux Textiles (GEMTEX), UPRES EA2461, Ecole Nationale Superieure des Arts et Industries Textiles (ENSAIT),
BP 30329, 59056 Roubaix Cedex 01, France
Received 25 October 2007; received in revised form 6 December 2007; accepted 12 December 2007
Available online 23 December 2007

Abstract
An experimental study was carried out in order to check the inuence of various parameters on the ageing of PLA laments performed in
a climatic room. Initially, two grades of PLA with different D-isomer contents were analysed. Even after several weeks of ageing, properties of
PLA laments with less than 0.5% D-isomer content did not vary extensively. On the other hand, the mechanical and thermal properties of PLA
laments with 4% D-isomer content underwent strong modications. Subsequently, a selected organomodied bentonite (Bentone104 e noted
as B104) was blended with PLA and then melt-spun to study the inuence of a nanoller on the ageing of PLA laments. Faster degradation of
PLA nanocomposite laments was then observed.
2008 Elsevier Ltd. All rights reserved.
Keywords: Polylactide; Nanocomposite; Melt spinning; Thermal properties; Mechanical properties; Ageing

1. Introduction
Polylactide (PLA) is a biodegradable polymer which can be
spun to produce bres [1,2]. PLA is very interesting because it
can be synthesized from renewable resources and it represents
an interesting way to replace petroleum based polymer.
Nanollers, such as clay and more particularly montmorillonite, are well known to modify the properties of polymers
when they are blended even at low ller level (generally under
5% in weight) [3,4]. Generally, the thermal, mechanical, ammability and barrier properties can be strongly improved. The
polymer nanocomposites are interesting to develop nanocomposite bres with new properties. The use of a polymeric matrix
to produce a nanocomposite multilament yarn has been
described for the rst time in 2002 by Bourbigot et al.[5].
The matrix used was polyamide-6 (PA6) reinforced with Cloisite30B (C30B). The ammability of knitted structure made
with PA6 and PA6/C30B bres was investigated and a strong
decrease of the heat release rate was measured. Then, some
nanocomposite matrices were used to develop some new kind
* Corresponding author. Tel.: 33 3 20 25 64 75; fax: 33 3 20 27 95 97.
E-mail address: manuela.ferreira@ensait.fr (M. Ferreira).
0141-3910/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2007.12.006

of bres: polyamide (PA) [6], poly(butylene terephthalate)

(PBT) [7], poly(trimethylene terephthalate) (PTMT) [8],
poly(ethylene terephthalate) (PET) [9e11], polypropylene
(PP) [12,13] and polyimideamide (PIA) [14,15]. Until now,
only few polymer/clay blends have been studied for production
of bres. When clay is added, the thermal, re and dimensional
stability properties of laments are generally improved.
In previous work, we have studied the possibility to develop
polylactide/clay nanocomposite laments [16,17]. The rst
clay used was Cloisite30B [16]. We have shown that problems in spinning occurred for PLA lled with more than
2 wt% of C30B. The elongation at break strongly decreased,
so laments with low tensile properties were obtained. For
this reason, a blend with dioctyl adipate as plasticiser
(10 wt%) was prepared and the resulting sample was extruded
and successfully melt-spun drawn. The laments obtained had
better elongation properties, so they could be used to produce
knitted fabrics. The second clay used was Bentone104 [17].
B104 is more suitable to develop polymer layered silicate
nanocomposite laments. Unlike C30B, this clay can be added
up to 4 wt% without detrimentally affecting tensile strength
properties of melt-spun laments, especially when laments
are drawn at high draw ratio. Moreover, it is not necessary

S. Solarski et al. / Polymer Degradation and Stability 93 (2008) 707e713

708

to use plasticiser, which simplies the extrusion of PLA and

B104.
The hydrolysis of PLA has already been extensively studied
in different media: hydrolysis in neutral media (such as phosphate-buffered solution, Ringer solution or water), in acidic or
alkaline solutions [18]. The biodegradability of PLA and PLA
organoclay nanocomposite has also been investigated under
compost [19e21]. An increase of the rate of biodegradation
of neat PLA after nanocomposites preparation was observed.
Tsuji et al. [22]. have studied the inuence of nano-structured
carbon llers (carbon nanotubes for example) and conventional carbon llers such as carbon black on the enzymatic
degradation of PLA. Depending on the kind of ller, the degradation of PLA was modied. Carbon nanotubes enhanced
the enzymatic degradation, whereas carbon black disturbed it.
The inuence of organoclay on the ageing of PLA laments
is not yet known. The aim of this study is to investigate the
ageing of two grades of PLA laments with different stereochemical compositions, and the inuence of the incorporation
of clay into the PLA matrix. The ageing of different kinds of
laments was accelerated using a climatic room. The properties of the laments were analysed using differential scanning
calorimetry (DSC), thermogravimetric analysis (TGA) and
tensile testing machine.

2.3. Melt spinning

PLA and PLA nanocomposite were spin-drawn with the
spinning device Spinboy I from Busschaert Engineering.
PLA and PLA nanocomposite multilament yarns were
obtained [17,23]. Pellets were rst melted in a single screw
extruder from 210 to 215  C. Then melted PLA passes through
two dies consisting of 40 channels with a diameter of 400 mm
to obtain a multilament continuous yarn which was coated
with Filapan CTC (blend of branched acid ester and branched
polyglycol), a spin nish supplied by Boehme. Finally, the
multilament yarn was hot drawn between two rolls: the
draw ratio (DR), which is the ratio between the rotation speeds
of the feeding and the draw rolls (rst and second rolls, respectively) was 3.5. The speed of the feed roll was maintained at
200 m/min, and the speed of the draw roll was 750 m/min.
The temperature of the rst roll was 70  C, and the temperature of the second roll was 110  C [23].
2.4. Investigation of the dispersion of B104
The dispersion of clay in PLA/4 wt% B104 laments was
analysed using Wide-Angle X-ray Diffraction (WAXD) and
Transmission Electron Microscopy (TEM).

2. Experimental
2.1. Materials
Two PLAs were used. Poly(L,L-lactide) (noted as PLAg) e
commercial name Galastic was supplied by Galactic S.A.
Poly(L,L-lactide) Biomer L9000 was obtained from Biomer.
The characteristics of these PLAs are described in Table 1.
An organomodied layer silicate supplied as Bentone104
(B104, supplier e Elementis Specialties) in which the exchange cation is benzyl dimethyl hydrogenated tallow ammonium (131 meq/100 g clay, w70% inorganic content) was
used to prepare PLA/clay hybrid nanocomposite (denoted as
PLA/4 wt% B104).
2.2. Nanocomposite preparation
PLA nanocomposites to be melt-spun were prepared through
melt-direct intercalation by using a conventional polymer
extrusion process and optimized parameters. PLA pellets
(Galastic) with 4 wt% B104 were blended using a co-rotating
extruder (Thermo Haake, diameter of screw 16 mm, L/D
25). The temperatures of the ve zones were 140  C/160  C/
170  C/180  C/190  C. The rotation speed was maintained at
Table 1
Characteristics of PLAg and PLAb

Mn (PLA)
D-isomer content (%)

150 rpm. PLA and B104 were incorporated together in a rst

feeding zone. The extrudate was then pelletized.

2.4.1. WAXD
The morphological analysis by X-ray diffraction was performed on a Siemens D5000 diffractometer using Cu Ka radi ) at room temperature in the range
ation (wavelength: 1.5406 A
of 2q 1.5e30 , by step of 0.04 and scanning rate of 2 /min.
2.4.2. TEM
Transmission electron micrographs were obtained with
a Philips CM100 apparatus using an accelerator voltage of
100 kV. The samples were 70e80 nm thick and prepared
with a Reichert Jung Ultracut 3E, FC4E ultracryomicrotome
cutting at 130  C. Reported microphotographs represent typical morphologies as observed at, at least, three various places
of, at least, three different slices.
2.5. Ageing
The ageing of PLA and PLA nanocomposite laments were
performed in a climatic room (Excal 2221-HA from Climats).
The relative humidity and temperature were maintained at, respectively, 95% and 50  C. This temperature was chosen to be
under the glass transition temperature of PLA, and to prevent
the modications of thermal properties of PLA.
2.6. Characterization of thermal properties

PLAg

PLAb

74,500
4.3

200,000
<0.5

The thermal characteristics of PLA and PLA nanocomposite

laments were investigated using a TA instruments DSC 2920.
Samples were placed in aluminium pan (about 5 mg) from 0 to

S. Solarski et al. / Polymer Degradation and Stability 93 (2008) 707e713

200  C. The heating rate was 10  C/min and the cooling rate
was controlled at 10  C/min. Two heating scans were carried
out: the rst one to observe the thermal properties of the
laments, the second one to observe the thermal properties of
the PLA itself, after the deletion of the thermo-mechanical
history. In order to measure the energies of melting, indium
standard was used. All experiments were carried out using
nitrogen as purge gas.
2.7. Characterization of thermal stability of laments
Thermogravimetric analyses (TGA) of PLA and PLA nanocomposites laments were performed using a TA 2050 Instruments at 10  C/min from 20 to 600  C under owing air
(50 ml/min). Filaments (about 10 mg) were placed in open
platinum pans. The precision on temperature measurements
is 0.5  C.

709

So, a nanocomposite with a majority intercalated structure is

obtained. On the other hand, as far as the PLA/4 wt% B104
laments are concerned, no peak is observed in the low angle
area. The disappearance of the characteristic peak suggests
that the nanocomposite structure of the laments is exfoliated
or disordered.
The nanocomposite structure of the PLA/4 wt% B104 laments has also been observed using TEM (Fig. 2A and B).
The image at low magnication shows a rather homogeneous
dispersion of the silicate layers, even if some little tactoids
are still present. A lot of exfoliated layers can be observed in
Fig. 2B. Drawing seems to have a strong effect on the nanocomposite structure. From an intercalated structure for PLA/4 wt%
B104 pellets, it turns to exfoliated when PLA/4 wt% B104 is
melt-spun and drawn. The shear induced during the drawing
would make the separation of silicate layers easier in the laments. The TEM images, which represent the cross-sections

2.8. Characterization of the tensile properties

The measurement of the tensile properties of PLA and PLA
nanocomposite laments have been carried out following the
standard NF EN ISO 5079 on a Zwick 1456 tensile testing
machine, the cell force used was 10 N. All the tests were
made at standard atmosphere (the temperature was 20  2  C
and the relative humidity 65  5%). The length between the
clamps was 20 mm. All the results represent an average value
of 30 tests.
3. Results and discussion
3.1. Dispersion of clay in PLA/4 wt% B104 laments
To conrm obtaining PLA/organoclay laments with nanocomposite structure, the corresponding laments were analysed using TEM and WAXD. Fig. 1 presents the WAXD
curves of B104, PLA/4 wt% B104 (pellets and laments
with a draw ratio of 3.5). The characteristic peak of B104, located at 4.4 , is shifted towards lower angle (2.5 ) when B104
is blended with PLA. The decrease of the diffraction angle
means that PLA macromolecules insert between the silicate
layers of B104. By using the Braggs law, it is possible to calculate the d001 value, which is the interlayer space. For B104
and PLA/B104 pellets, d is, respectively, 2.00 and 3.53 nm. It
represents an increase of the interlayer space, d001, of 1.53 nm.
(a)

Intensity (a.u.)

1000

B104 (a)
PLA / 4 wt% B104 pellets (b)
PLA / 4 wt% B104 filaments (DR = 3.5) (c)

800
600
(b)
400
200

(c)

0
0

10

12

14

2Theta
Fig. 1. XRD curves of B104, PLA/4 wt% B104 (pellets and laments).

Fig. 2. TEM images of PLA/4 wt% B104 laments. (A) and (B) represent, respectively, the cross-sections at low (500 nm) and high (200 nm)
magnication.

S. Solarski et al. / Polymer Degradation and Stability 93 (2008) 707e713

710

of the laments, show rather well-dened dark lines (i.e., borders of the silicate layers). An orientation of the silicate layers
in the drawing direction can be assumed.
PLAg, PLAg/4 wt% B104 and PLAb laments were stored
in a climatic room at 50  C and 95% relative humidity, in order
to accelerate the ageing. The mechanical and thermal properties and the thermal stability of the yarns were nally measured
to observe the inuence of the stereochemistry and the incorporation of clay into the PLA matrix on these properties.
3.2. Thermal properties

3.2.2. Thermal properties of PLA regardless the thermomechanical history

To observe the effect of ageing on the glass transition
temperature of the different PLA, Tg was measured during the
second heating scan. The Tg values for PLAg, PLAg/4 wt%
B104 and PLAb are presented in Fig. 5. The dependence of Tg
on the number-average molar mass can be expressed according
to the equation proposed by Fox and Flory [25]:
Tg TgN 

K
Mn

where K is a constant depending on the polymer and TgN is the

glass transition temperature value of the polymer with a supposed innite molar mass. For PLAb, Tg remains constant
around 56  C. So we can suppose that the variation of Mn is
not sufcient to lead to a decrease of Tg. Concerning PLAg,
after an induction period until 40 days where Tg remains constant around 51  C, then Tg decreases to 28.5  C. So after 40
days ageing, Tg of PLAg decreases which means that Mn
has also decreased, due to hydrolysis. It is interesting to
note that the incorporation of B104 into PLA leads to a faster
hydrolysis. In this case, there is no induction period, Tg decreasing from the beginning of the ageing. It conrms a faster
degradation of the PLA matrix in the presence of clay dispersed at nanoscale level.

70
80

60

70

Glass transition
temperature (C)

Degree of cristallinity (%)

3.2.1. Thermal properties of laments

Fig. 3 presents the degree of crystallinity of PLA and PLA
nanocomposite laments as a function of ageing time. At initial
time, PLAg and PLAg/4 wt% B104 laments have similar degree of crystallinity (around 35%). Concerning PLAb laments,
it is higher (54%). This difference is explained by the different
D-contents of PLAg and PLAb. The lower the D-content, the
higher the degree of crystallinity. The D-content of PLAb is
less than 0.5%, while it is 4.3% for PLAg, so higher degree
of crystallinity can be reached with PLAb.
An increase of the degree of crystallinity can be observed
for each lament. This increase is due to the hydrolysis of
the PLA chains, in the amorphous regions rather than in the
crystalline areas, the amorphous regions being more accessible. So, the rst step of the hydrolytic degradation occurs in
the amorphous areas. The remaining PLA chains then have
higher mobility. They can reorganize themselves, which leads
to an increase of the degree of crystallinity. But this increase is
different for each kind of laments. The degree of crystallinity
of PLAb laments increases by only 15%, while it is 50% for
PLAg laments. So it seems that PLAb laments, with low Dcontent, degrade slower than PLAg laments. This slower degradation can be explained by the high degree of crystallinity of
PLAb laments which reduces the possibility to hydrolyse
PLA macromolecules.
The presence of clay seems to increase the hydrolysis of
PLA. The degree of crystallinity of PLAg/4 wt% B104 laments increases by 59%, while it is 50% for PLAg laments.
This faster degradation may be due to the presence of

hydroxyl groups of the silicate. These hydroxyl groups would

promote the hydrolysis of PLA macromolecules [21].
Fig. 4 represents the glass transition temperature of PLA and
PLA nanocomposite laments as a function of ageing time. At
rst, an increase of Tg is observed between initial time and 7
days, whatever the laments analysed. This increase may be assigned to an annealing effect. Tsuji et al. [24] observed the same
effect during the in vitro hydrolysis of PLA lm in phosphatebuffered solution. Then, Tg reaches a maximum value. Only Tg
of PLAg/4 wt% B104 laments decreases slightly. So, no clear
conclusions can be deduced here. The high orientation of PLA
macromolecules in the laments prevents to observe any modications of the glass transition. So, it is necessary to observe
the second heating scan which represents the thermal properties
of PLA, regardless of its thermo-mechanical history.

50
40
30

PLAg
PLAg / 4 wt% B104
PLAb

20
10
0

60
50
40
30
20

PLAg
PLAg 4 wt% B104

10

PLAb

10

20

30

40

50

60

70

80

Time (days)
Fig. 3. Degree of crystallinity of PLA and PLA nanocomposite laments as
a function of ageing time.

10

20

30

40

50

60

70

80

Time (days)
Fig. 4. Glass transition temperature of PLA and PLA nanocomposite laments
as a function of ageing time.

70

Glass transition
temperature (C)

60
50
40
30

PLAg
PLAg / 4 wt% B104
PLAb

20
10
0
0

10

20

30

40

50

60

70

80

Enthalpy of crystallization (J/g)

S. Solarski et al. / Polymer Degradation and Stability 93 (2008) 707e713

711

40
35
30
25
20
15
10

PLAg / 4 wt% B104

PLAb

5
0
0

10

20

30

Time (days)

40

50

60

70

80

Time (days)

Fig. 5. Glass transition temperature of PLA and PLA nanocomposite as a function of ageing time (second heating scan).

Fig. 7. Enthalpy of crystallization of PLAb and PLA/4 wt% B104 as a function

of ageing time (cooling scan).

The ageing of PLAg has also strong inuence on the crystallization process. During the second heating scan, a strong
decrease of the temperature of cold crystallization (Tcc) can
be observed for PLAg (cf. Fig. 6). At initial time, Tcc is
120  C, it falls to 88  C after 70 days. This decrease is due
to the hydrolysis of PLA macromolecules. The chains being
shorter, their ability to crystallize increases. Concerning
PLAg/4 wt% B104, Tcc is lower at initial time (104  C).
Clays were found to display a strong inuence on the crystallization rate of PLA, as well as on other polymers where they
play the role of nucleating agent and promote crystallization
[26e29] allows increasing the crystallinity rate. So the silicate layers of B104 which are delaminated can act as nucleating agents and promote the crystallization of the PLA
macromolecules. After 17 ageing days, there is no more
cold crystallization. In fact, PLAg/4 wt% B104 fully crystallizes during the cooling scan. Fig. 7 which represents the enthalpy of crystallization of PLAb and PLA/4 wt% B104 as
a function of ageing time shows clearly that PLAg/4 wt%
B104 fully crystallizes after 20 ageing days, and reaches
a maximal value at 35 J/g. For PLAb, Tcc remains constant
around 92  C (cf. Fig. 6).
Fig. 8 represents the enthalpy of cold crystallization (DHcc)
of PLA and PLA/4 wt% nanocomposite as a function of ageing time. Concerning PLAb and PLAg/4 wt% B104, a decrease

of DHcc is observed. This effect is due to the ability of PLAb

and PLAg/4 wt% B104 to crystallize during the cooling scan.
Concerning PLAg, it does not crystallize during cooling, so an
increase of DHcc is observed until 40 ageing days where it reaches a maximum value of 34 J/g. These results conrm the
faster degradation of PLAg/4 wt% B104 compared with
PLAg. But for PLAb, if there was no modication of Tg and
Tcc, a modication of the crystallization is observed. PLAb
crystallizes more easily during the cooling scan. It means
that a slight hydrolysis of PLAb occurs during ageing.
3.3. Thermal stability of PLA laments
The PLA laments were analysed using TGA in order to
check the release of low molecular weight compounds generated during the hydrolysis. These low molecular weight compounds have lower thermal stability and should be degraded
and/or volatilized more easily. Fig. 9 presents the TG curves
for PLAg, PLAg/4 wt% B104 and PLAb at initial and nal
ageing times. Concerning PLAg, a faster thermal degradation
of the resin is clearly observed after ageing. At initial time, the
onset of degradation temperature at 10% weight loss (T10%) of
PLAg is 307  C, and it falls to 244  C after ageing. It represents a decrease of 63  C. This effect is amplied when
PLAg contains 4 wt% B104. Before ageing, the stability of
PLAg/4 wt% B104 is higher than PLAg, the silicate layers

120

40

110

Enthalpy of cold
cristallyzation (J/g)

Cold crystallization
temperature (C)

130

100
90
80

PLAg E3
PLAg 4 wt% B104 E3.5
PLAb E3

70

35
30
25
20
15
PLAg
PLAg / 4 wt% B104
PLAb

10
5
0

60
0

10

20

30

40

50

60

70

80

Time (days)
Fig. 6. Cold crystallization temperature of PLA and PLA nanocomposite as
a function of ageing time (second heating scan).

10

20

30

40

50

60

70

80

Time (days)
Fig. 8. Enthalpy of cold crystallization of PLA and PLA/4 wt% nanocomposite
as a function of ageing time (second heating scan).

S. Solarski et al. / Polymer Degradation and Stability 93 (2008) 707e713

712
100

80

Tensile strength (MPa)

(1)
(3)
(5)
(2) (6)

Weight (%)

(4)
60

(1)
(2)
(3)
(4)
(5)
(6)

40

20

PLAg it
PLAg ft
PLAg 4 wt% B104 it
PLAg 4 wt% B104 ft
PLAb it
PLAb ft
200

100

PLAg

400

PLAg / 4 wt% B104

PLAb

350
300
250
200
150
100
50
0
0

10

20

30

40

50

60

70

80

Time (days)

0
0

450

300

400

500

600

Fig. 11. Tensile strength of PLA and PLA nanocomposite laments as a function of ageing time.

Temperature (C)
Fig. 9. TG curves for PLAg, PLAg/4 wt% B104 and PLAb at initial (noted as
it) and nal (noted as ft) ageing times.

acting as an insulating barrier. T10% is then 328  C. After ageing, the thermal stability of PLA/4 wt% B104 strongly decreases, and T10% is only 233  C, which represents
a decrease by 95  C. These results conrm the trend observed
using DSC. The degradation of the PLA matrix is faster in the
presence of clay dispersed at nanoscale level.
For PLAb, the thermal stability is the same before and after
ageing, T10% being 311  C. Even if PLAb undergoes a slight
hydrolysis, as shown using DSC, it does not lead to the formation of low molecular weight compounds with lower thermal
stability than PLA.

3.4. Tensile properties of PLA laments

In order to observe the inuence of the ageing on the mechanical properties, each kind of laments has been tested.
Fig. 10 represents the Youngs modulus values of PLAg,
PLAg/4 wt% B104 and PLAb laments. The initial Youngs

Young's Modulus (GPa)

7
6
5
4
3
PLAg

PLAg / 4 wt% B104

PLAb

1
0
0

10

20

30

40

50

60

70

80

Time (days)
Fig. 10. Youngs modulus of PLA and PLA nanocomposite laments as a function of ageing time.

modulus values of PLAg and PLA/4 wt% B104 are similar

(5.9 GPa). Then, these two kinds of laments follow the
same trend. The Youngs modulus slightly decreases until the
laments are too weak to be tested, that is to say from 60 ageing days for PLAg laments and 50 ageing days for PLAg/4
wt% B104 laments. For PLAb, it remains almost constant.
Only a small decrease is observed at the end of the test. Concerning the tensile strength (cf. Fig. 11) of PLAg and PLAg/
104, it continuously decreases. This decrease is slightly
quicker concerning PLA/4 wt% B104. For PLAb, it also decreases, but slower. These results conrm the previous observations. When PLAg is lled with 4 wt% B104, the ageing
is promoted and the hydrolysis occurs faster which leads to
a quicker degradation of the tensile properties of the laments.
For PLAb, the D-content being lower, the degree of crystallinity is higher, which limits the hydrolysis and the decrease of
the tensile properties.
4. Conclusions
Two parameters, the stereochemistry of PLA and the incorporation of clay, have been studied to understand their inuence on the ageing of PLA laments. It was shown that the
D-content played a key role in the properties of PLA laments.
The lower the D-content, the higher the degree of crystallinity.
So, PLAb laments had higher degree of crystallinity, were
less sensitive to hydrolysis and kept their tensile properties
for a longer time during ageing in comparison with PLAg
laments.
The effect of the incorporation of silicate layers in PLA laments has also been demonstrated. It tended to promote the
hydrolysis of PLA, so it detrimentally affected the tensile
properties. This phenomenon could be explained by the presence of hydroxyl groups of the silicate, which would promote
the hydrolysis of PLA macromolecules.
So these two parameters can be adjusted to modulate the
lifetime of PLA laments. For long-time applications, PLA
with low D-content should be favoured. For short time applications, PLA with higher D-content and lled with organoclay
can be used.

S. Solarski et al. / Polymer Degradation and Stability 93 (2008) 707e713

Acknowledgements
This research programme is realized within the framework
of INTERREG III France-Wallonie. The authors thank the
FEDER funds (European Union), the Walloon region and the
Nord Pas-de-Calais region for the nancial support.
References
[1] Agrawal AK, Bhalla R. Advances in the production of poly(lactic acid) bres.
A review. J Macromol Sci Part C Polym Rev 2003;43(4):479e503.
[2] Gupta B, Revagade N, Hilborn J. Poly(lactic acid) bre: an overview.
Prog Polym Sci 2007;32(4):455e82.
[3] Alexandre M, Dubois P. Polymer layered silicate nanocomposites: preparation, properties and uses of a new class of materials. Mater Sci Eng
2000;28(1e2):1e63.
[4] Sinha Ray S, Okamoto M. Polymer/layered silicate nanocomposites: a review from preparation to processing. Prog Polym Sci 2003;28(11):1539e
641.
[5] Bourbigot S, Devaux E, Flambard X. Flammability of polyamide-6/clay
hybrid nanocomposite textiles. Polym Degrad Stab 2002;75(2):397e402.
[6] Yoon K, Polk MB, Min BG, Schiraldi DA. Structure and property study
of nylon-6/clay nanocomposite bre. Polym Int 2004;53(12):2072e8.
[7] Chang JH, An YU, Kim SJ, Im S. Poly(butylene terephtalate)/organoclay
nanocomposites prepared by in situ interlayer polymerization and its bre (II). Polymer 2003;44(19):5655e61.
[8] Chang JH, Kim SJ, Im S. Poly(trimethylene terephthalate) nanocomposite bres by in situ intercalation polymerization: thermo-mechanical
properties and morphology (I). Polymer 2004;45(15):5171e81.
[9] Chang JH, Kim SJ, Joo YL, Im S. Poly(ethylene terephthalate) nanocomposites by in situ interlayer polymerization: the thermo-mechanical
properties and morphology of the hybrid bres. Polymer 2004;45(3):
919e26.
[10] Chang JH, Kim SJ. Polyester nanocomposite bres: comparison of their
properties with poly(ethylene terephthalate) and poly(trimethylene terephthalate). Polym Bull 2004;52(3e4):289e96.
[11] Xiao W, Yu H, Han K, Yu M. Study on PET bre modied by nanomaterials: improvement of dimensional thermal stability of PET bre by
forming PET/MMT nanocomposites. J Appl Polym Sci 2005;96(6):
2247e52.
[12] Pavlikova S, Thomann R, Reichert P, Mulhaupt R, Marcincin A,
Borsig E. Fibre spinning from poly(propylene)eorganoclay nanocomposite. J Appl Polym Sci 2003;89(3):604e11.
[13] Zhang X, Yang M, Zhao Y, Zhang S, Dong X, Liu X, et al. Polypropylene/montmorillonite composites and their application in hybrid bre
preparation by melt-spinning. J Appl Polym Sci 2004;92(1):552e8.
[14] Miko1ajczyk T, Olejnik M. Analysis of the structure and properties of
polyimidoamide nanocomposite bres containing variously modied
montmorillonite. J Appl Polym Sci 2006;101(2):1103e8.

713

[15] Miko1ajczyk T, Rabiej S, Olejnik M, Urbaniak-Domaga1a W. Strength

properties of polyimideamide nanocomposite bres in terms of their
porous and supermolecular structure. J Appl Polym Sci 2007;104(1):
339e44.
[16] Solarski S, Mahjoubi F, Ferreira M, Devaux E, Bachelet P, Bourbigot S,
et al. (Plasticized) polylactide/clay nanocomposite textile: thermal,
mechanical, shrinkage and re properties. J Mater Sci 2007;42(13):
5105e17.
[17] Solarski S, Mahjoubi F, Ferreira M, Devaux E, Bachelet P, Bourbigot S,
et al. Designing polylactide/clay nanocomposites for textile applications:
effect of processing conditions, spinning and characterization. J Appl
Polym Sci, in press.
[18] Tsuji H, Ikarashi K, Fukuda N. Poly(L-lactide): XII. Formation, growth,
and morphology of crystalline residues as extended-chain crystallites
through hydrolysis of poly(L-lactide) lms in phosphate-buffered solution. Polym Degrad Stab 2003;84(3):515e23.
[19] Sinha Ray S, Yamada K, Ogami A, Okamoto M, Ueda K. New polylactide/layered silicate nanocomposite: nanoscale control over multiple
properties. Macromol Rapid Commun 2002;23(16):943e7.
[20] Sinha Ray S, Yamada K, Okamoto M, Ueda K. New polylactide-layered
silicate nanocomposites. 2. Concurrent improvements of material properties, biodegradability and melt rheology. Polymer 2003;44(3):857e66.
[21] Sinha Ray S, Yamada K, Okamoto M, Ueda K. Control of biodegradability of polylactide via nanocomposite technology. Macromol Mater Eng
2003;288(3):203e8.
[22] Tsuji H, Kawashima Y, Takikawa H, Tanaka S. Poly(L-lactide)/nanostructured carbon composites: conductivity, thermal properties, crystallization, and biodegradation. Polymer 2007;48(14):4213e25.
[23] Solarski S, Ferreira M, Devaux E. Thermal and mechanical characteristics of polylactide laments drawn at different temperatures. J Text Inst
2007;98(3):227e36.
[24] Tsuji H, Mizuno A, Ikada Y. Properties and morphology of poly(L-lactide). III. Effects of initial crystallinity on long-term in vitro hydrolysis
of high molecular weight poly(L-lactide) lm in phosphate-buffered solution. J Appl Polym Sci 2000;77(7):1452e64.
[25] Fox TG, Flory PJ. Second-order transition temperatures and related properties of polystyrene. I. Inuence of molecular weight. J Appl Phys
1950;21(6):581e91.
[26] Pluta M, Galeski A, Alexandre M, Paul MA, Dubois P. Polylactide/montmorillonite nanocomposites and microcomposites prepared by melt
blending: structure and some physical properties. J Appl Polym Sci
2002;86(6):1497e506.
[27] Di Y, Iannace S, Di Maio E, Nicolais L. Poly(lactic acid)/organoclay
nanocomposites: thermal, rheological properties and foam processing. J
Polym Sci Part B Polym Phys 2005;43(6):689e98.
[28] Pluta M. Morphology and properties of polylactide modied by thermal
treatment, lling with layered silicates and plasticization. Polymer
2004;45(24):8239e51.
[29] Sinha Ray S, Okamoto M. Biodegradable polylactide and its nanocomposites: opening a new dimension for plastics and composites. Macromol
Rapid Commun 2003;24(14):815e40.