Composites Science and Technology 70 (2010) 815–821

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Composites Science and Technology

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Functionalized cellulose nanocrystals as biobased nucleation agents

in poly(L-lactide) (PLLA) – Crystallization and mechanical property effects
Aihua Pei a, Qi Zhou a,b,*, Lars A. Berglund a,c
a
Department of Fiber and Polymer Technology, Royal Institute of Technology, SE-100 44 Stockholm, Sweden
b
School of Biotechnology, Royal Institute of Technology, AlbaNova University Center, SE-106 91 Stockholm, Sweden
c
Wallenberg Wood Science Center, Royal Institute of Technology, SE-100 44 Stockholm, Sweden

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

Article history: The important industrial problem of slow crystallization of poly(L-lactide) (PLLA) is addressed by the use
Received 9 November 2009 of cellulose nanocrystals as biobased nucleation reagents. Cellulose nanocrystals (CNC) were prepared by
Received in revised form 26 January 2010 acid hydrolysis of cotton and additionally functionalized by partial silylation through reactions with n-
Accepted 27 January 2010
dodecyldimethylchlorosilane in toluene. Such silylated cellulose nanocrystals (SCNC) were dispersible
Available online 1 February 2010
in tetrahydrofuran and chloroform, and formed stable suspensions. Nanocomposite films of PLLA and
CNC or SCNC were prepared by solution casting. The effects of surface silylation of cellulose nanocrystals
Keywords:
on morphology, non-isothermal and isothermal crystallization behavior, and mechanical properties of
Cellulose nanocrystals
A. Nano composites
these truly nanostructured composites were investigated. The unmodified CNC formed aggregates in
A. Particle-reinforced composites the composites, whereas the SCNC were well-dispersed and individualized in PLLA. As a result, the tensile
E. Casting modulus and tensile strength of the PLLA/SCNC nanocomposite films were more than 20% higher than for
B. Mechanical properties pure PLLA with only 1 wt.% SCNC, due to crystallinity effects and fine dispersion.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction nucleation density and thus to enhance the crystallization rate is

Poly(lactic acid) (PLA) is a biodegradable thermoplastic with
high-strength (50–70 MPa), high-modulus (3 GPa), and relatively
good biocompatibility. PLA has attracted much attention from mate-
rial researchers and industry due to its potential in biomedical appli-
cations, and as an engineering polymer based on renewable
resources. Because of the inherent brittleness and lower impact
resistance of PLA, considerable efforts have been made to improve
its properties in order to achieve the compatibility with thermoplas-
tics processing and manufacturing, and compete with commodity
polymers. Composites of PLA reinforced with natural and man-made
cellulose fibers [1] including regenerated cellulose fibers [2], wood
fibers [3], recycled newspaper fibers [4], plant fibers from kenaf
[5], and microfibrillated cellulose (MFC) [6–8] have been prepared
and exhibited improved biodegradability, thermal stability, and
mechanical properties. Such biocomposites are of great interest as
replacement of petroleum-based polymers since they are com-
pletely based on renewable resources. However, the slow crystalli-
zation of PLLA is a major problem industrially, since practical melt-
processing conditions results in products where the PLLA often is
in a state of very low crystallinity. An efficient method to increase
* Corresponding author. Address: School of Biotechnology, Royal Institute of
Technology, AlbaNova University Center, SE-106 91 Stockholm, Sweden. Tel.: +46 8
55378383; fax: +46 8 55378468.
E-mail address: qi@kth.se (Q. Zhou).
the addition of heterogeneous nucleating agents [9]. To broaden
the utilization of PLA, environmentally friendly and biocompatible
nucleating agents having excellent nucleation ability without any
limitations or drawbacks are desired.
Cellulose fibers have been used as a nucleating and reinforcing
material in the lignocellulosic/thermoplastic composites, in partic-
ularly the cellulose/polypropylene systems [10–13]. Transcrystal-
line morphology was observed on the surface of the cellulose
fibers. In addition, a transcrystalline layer of polypropylene at the
edge of films cast from cellulose nanocrystal suspensions has been
demonstrated by Gray [14]. Cellulose nanocrystals are highly crys-
talline cellulose particles produced by acid hydrolysis through par-
tially dissolving cellulose fibrils [15]. Using nanoscale cellulose
crystallites as fillers for PLA has advantages over inorganic fillers
because of their exceptionally unique characteristics such as bio-
degradability and biocompatibility, high stiffness, high aspect ratio
(length/diameter), and low density. A specific challenge to achieve
maximum performance of nanocomposites from PLA and cellulose
nanocrystals is the difficulty to obtain well-dispersed cellulose
nanocrystals in the PLA polymer matrix.
In our previous work [16], a high-strength elastomeric nanocom-
posite has successfully been prepared by dispersing microcrystalline
cellulose (MCC) in a polyurethane matrix with the addition of a small
amount of lithium chloride (LiCl). Biodegradable nanocomposites
from PLA and MCC have been prepared previously [17,18]. MCC
has higher capacity to act as a nucleating agents compared to cellu-

0266-3538/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2010.01.018
816 A. Pei et al. / Composites Science and Technology 70 (2010) 815–821
lose fibers due to the surface topography of the fiber [18]. MCC cellu-
lose fibrils remained as aggregates in the composites and had poor
adhesion with the PLA matrix, which resulted in poor mechanical
properties [17]. In order to improve the dispersion of MCC in PLA,
MCC was treated with N,N-dimethylacetamide (DMAc) containing
LiCl to swell and separate the cellulose whiskers. The mechanical
properties of the PLA/MCC composite were improved but DMAc/LiCl
caused degradation of the composite at high temperature processing
[19]. Further, cellulose nanowhiskers (CNW) were produced by acid
hydrolysis of MCC. An anionic surfactant [20], the acid phosphate es-
ter of ethoxylated nonylphenol, was utilized to improve the disper-
sion of CNW in the PLA matrix [21,22]. However, increased
surfactant content caused degradation of PLA.
In this study, cellulose nanocrystals were partially surface sily-
lated to improve their dispersion in PLLA. The PLLA/cellulose nano-
crystals composite films containing 1 wt.% and 2 wt.% of cellulose
were prepared by the solution casting method. The effect of surface
silylation of cellulose nanocrystals on morphology, non-isothermal
and isothermal crystallization behaviors, and mechanical proper-
ties of the nanocomposites were investigated by field emission
scanning electron microscopy (FE-SEM), polarized optical micros-
copy (POM), differential scanning calorimetry (DSC), and tensile
test.
2. Experimental
2.1. Materials
Poly(L-lactide) (PLLA, BiomerÒ L9000; weight average molecular
mass, Mw = 220 kDa, number average molecular mass, Mn =
101 kDa) was obtained from Biomer Inc. (Krailling, Germany). PLLA
resins were dried in a vacuum oven at 60 °C for 24 h before use.
The cellulose nanocrystal suspension was prepared from cotton
cellulose by sulfuric acid hydrolysis, following the recipe used by
Cranston and Gray [23].
2.2. Partial silylation of the cellulose nanocrystals
The cellulose nanocrystals were partially silylated following the
route developed by Gousse et al. [24]. CNC in aqueous suspension
(100 mg/mL) were solvent exchanged to acetone and then to dry
toluene in which they were precipitated because of the aggregates
formation. The n-dodecyldimethylchlorosilane (DDMSiCl) (Aldrich)
was then added with a molar ratio of 3:1 for DDMSiCl and anhy-
droglucose units (AGU) in cellulose. Imidazole used for trapping
the HCl released during the reaction was added in quantity equi-
molar to that of DDMSiCl. The graft reaction was conducted for
12 h at room temperature (22 °C) under vigorous stirring, and then
was terminated by adding a mixture of tetrahydrofuran (THF) and
methanol (80/20, v/v). The partially silylated cellulose nanocrystals
product was washed thoroughly with THF twice to remove the
impurities (e.g. imidazolium chloride and disilyl ether) by centrifu-
gation at 12,000g for 10 min at 4 °C and subsequent dispersion in
fresh THF. Such partially silylated cellulose nanocrystals (SCNC)
can be suspended in organic solvents such as THF and chloroform
and form stable homogeneous suspensions after sonication (Bran-
son SonifierÒ Model 250 ultrasonic cell disruptor/homogenizer) at
80% output (with cooling in an ice bath) for 1 min, while unmodi-
fied CNC aggregated and precipitated from THF and chloroform
solution after sonication.
2.3. Preparation of PLLA/cellulose nanocrystals composites
PLLA/cellulose nanocrystals nanocomposite films were pre-
pared by the solution casting method [25]. PLLA (0.2 g) was dis-
solved in 2 mL chloroform with vigorous stirring at room
temperature. The dissolved solution was poured onto a leveled
glass Petri dish with a diameter of 5 cm, and then allowed to dry
for about 24 h at room temperature. For the preparation of the
nanocomposite films, a predetermined amount of SCNC suspension
in chloroform (20 mg/mL) was mixed with the previously prepared
PLLA solution. The mixture solutions were stirred for 4 h before
they were cast onto the glass Petri dish and dried. The resultant
films with a thickness of ca. 70 lm were peeled from the glass Petri
dish after drying. PLLA/SCNC nanocomposite films with 1 wt.% and
2 wt.% of SCNC were prepared and coded as PLLA–SCNC-1 and
PLLA–SCNC-2, respectively. For comparison, PLLA/CNC nanocom-
posite films with 1 wt.% and 2 wt.% of CNC were prepared
following the same procedures as described above and coded as
PLLA–CNC-1 and PLLA–CNC-2, respectively. The pure PLLA film
was coded as PLLA. All films were dried in vacuum oven at room
temperature for 48 h to constant weight before further analysis.
2.4. Characterization
Fourier transform infrared spectroscopy (FTIR) were conducted
on a Perkin–Elmer Spectrum 2000 FTIR equipped with a MKII Gold-
en Gate, single reflection attenuated total reflectance (ATR) system
(Specac Ltd., London, UK). The ATR crystal was a MKII heated dia-
mond 45° ATR top plate. To avoid the superposition of many layers
of nanocrystals, a drop of the diluted CNC or SCNC suspensions in
THF (0.1% w/w) was mounted directly on a carbon-coated electron
microscopy grid. The specimens were observed using a Philips Tec-
nai 10 electron microscope operated at 80 kV. Although this meth-
od can create some drying artifacts, it is commonly used for the
observation of cellulose nanocrystals. A Hitachi S-4800 scanning
electron microscope was used to capture secondary electron
images of the cross section of the nanocomposite films. The films
were frozen in liquid nitrogen and fractured. The specimens were
fixed on a metal stub using carbon tape and coated with a dou-
ble-layer coating (5 nm) consisting of graphite and gold–palladium
using Agar HR sputter coaters. Differential Scanning Calorimetry
(DSC) measurements were taken on a Mettler Toledo DSC 820
using nitrogen as the purge gas. Samples of about 7.0 mg were en-
closed in aluminum pans. In the non-isothermal procedure, the
sample was first heated to 210 °C and held for 5 min, and then it
was cooled to 0 °C at a heating and cooling rates of 10 °C/min.
The melting temperature (Tm) and the enthalpy of cold crystalliza-
tion and melting (DHcc and DHm, respectively) were calibrated
using indium and tin as standards. For isothermal crystallization,
all samples were heated from room temperature to 210 °C and kept
for 5 min to completely eliminate any possible crystalline phase.
Then the samples were quenched to a desired isothermal crystalli-
zation temperature (125 °C, 120 °C, 115 °C, and 110 °C) and held
for sufficient time to allow crystallization completely from the qui-
escent melt. The exothermic curves of heat flow as a function of
time were recorded. Polarized Optical Microscopy (POM) was car-
ried out on a Leitz Ortholux POL BKII optical microscope equipped
with a Mettler Toledo Hot Stage FP82 controlled by Mettler FP90
Central Processor. Samples were prepared by melting a sample be-
tween two cover slips on a hot plate and gently pressing them to-
gether with tweezers. Isothermal crystallization was recorded by
heating the sample to 210 °C and holding for 5 min, then quench-
ing (20 °C/min) to 125 °C. Pictures were taken at specified inter-
vals. The mechanical properties of composites were measured
using a horizontal Miniature materials tester (MiniMat 2000) with
a 200 N load cell at a cross-head speed of 2 mm/min. The gauge
length is 10 mm. Samples were cut into rectangular pieces with
width of 3 mm. The results obtained from the Minimat 2000 can
only be used for comparison the samples in this study, because
the values are based on the rotational movement of the drive shaft.
 A. Pei et al. / Composites Science and Technology 70 (2010) 815–821 817

3. Results and discussion

3.1. Surface modification of cellulose nanocrystals

Cellulose nanocrystals are very difficult to disperse in a hydro-

phobic polymeric matrix as they have a large surface area and pos-
sess large hydrogen forces among themselves. Cellulose
nanocrystals can be dispersed in a polar organic solvent, N,N-
dimethylformamide (DMF) [26]. In addition, stable suspensions
of cellulose nanocrystals dispersed in organic medium have been
achieved by using a surfactant [20], or by surface chemical modifi-
cation, e.g. partially silylation [24]. As inspired by the PLA/clay
nanocomposites [27,28], in which organically modified montmo-
rillonite (MMT) was often applied to increase the hydrophobicity
and enhance the dispersion, we employed the surface chemical
modification method to disperse cellulose nanocrystals in organic
solvents and the PLLA matrix.
The FTIR spectra of unmodified and partially silylated cellulose
nanocrystals are shown in Fig. 1. The band at around 1050 cm–1,
which is the most intensive in the spectrum of CNC (Fig. 1a), has
been identified in the SCNC sample (Fig. 1b) as corresponding to
the pyranose ring ether band of cellulose. The successful silylation
of cellulose nanocrystals was proved by the presence of the charac-
teristic bands at 779 cm–1 and 840 cm–1 that were attributed to Si–
CH3 stretching and bending, respectively [29]. In addition, new
bands at 2922 cm–1 (asymmetrical CH2 stretching vibration) and
2852 cm–1 (symmetrical CH2 stretching vibration) introduced by
the silylating agent n-dodecyldimethylchlorosilane were also Fig. 2. Transmission electron micrographs of (a) CNC and (b) SCNC from THF
detected. suspension (scale bar, 1000 nm).
The dispersion quality of SCNC in non-polar organic solvents
was confirmed by the visualization of the individualized nanocrys-
tals using transmission electron microscopy (TEM). The formation in the form of bundles is a typical feature observed previously
of aggregates was observed for unmodified cellulose nanocrystals for cotton microcrystals in aqueous suspensions [30].
as shown in Fig. 2a. After surface silylation, a good dispersion
was observed for the cellulose nanocrystals suspension in THF.
3.2. Morphology of nanocomposite films
Fig. 2b displays the TEM micrograph of SCNC dried from dilute
THF suspension. The nanocrystals were well individualized with
Fig. 3 shows FE-SEM images of the cryo-fractured surfaces of
typical dimensions ranging mostly from 200 to 300 nm in length
pure PLLA and cellulose nanocrystals nucleated PLLA composite
and around 15 nm in width. The level of dispersion of SCNC in
films. In the PLLA–CNC-2 composite with unmodified CNC
THF is better than the surfactant assisted dispersion of cotton cel-
(Fig. 3b), the cellulose nanocrystals were agglomerated in the PLLA
lulose nanocrystals in toluene, in which bundles of nanocrystal
matrix. Fig. 3c shows that the dispersion of cellulose nanocrystals
aggregates were observed [20]. Aggregates of a few nanocrystals
in PLLA was dramatically improved with surface partial silylation
on CNC. The surface of the PLLA–SCNC-2 composite sample was
smooth as the pure PLLA surface (Fig. 3a) and no visible micro-
100
scale aggregations of SCNC were observed. Such morphology is dif-
a ferent from the cryo-fractured surfaces of tunicin whiskers filled
Transmittance (%)

80 nanocomposites prepared from a DMF solution, where tunicin

whiskers appear like white dots corresponding to the transversal
60
sections of the cellulose whiskers [26]. This is due to the fact that
40 the length of tunicin cellulose whisker is in the range of microme-
ters, while it is only 200–300 nm for cellulose nanocrystals. In con-
20 clusion, the smooth fracture surface in Fig. 3c indicates the
4000 3500 3000 2500 2000 1500 1000 600
presence of well-dispersed SCNC particles and successful prepara-
100
tion of a truly nanostructured composite based on PLLA and SCNC.
Transmittance (%)

b
80
3.3. Crystallization and melting behaviors
60
The non-isothermal crystallization and melting behavior of the
40 PLLA/cellulose nanocrystal composites were investigated by DSC.
In the heating scans (Fig. 4a), all samples showed a distinct exo-
20
4000 3500 3000 2500 2000 1500 1000 600 thermic peak, attributing to the cold crystallization during heating
process. The melting temperatures (Tm) of PLLA in the nanocom-
Wavenumber (cm -1)
posites were similar to that of pure PLLA. For semicrystalline poly-
Fig. 1. FTIR spectra of (a) cellulose nanocrystals (CNC) and (b) cellulose nanocrys- mers, crystallinity may strongly influence mechanical properties.
tals that were partially silylated with n-dodecyldimethylchlorosilane (SCNC). The degree of crystallinity (Xc) estimated from DSC curves for PLLA
818 A. Pei et al. / Composites Science and Technology 70 (2010) 815–821

PLLA

PLLA-CNC-1

PLLA-CNC-2

Endo
PLLA-SCNC-1

PLLA-SCNC-2

0 50 100 150 200

Temperature (oC)

PLLA

PLLA-CNC-1
Endo PLLA-CNC-2

PLLA-SCNC1

PLLA-SCNC2

0 50 100 150 200

Temperature (oC)

Fig. 4. DSC (a) heating and (b) cooling scans of PLLA and PLLA/cellulose nanocrys-
tals nanocomposites.

Table 1
Fig. 3. FE-SEM micrographs of the cryo-fractured surfaces of (a) pure PLLA film, (b) Thermal parameters of PLLA and PLLA/cellulose nanocrystals composites derived
PLLA–CNC-2 and (c) PLLA–SCNC-2 nanocomposite films. from the heating DSC scans.

Tm (°C) DHm (J/g)a DHcc (J/g)a Xc (%)

PLLA 171.4 25.8 12.5 14.3
and PLLA/cellulose nanocrystals composites are summarized in Ta-
PLLA–CNC-1 171.4 28.2 12.9 16.4
ble 1. The following equation was used to calculate Xc, PLLA–CNC-2 171.8 30.0 16.0 15.0
PLLA–SCNC-1 171.8 32.3 4.0 30.4
PLLA–SCNC-2 171.4 29.4 10.1 20.7
DHm  DHcc
Xc ¼  100% ð1Þ
DH 1
m
a
Data corrected for the percentage of PLLA in the nanocomposites.

where DHm is the measured endothermic enthalpy of melting and
DHcc is the exothermic enthalpy that is absorbed by the crystals
formed during the DSC heating scan. The theoretical melting enthal-
py of 100% crystalline PLLA was taken (DH1 m = 93.0 J/g) [28]. Com-
pared with the pure PLLA sample, the Xc values of PLLA in the
PLLA/CNC nanocomposites were increased slightly, while the Xc val-
ues of PLLA in the PLLA/SCNC nanocomposites were increased sig-
nificantly by using surface silylated cellulose nanocrystals as the
nucleating agents, e.g. from 14.3% to 30.4% for PLLA–SCNC-1. This
result is comparable with the composite of PLA containing 25%
(by weight) MCC where an increase from 19.2% to 44.5% was re-
ported [18]. In the cooling scans (Fig. 4b), the exothermic peaks
with very low intensity were observed for the pure PLLA and
PLLA/CNC nanocomposite samples, indicating a rather low crystalli-
zation capability. As for the PLLA/SCNC nanocomposite samples, the
crystallization peaks had relatively higher intensity and started
from higher temperature as a result of enhanced crystallizability.
The nucleation effect was remarkably enhanced when homoge-
neous cellulose nanocrystals dispersion in PLLA was achieved.
3.4. Polarized optical microscopy observations
The effect of the addition of unmodified and surface silylated cel-
lulose nanocrystals in the PLLA matrix as nucleation agents on the
crystallization behavior were observed by polarized optical micro-
scope. Optical micrographs were taken on the 0, 5th and 10th min
at 125 °C after quenched from melt at 210 °C for the PLLA, PLLA–
CNC-1 and PLLA–SCNC-1 samples (Fig. 5). Both PLLA and PLLA–
SCNC-1 samples showed clean and uniform melt, while micro-scale
aggregates of cellulose nanocrystals were found in the PLLA–CNC-1
sample before crystallization (0 min). This further indicated that
surface silylated cellulose nanocrystals were better dispersed in
the PLLA matrix compared to the unmodified ones. The processes
of nucleation and growth control the crystallization kinetics. When
 A. Pei et al. / Composites Science and Technology 70 (2010) 815–821
Fig. 5. Polarized optical microscope images of PLLA, PLLA–CNC-1, and PLLA–SCNC-1 acquired on the 0, 5th and 10th min at 125 °C after quenched from melt at 210 °C. Scale
bar, 200 lm.
the heterogeneous nucleating agent is added, an increase in the
overall crystallization rate occurs with a reduction of the nucleation
induction period and also an increase in the number of primary
nucleation sites [31]. With the addition of CNC, the nucleus density
of PLLA crystallites increased at 5 min and 10 min as compared to the
pure PLLA. Furthermore, the nucleus density increased significantly
with the addition of SCNC, due to improved dispersion of cellulose
nanocrystals in the PLLA matrix. As a result, more crystals were able
to nucleate and grow on the increased surface area of the interfaces
due to increasing numbers of nucleating particles. Similar phenom-
ena were reported by Gurato et al. [32], who found that smaller talc
particles were more effective in increasing crystallization rate than
larger ones for nylon 6.
3.5. Isothermal crystallization kinetics
In order to fully understand the effect of the addition of unmod-
ified and surface silylated cellulose nanocrystals on the bulk crys-
tallization rate of PLLA, isothermal crystallization behaviors of the
PLLA/cellulose nanocrystals nanocomposites were also studied.
The isothermal crystallization exotherms of (a) PLLA, (b) PLLA–
CNC-1, and (c) PLLA–SCNC-1 under different crystallization tem-
perature (Tc) are shown in Fig. 6. Within the same sample, the shift
of exotherms to longer time with increasing Tc indicated a decrease
of the crystallization rate. As for the same Tc, it is clear that the
crystallization time of PLLA–SCNC-1 (Fig. 6c) was much shorter
than that of PLLA and PLLA–CNC-1. These results indicated that
the crystallization rate of PLLA increased with surface silylated cel-
lulose nanocrystals as nucleating agents.
The relative crystallinity (Xt) as a function of crystallization time
(t) is calculated as follows:
Rt
ðdH=dtÞdt
0
Xt ¼ R 1
ðdH=dtÞdt
0
819
To describe the isothermal crystallization kinetics, the classical
Avrami equation was employed:
log½ lnð1  X t Þ ¼ log k þ n log t ð3Þ
where k is the overall kinetic constant depending on the geometry
of the growing crystalline phase, and n is the Avrami exponent cor-
relating with the nucleation mechanism and crystal growth dimen-
sion. The values of log[ln(1  Xt)] were plotted versus log t, and
the Avrami exponent n and the crystallization rate constant k were
calculated from the slope and intercept of the linear fit. The Avarmi
equation rarely describes the whole crystallization process and is
usually valid at the primary crystallization stage [33]. Thus, the ini-
tial linear portions of the plots were analyzed and the results are
summarized in Table 2. The k values of the PLLA/SCNC samples were
higher compared to those of the PLLA and PLLA/CNC samples, in
particular, the k values increased by almost one order of magnitude
at Tc of 125 °C. The Avrami exponent, n, relates to the nature of
nucleation and the dimensionality of the growing crystals. The n
values of PLLA were around 2.8–3.3, suggesting a three-dimensional
crystallization growth and homogeneous nucleation mechanism
[27,34]. The obtained n values were similar to those reported for
pure PLLA (2.3–3.2 at Tc = 90–130 °C by Tsuji et al. [35], and 2.8–
3.2 at Tc = 90–130 °C by Iannace and Nicolais [36]). The n values
of PLA/SCNC biocomposites were around 3.5–4.9, indicating a crys-
tallization mode of heterogeneous nucleation [37,38]. Similar n val-
ues were reported for PLA/nucleating agent (BaSO4, CaCO3, and
TiO2) composites, where the Avrami exponent n is in the range of
4.0–5.2 [39].
Half-time of crystallization (t1/2) is defined as the time when Xt
is equal to 0.5 and is calculated as follows [40]:
 1=n
ln 2
ð2Þ t1=2 ¼ ð4Þ
k
820 A. Pei et al. / Composites Science and Technology 70 (2010) 815–821

Table 2
a Avrami kinetic parameters for the isothermal crystallization of the PLLA and PLLA/
cellulose nanocrystals composites.

Sample Tc (°C) n k (minn) t1/2 (min)

PLLA 110 2.81 1.62  10–3 8.6
115 2.92 9.12  10–4 9.7
120 3.16 7.94  10–5 17.7
125 3.28 1.25  10–5 27.9
o
Endo

125 C
PLLA–CNC-1 110 3.47 3.16  10–4 9.2
115 3.34 3.09  10–4 10.1
120 3.32 1.99  10–4 11.7
o 125 3.24 6.02  10–5 17.9
120 C
o
o
115 C PLLA–CNC-2 110 3.30 3.82  10–4 9.7
110 C 115 3.15 3.78  10–4 10.9
120 3.24 1.78  10–4 12.8
125 3.31 4.07  10–5 19.0
10 20 30 40 50 60
PLLA–SCNC-1 110 4.07 2.09  10–3 4.2
Crystallization time (min) 115 4.13 1.02  10–3 4.9
120 4.26 4.68  10–4 5.5
125 3.61 4.17  10–4 7.8
b
PLLA–SCNC-2 110 4.91 1.14  10–3 5.9
115 4.35 7.76  10–4 4.8
120 4.08 4.78  10–4 6.0
125 3.82 2.18  10–4 8.3
Endo

o
125 C
Table 3
o
120 C Mechanical properties of PLLA and cellulose nanocrystals nucleated PLLA composite
films at room temperature.
o
115 C
Tensile Tensile Elongation
o modulus (GPa) strength (MPa) at break (%)
110 C
PLLA 1.1 ± 0.01 48.3 ± 2.9 31.1 ± 3.0
PLLA–CNC-1 1.0 ± 0.02 49.2 ± 0.4 10.5 ± 2.0
10 20 30 40 50 60 PLLA–CNC-2 1.2 ± 0.03 48.3 ± 0.4 12.2 ± 0.2
PLLA–SCNC-1 1.4 ± 0.08 58.6 ± 3.1 8.3 ± 0.6
Crystallization time (min) PLLA–SCNC-2 1.4 ± 0.04 53.8 ± 2.1 7.1 ± 1.8

c
the micro-scale agglomeration of CNC as shown in Fig. 2a, did
not show improvements in tensile modulus and tensile strength
compared to pure PLLA. Meanwhile, the addition of only 1 wt.%
of SCNC in PLLA resulted in a 27% increase in tensile modulus
o
and a 21% increase in the tensile strength compared to pure PLLA.
Endo

125 C
The main reason is increased degree of crystallinity (see Table 1),
and the associated truly nanostructural characteristics resulting
120 C
o from more efficient dispersion and alignment of the functionalize
115 C
o nanocrystals (SCNC) as shown in Fig. 2b. The elongation to break
110 C
o is affected by the volume fraction of the added reinforcement,
the dispersion of the reinforcement in the matrix, and the interac-
tion between the reinforcement and the matrix. The elongation at
10 20 30 40 50 60 break was reduced in both PLLA/CNC and PLLA/SCNC composite
Crystallization time (min) samples. The reason is that stiff reinforcements of cellulose nano-
crystals cause substantial local stress concentrations and failure at
reduced strain. In addition, although the partial surface silylation
Fig. 6. Isothermal crystallization exotherms of PLLA (a), PLLA–CNC-1 (b), and PLLA– of cellulose nanocrystals improved their degree of dispersion, it
SCNC-1 (c) under different crystallization temperatures (Tc). seems unlikely that the interfacial adhesion between PLLA and cel-
lulose nanocrystals was enhanced.
The results are also listed in Table 2. Generally, the t1/2 value in-
creased with increasing of Tc. The t1/2 values of PLLA/SCNC biocompos-
ites were lower than those of pure PLLA and PLLA/CNC biocomposites, 4. Conclusions
indicating rapid bulk crystallization rate by the addition of well-dis-
persed surface silylated cellulose nanocrystals in the PLLA matrix. The slow crystallization of PLLA was addressed by addition of a
biobased nucleating agent in the form of cellulose nanocrystals.
3.6. Mechanical properties The hypothesis of silane-treatment as a means to improve nucle-
ation efficiency was tested. Fine nanocrystals of 15 nm width and
The mechanical properties are summarized in Table 3. The 200–300 nm length were functionalized by partial silylation (SCNC
PLLA/CNC samples, which were actually microcomposites due to particles), in order to improve their dispersion in PLLA. Their fine dis-
 A. Pei et al. / Composites Science and Technology 70 (2010) 815–821
persion in organic solvents was confirmed experimentally. The crys-
tallization rate was strongly increased by only 1% SCNC addition,
whereas CNC particles did not have as strong effects. Compared with
PLLA/CNC, the PLLA/SCNC composites were truly nanostructured
with a highly dispersed nanocrystal phase and the associated larger
specific surface area for crystallite nucleation. This observation is in
support of the presented hypothesis of silane-functionalized cellu-
lose nanocrystals. Furthermore, the increased degree of crystallinity
significantly improved tensile modulus and strength of the nano-
composite. The strain-to-failure decreased with SCNC and CNC addi-
tion, and possibly the interfacial PLLA–nanocrystals adhesion could
be improved in order to address this problem. Reducing the length of
cellulose nanocrystals (i.e. to obtain nanospheres instead of rods) is
expected to increase the nucleation efficiency, although this may de-
crease the potential reinforcement effect associated with the high
aspect ratio of nanocrystals.
Acknowledgements
This work was performed at the Swedish Center for Biomimetic
Fiber Engineering (Biomime; http://www.biomime.org/) funded by
the Swedish Foundation for Strategic Research (SSF). For A. Pei and
L.A. Berglund, part of the funding was from Wallenberg Wood Sci-
ence Center.
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