COMPOSITES

SCIENCE AND
TECHNOLOGY
Composites Science and Technology 66 (2006) 2776–2784
www.elsevier.com/locate/compscitech

Manufacturing process of cellulose whiskers/polylactic acid

nanocomposites
K. Oksman *, A.P. Mathew, D. Bondeson, I. Kvien
Department of Engineering Design and Materials, Norwegian University of Science and Technology, Richard Birkelands vei 2b, NO-7491 Trondheim, Norway

Received 22 November 2005; received in revised form 28 February 2006; accepted 2 March 2006
Available online 18 April 2006

Abstract

Cellulose whiskers separated from commercially available microcrystalline cellulose (MCC) and polylactic acid (PLA) were used to
develop novel nanostructured biocomposites by compounding extrusion. MCC was treated with N,N-dimethylacetamide (DMAc) con-
taining lithium chloride (LiCl) in order to swell the MCC and partly separate the cellulose whiskers. The suspension of whiskers was
pumped into the polymer melt during the extrusion process. Different microscopy techniques, thermogravimetric analysis, X-ray diffrac-
tion and mechanical testing were used to study the structure and properties of the whiskers and composites. The results showed that
DMAc/LiCl can be used as swelling/separation agent for MCC but seems to cause degradation of the composites at high temperature
processing. The structure of composites was made up of partly separated nanowhiskers when PEG was used as processing aid. The
mechanical properties of nanocomposites were improved and compared to reference material the elongation to break was increased
about 800% for one material combination. The future studies will be focused on process optimization, dispersion of nanowhiskers
and finding a more suitable pumping medium to avoid thermal degradation of the composite.
 2006 Elsevier Ltd. All rights reserved.

Keywords: A. Nanostructures; E. Extrusion; B. Mechanical properties; D. Thermogravimetric analysis (TGA); D. Transmission electron microscopy
(TEM); D. X-ray diffraction (XRD)

1. Introduction Lately, inspired by the growing environmental aware-

Nanocomposite describes a two-phase material where
one of the phases has at least one dimension in nanometer
range (1–100 nm) and usually results in composites with
superior thermal, barrier and mechanical properties. A
large variety of clay based nanocomposites have been pre-
pared using different polymer matrices like nylon, polypro-
pylene, polystyrene, polyurethane, etc. The preparation
methods are usually solution casting, in situ polymerization
or melt compounding. The advantage of nanocomposite
materials is their superior thermal, mechanical and barrier
properties even at very low reinforcement content
(5 wt%) and also better recyclability and low weight com-
pared to conventional composites [1–4].
*
Corresponding author. Tel.: +47 735 93626; fax: +47 735 94129.
E-mail address: kristiina.oksman@ntnu.no (K. Oksman).
ness and new standards, there is a deliberate attempt and
interest to develop environmental friendly and biodegrad-
able systems with improved performance. The production
of ‘green materials’ based on raw materials derived from
natural resources of plant or animal origin are of great
interest both in the academic and industrial fields. Some
studies based on bio-nanocomposites using clay as nano
reinforcement in polylactic acid (PLA), poly(butylene suc-
cinate) (PBS), polycaprolactone (PCL), polyhydroxy buty-
rate (PHB) and aliphatic polyesters have been reported by
scientists in recent years [5–9]. Substituting the clay rein-
forcement with cellulose based reinforcement will lead to
fully degradable and renewable nanocomposites and dur-
ing the last decade there has been a growing interest in
incorporating cellulose whiskers [10–13].
Cellulose fibres are bundles of microfibrils (elementary
fibrils) where the cellulose molecules are stabilized laterally

0266-3538/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2006.03.002
 K. Oksman et al. / Composites Science and Technology 66 (2006) 2776–2784
by hydrogen bond between hydroxyl groups. The microfi-
brils consist of monocrystalline cellulose domains linked
by amorphous domains. The fibril can be about 5–10 nm
in diameter and the length varies from 100 nm to several
micrometers depending of the source of cellulose. Upon
acid hydrolysis the microfibrils undergo transverse cleavage
along the amorphous regions and releasing crystalline cel-
lulose or whiskers. Due to the near perfect crystalline
arrangement of whiskers they have high modulus and will
potentially act as efficient reinforcing materials. Properties
of cellulose crystallites from different earlier reports are
concluded and shown in Table 1 [10–12,14–16].
The interest for preparing cellulose nanocomposites
started by a research group at CERMAV-CNRS, Grenoble,
France around 1994. They prepared nanocomposites by
solution casting of various biodegradable matrices and
nanoreinforcements in aqueous medium [11,12,16]. Nanore-
inforcements used were of plant or animal origin like wheat
straw, tunicin, chitin, sugar beet, etc. They succeeded in
developing nanocomposites with uniform dispersion and
significant improvement in mechanical strength even at very
low reinforcement content. One drawback using cellulose
whiskers is the difficulty to disperse them uniformly in
non-polar medium because of their polar surface. Therefore,
the use of cellulose whiskers in nanocomposites has mainly
been limited to aqueous or polar environment. However,
Fleury and his group have recently reported a new method
of preparing stable suspension of cellulose whiskers in
organic solvents by partial and controlled silylation of the
whiskers using alkyldimethylchlorosilanes [17]. Another
recent approach is the mixing of surfactants with cellulose
whiskers in aqueous suspensions, followed by freeze–drying
and redispersing in organic solvents [18]. Cellulose nano-
composites based on cellulose nanocrystals from bacterial
cellulose and cellulose acetate butyrate prepared by solution
casting was reported by Grunert and Winter [13]. Wu et al.
prepared elastomeric PU/cellulose nanocomposites by
in situ polymerization [19]. The conclusion from these earlier
works is that the separation of nanoreinforcements from
natural materials and the processing techniques have been
limited to laboratory scale (few grams). Therefore, it will
be important to develop new processing techniques which
will be possible to use industrially. Until now, no reports
are available on processing of bio-nanocomposites with
matrices like PLA reinforced with cellulose whiskers by melt
compounding technique.
Polylactic acid is a versatile polymer made from renew-
able agricultural raw materials and is fully biodegradable.
Table 1
Properties of cellulose crystallites [10–12,14–16]
Property Cellulose crystallites
Length (nm) 300–2000
Diameter (nm) 5–20
Aspect ratio (L/d) 20–60
Tensile strength (MPa) 10,000
E-modulus (GPa) 150
2777
Another interesting feature that makes this polymer inter-
esting is the fact that it can be processed similarly like poly-
olefins. Furthermore, PLA owns good stiffness and
strength. Today, there is a large interest to use PLA in
packaging, medical but also in automotive applications
where also other properties than strength and stiffness are
important. It is therefore interesting to study if the incorpo-
ration of nanowhiskers can improve the toughness, thermal
stability and also barrier properties of the PLA. The pro-
cessing of novel biomaterials will set new challenges in
the field of plastics engineering, and especially the process-
ing of nanocomposites sets new requirements to processing
equipment, optimization and control.
Generally, the main difficulty in melt compounding of
nanocomposites is to achieve well dispersed nano-rein-
forcements in the polymer matrix. Today, it is possible to
find surface modified clays for different polymer systems
which can be directly dry mixed with the polymer to make
a nanocomposite or a master batch [20–22]. However,
when using commercially available MCC the surface is
not modified and therefore MCC exists as aggregates which
are difficult to separate during the extrusion process [23].
The main focus of this work has been to identify new
sources of cellulose whiskers, finding a suitable medium
to separate the cellulose whiskers, and to develop a new
processing technique for a larger scale production of cellu-
lose nanocomposites. Different microscopic techniques,
thermogravimetric analysis (TGA) and X-ray diffraction
were used to study the structure of the whiskers and com-
posites. The mechanical properties were studied in order to
evaluate how the addition of cellulose whiskers and pro-
cessing aids affected the composites modulus, strength
and elongation to break.
This study is the first attempt to prepare cellulose nano-
composites by melt extrusion technique using a commer-
cially available grade of MCC in a biodegradable
polyester matrix. To the best of our knowledge, this is
the first report on melt compounding of biopolymer based
cellulose nanocomposite.
2. Experiment
2.1. Materials
Matrix: Poly lactic acid (PLA), Nature WorksTM 4031 D,
supplied by Cargill Dow LLC, Minnetonka, MN, USA.
The density is 1.25 g/cm3, glass transition temperature
(Tg) 58 C and melting point (Tm) 160 C. The molecular
weight (Mw) is between 195,000 and 205,000 g/mol and
the melt flow index (MFI) is 2–5 g/10 min (190 C,
2.16 kg).
Reinforcement: Micro crystalline cellulose (MCC), Ceo-
lus KG-802, supplied by Asahi Kasei Corp. Tokyo, Japan.
Ceolus KG-802 is commercially available and was used as
raw materials for the swelling/separation of the whiskers. It
is pure microcrystalline cellulose and the particle size is
between 10 and 15 lm.
2778 K. Oksman et al. / Composites Science and Technology 66 (2006) 2776–2784
Chemicals: N,N-Dimethyl acetamide (DMAc) and lith-
ium chloride (LiCl) was used as swelling/separation and
pumping medium. Polyethylene glycol (PEG1500) was
used as processing aid to decrease the viscosity of the sys-
tem. Maleic anhydride (MA) was used to modify PLA.
These chemicals were purchased from Merck-Schuchardt,
Germany. Maleated PLA (PLA-MA), with a maleic anhy-
dride content of 2.2%, was prepared according to Shiraishi
and Ajoika [24] and was used as processing aid as well as
coupling agent.
2.2. Processing of cellulose nanocomposites
2.2.1. Swelling and separation of microcrystalline cellulose
The microcrystalline cellulose was swelled and partly
separated to whiskers by chemical and ultra sonification
treatments. DMAc with 0.5 wt% LiCl solution was used
as swelling agent. The initial concentration of MCC in
DMAc/LiCl was 10 wt% which was agitated using a mag-
netic stirrer for 12 h at 70 C to swell the MCC particles.
The slightly swelled particles were then sonified in an ultra-
sonic bath for 3 h over a period of 5 days with long inter-
vals between each sonification treatment, to separate
cellulose nano whiskers (CNW). The processed CNW sus-
pension was concentrated from 10% to 17% (percent by
weight) by vacuum drying before pumping it into the extru-
der to minimize the amount of chemicals introduced.
2.2.2. Extrusion
The composite materials were compounded using a co-
rotating twin screw extruder (Coperion Werner & Pflei-
derer ZSK 25 WLE, Germany) with a gravimetric feeding
system for dry materials (K-Tron AG, Switzerland) and a
peristaltic pump (Drive PD 5006, Heidolph Instruments
GmbH, Germany) for the cellulose whiskers suspension.
The pumping speed was 1.5 kg/h and it was calibrated to
ensure the cellulose content of 5 wt% in the final composi-
tion. The extrusion was carried out in the temperature
range of 170–200 C and the screw speed was held constant
at 150 rpm. The total throughput was 5 kg/h and the max-
imum capacity of this extruder is 50 kg/h. Fig. 1 shows a
schematic picture of the compounding process. PLA poly-
mer was fed in zone 1 and the cellulose whiskers suspension
was pumped into the melted polymer at zone 4. The liquid
phase was removed by atmospheric venting in zones 7 and
8 and by vacuum venting in zone 10. Both PLA-MA and
PEG were premixed with PLA depending on the formula-
tions and fed in zone 1. Table 2 summarizes the processing
Fig. 1. Schematic picture of the compounding process: Feeding of PLA in
zone 1, pumping of dispersed of CNW in zone 4 and removal of the liquid
using atmospheric and vacuum venting in zones 7, 8 and 10.
Table 2
Processing parameters
Parameter Value
Main feeder (kg/h) 4.75–5
Pumping rate (kg/h) 1.5
Screw rotation speed (rpm) 150
Motor load (torque) (%) 40–55
Pressure at the die (bar) 2
parameters and the formulations and the final composition
are summarized in Table 3. The amount of DMAc/LiCl
was 20 wt% and it was removed by the venting system dur-
ing the extrusion. The extruded materials were compression
moulded to 1.3 mm thickness, test samples were prepared
by cutting strips of the materials with a width of 7 mm.
2.3. Characterization of nanostructures
2.3.1. Microscopy
The morphology of the raw material (MCC) was studied
using a scanning electron microscope (SEM), Cambridge
360, using 10 kV acceleration voltage and the studied mate-
rial was sputter coated with Au to avoid charging. The
swelling/separation process of cellulose whiskers from
MCC was studied using optical microscope (OM) (Leica
DMLB). The cellulose whiskers as well as prepared com-
posites were studied using a Philips CM30 transmission
electron microscope (TEM), at an acceleration voltage of
100 kV. To examine the cellulose whiskers, one droplet of
1% diluted suspension was put on a Cu-grid covered with
a thin carbon film. To enhance contrast in TEM, the
nano-sized whiskers were negatively stained in a 1 wt%
solution of uranyl acetate (a heavy metal salt) in de-ionized
water for 1 min. To study the bulk morphology of compos-
ites, a small piece with a cross-sectional area of 2 · 7 mm2
was embedded in epoxy and cured overnight in room tem-
perature. The final ultra microtoming was performed with
a diamond knife at room temperature generating electron
transparent foils, being app. 50 lm in thickness.
2.3.2. Mechanical testing
Tensile testing was carried out using a miniature material
tester MiniMat 2000 (Rheometric Scientific), using a load
cell of 1000 N and the cross head speed was 3 mm/min.
The length between the gaps was 60 mm. At least five sam-
ples for every material were tested and the test results are
presented as relative values compared to pure PLA. The
reason for this is that data from MiniMat are just qualita-
tive because the strain values are not based on an extensom-
eter but on the rotational movement of a drive shaft.
2.3.3. Thermogravimetric analysis
Thermogravimetric analysis (TGA) was performed
using a TA Instruments SDT 2960 analyzer. The isother-
mal tests were carried out in air atmosphere at 180 C dur-
ing 40 min to see if DMAc/LiCl is degrading the cellulose
whiskers.
 K. Oksman et al. / Composites Science and Technology 66 (2006) 2776–2784 2779

Table 3
Formulations of prepared materials during processing and the final composition (% by weight)
PLA PLA-MA PEG DMAc/LiCl DMAc/LiCl/CNW Final composition
100 – – – – PLA (100)
90 10 – – – PLA/PLA-MA (90/10)
100 – – 20a – PLADMAc (100)
85 – 15 – – PLA/PEG (85/15)
85 10 – – 20a/5 PLA/PLA-MA/CNW (85/10/5)
70 10 15 – 20a/5 PLA/PLA-MA/PEG/CNW (70/10/15/5)
a
Pumped liquid which is removed during extrusion.

2.3.4. X-ray studies between the crystallites. The swollen MCC was then partly
Wide angle X-ray diffraction (WAXD), Siemens Diffrac- separated to cellulose nano whiskers (CNW) by ultrasonic
tometer D5005, was used to study the crystallinity of the treatment. It was expected that the shearing forces in the
pure components and prepared composites. The samples extrusion process would further contribute to the separa-
were exposed for a period of 11 s for each angle of inci- tion of the cellulose whiskers from the swollen MCC.
dence (h) using a Cu X-ray source with a wavelength (k) Fig. 3 shows the optical micrographs of MCC at the start
of 1.541 Å. The angle of incidence was varied from 1.5 to of the swelling and separation process and after the treat-
40 by steps of 0.06. ments. Fig. 3a shows large aggregates of MCC and
Fig. 3b shows how these large aggregates have broken
3. Results down after the treatments.
To confirm the separation of individual crystallites or
3.1. Swelling/separation of cellulose whiskers whiskers, a diluted suspension was observed using TEM
and is shown in Fig. 4. The figure shows separated cellulose
Microcrystalline cellulose is highly crystalline and is
obtained by the acid hydrolysis of wood pulp. Our earlier
study on microcrystalline cellulose showed that each parti-
cle of MCC is an aggregation of a large number of crystal-
lites [23]. Fig. 2 shows a detailed view of MCC and it is
possible to see that it is an aggregation of crystalline enti-
ties with voids and pores in between. As a first step, to sep-
arate individual whiskers the MCC was swollen in a
swelling agent followed by sonification. DMAc with low
concentration of LiCl has been reported to be a good swell-
ing agent for cellulose [25]. In an earlier study, we showed
that DMAc containing 1 wt% LiCl was an effective swell-
ing/separation agent for MCC [26] but Potthast et al.
reported that LiCl can cause degradation of cellulose
[27]. Therefore, DMAc containing a lower amount of LiCl
(0.5 wt%) was chosen as swelling agent in this study. This
swelling agent was expected to widen the pores and voids
in MCC and decrease the amount of hydrogen bonds

Fig. 2. SEM picture of MCC showing the aggregate of cellulose Fig. 3. The swelling and separation of 1% of MCC in DMAc/LiCl: (a)
crystallites. start, (b) after the sonification process.
2780 K. Oksman et al. / Composites Science and Technology 66 (2006) 2776–2784

Fig. 5. TGA Isotherms of MCC and isolated MCC with DMAc/LiCl,

(CNW) in 180 C during 30 min.

process temperature. Fig. 5 shows the isothermal TGA

curves. It can be seen that the whiskers were influenced
by the swelling/separation treatment and seemed to
degrade faster compared to MCC before treatment. The
materials were not exposed as long to this high temperature
during the processing but it is a clear indication that the
Fig. 4. Transmission electron micrograph of diluted suspension of CNW
in DMAc/LiCl. separation of MCC with DMAc/LiCl was the reason for
the colour change of the composites. The dispersion and
whiskers in nanometer scale. The size of the whiskers was distribution of nanowhiskers can also be affected and
estimated to be less than 10 nm in width and between 200 improved by optimizing the compounding process (screw
and 400 nm in length [26]. This correlates with other design, temperature and speed), which will be done in
TEM analysis on cellulose whiskers from wood sources future studies.
[28,29].
3.3. Characterization
3.2. Extrusion
The extruded composites were examined using transmis-
The extrusion process of cellulose nanocomposites ren- sion electron microscope (TEM) to study the composite
ders several challenges. The major difficulty is to feed the morphology at nanoscale. Fig. 6 shows an overview picture
CNW into the extruder and achieve uniformly dispersed
whiskers in the polymer matrix. The CNWs have a very
high surface area and have a tendency to aggregate when
dried. Therefore, to avoid the re-aggregation during dry-
ing, the whisker suspension was directly fed into the poly-
mer melt during the extrusion process. It is difficult to feed
a high amount of liquid into the hot polymer melt because
of vapour generation. But it was possible to carry out the
liquid feeding by using several separate venting systems
to remove the vapour and by using low screw speed and
keeping total throughput low. It was thus possible to use
DMAc/LiCl as both swelling/separation and pumping
medium. However, the composite materials were slightly
brown after the processing and also contained some dark
spots. No colour change was observed in the PLADMAc
sample. The colour change may therefore be due to degra-
dation of the cellulose whiskers caused by the pumping
medium. However, more studies need to be done to find
how the DMAc/LiCl is affecting the PLA and cellulose
whiskers in processes where high temperatures are used.
As a first step to investigate the thermal properties of the
whiskers, a thermogravimetric analysis of MCC before
and after DMAc/LiCl treatment was done. The analysis Fig. 6. An overview of the PLA/PLA-MA/CNW composites taken with
was carried out at 180 C, which is similar to the extrusion TEM.
 K. Oksman et al. / Composites Science and Technology 66 (2006) 2776–2784
of the PLA/PLA-MA/CNW composite. It was difficult to
see any cellulose whiskers in this sample. Fig. 7a, the com-
posite with PEG, shows a similar overview picture com-
pared to Fig. 6 except that there are more dark spots.
These small spots indicate that the whiskers were not uni-
formly dispersed in the PLA matrix and possibly that the
cellulose is degraded during processing. In Fig. 7b a more
detailed view of the composite with PEG is shown. It can
be seen that the CNWs were partly dispersed in PLA. It
was not possible to observe dispersed whiskers in compos-
ites without PEG which indicates that the PEG also facili-
tated the dispersion of whiskers.
The results from mechanical tests are presented in Figs.
8 and 9 and in Table 4. Fig. 8 shows the effect of compat-
Fig. 7. Transmission electron micrograph of the PLA/PLA-MA/PEG/
CNW composite: (a) an overview and (b) detailed view.
2781
Fig. 8. Comparison of mechanical properties of different materials
combinations (presented as normalized values).
Fig. 9. Typical tensile stress–strain curves of PLADMAc, PLA/PLA-MA/
CNW and PLA/PLA-MA/PEG/CNW.
ibilizer (PLA-MA), processing aid (PEG) and pumping
medium (DMAc/LiCl) on the stiffness, tensile strength
and elongation to break compared with pure PLA. The
results show that these additives generally had a negative
effect on the mechanical properties of PLA and that this
effect was most significant when DMAc/LiCl was used.
PEG was expected to act, not just as a processing aid,
but also as a plasticizer for PLA and therefore improve
the elongation to break. This effect has also been reported
by Kulinski and Piorkowska [30]. However, as shown in
Fig. 8, the addition of PEG did not show any significant
change in the elongation to break but decreased the mod-
ulus as well as the maximum strength. The maleic anhy-
dride grafted PLA (PLA-MA) did also affect the PLA
negatively but the effect was not as significant as for PEG
and DMAc/LiCl. DMAc/LiCl was expected to be removed
by vacuum venting during the extrusion, but probably res-
idues of DMAc/LiCl were left in the material after process-
ing. This, combined with high processing temperatures,
was most likely degrading the PLA and thus caused deteri-
oration in the mechanical properties.
2782 K. Oksman et al. / Composites Science and Technology 66 (2006) 2776–2784

Table 4
Composites mechanical properties compared with PLADMAc
Property PLADMAc PLA/PLA-MA/CNW PLA/PLA-MA/PEG/CNW
E-modulus (GPa) 2.9 (±0.1) 3.9 (±0.3) 2.6 (±0.2)
Max. strength (MPa) 40.9 (±3.2) 77.9 (±6.7) 48.4 (±3.8)
Elongation to break (%) 1.9 (±0.2) 2.7 (±0.5) 17.8 (±8.5)

Fig. 9 and Table 4 shows the composites mechanical

properties compared with PLADMAc in more detail. The
PLADMAc was used as reference material to see how the
addition of CNW is affecting the mechanical properties.
In this case the results were much more positive, both com-
posites showed better mechanical properties and the com-
posite with partly dispersed cellulose nano whiskers PLA/
PLA-MA/PEG/CNW showed an increase in elongation
to break around 800%. The ductility of this material was
clearly much better than the others. The strength was
improved 20% but E-modulus was slightly decreased
(10%) for this composite. The E-modulus for composite
without PEG was improved about 35%, the strength about
90% and elongation to break about 35%. It is clear that the
addition of CNW had a positive effect for this composite
and the effect was most visible on the composite strength.
It is difficult to explain why CNW together with PEG
had so large effect on the elongation to break and ductility
but similar results have been obtained in another cellulose
nanocomposite system. Petersson and Oksman [31] Fig. 10. WAXD pattern of PLA, PLADMAc and MCC.
reported an increase in all mechanical properties including
elongation to break when cellulose acetate butyrate (CAB)
was used as matrix. The reason for this behaviour might be
a combination of nano-sized whiskers dispersed together
with a low molecular weight polymer (PEG) in a brittle
matrix. It is possible that the PEG interacts with cellulose
whiskers, covers them and by that improves the dispersion
of the CNW. This might result in improved toughness but
lower reinforcing effect of CNW. This can also be seen in
Fig. 9. Similar observation was made for wood thermoplas-
tic composites [32], when wood fibers were covered by an
elastomeric polymer the composites toughness was effec-
tively increased with an expense of decreased modulus.
Generally, the addition of CNW had a positive effect on
the mechanical properties of the composites.
The X-ray (WAXD) analysis of the raw materials and
the nanocomposites was done to obtain further insight into
the materials crystallinity. The WAXD patterns of raw
materials, PLA, PLADMAc and MCC are shown in
Fig. 10. PLA exhibits a small peak at 2h = 16.4 and can
be considered as semicrystalline in nature. PLADMAc also
Fig. 11. WAXD pattern of PLA/PLA-MA/CNW and PLA/PLA-MA/
shows a prominent peak at 2h = 16.4 together with other
PEG/CNW composites.
less prominent peaks and exhibits more crystalline nature
than pure PLA. MCC shows peaks at 2h = 15.4, 16.2 and
22.5. The peaks are more prominent and sharp for MCC for the composites with and without PEG. It is possible
showing the crystalline nature of this reinforcement. The to see peaks at 2h = 15.2 and 22.5 indicating cellulose I
d values associated with 2h = 15.4, 16.2 and 22.5 are structure. This is an indication that the cellulose structure
6.14, 5.46 and 3.95 Å which is corresponding to cellulose was retained after the chemical treatments and even after
I polymorph structure. Fig. 11 shows the WAXD pattern the compounding process (see Fig. 11).
 K. Oksman et al. / Composites Science and Technology 66 (2006) 2776–2784
4. Conclusions
The goal of this work was to identify new and commer-
cially available sources for cellulose whiskers and to
develop a new processing technique for the preparation
of cellulose based nanocomposites.
The results showed that MCC can be used as a starting
material for the preparation of cellulose nanowhiskers.
MCC contains a large number of whiskers which are aggre-
gated by the strong hydrogen bonds between the individual
cellulose crystallites and can be separated using a suitable
chemical and mechanical treatment. In this study, DMAc
with 0.5 wt% LiCl was used as swelling/separation agent.
The TEM study of the whiskers showed that the size was
approximately 10 nm in width and 200–400 nm in length.
It was found that the extrusion process using liquid feed-
ing of the CNW suspension is a promising way to produce
cellulose nanocomposites. It was practically possible to feed
a liquid suspension of the whiskers into the hot polymer melt
but it was necessary to use a proper venting system to
remove the liquid during the extrusion. TEM analysis of
the composite structures showed partly dipersed nanowhis-
kers when PEG and maleated PLA were used. The compos-
ite in which PLA-MA was the only additive, single
nanowhiskers were not observed. This indicates that a pro-
cessing aid is needed to disperse the whiskers in the matrix.
Thermal characterization of separated CNW showed
that the whiskers were more sensitive to degradation at
higher temperatures compared to MCC. This may be due
to the presence of the DMAc/LiCl.
The mechanical results did not show improvements as
expected if compared to pure PLA. A possible explanation
for decreased mechanical properties is combination of used
additives (DMAc/LiCl, PEG and PLA-MA) and the high
processing temperature. A comparison between PLADMAc
and produced nanocomposites showed a more positive pic-
ture of the reinforcing effect of CNW. The mechanical
properties of composites without PEG improved E-modu-
lus, strength as well as the elongation to break. The
strength was improved about 90% compared to PLADMAc.
The composites with PEG showed an increase in the elon-
gation to break with 800% compared to PLADMAc. This
efficient increase on the elongation to break is expected
to be due to PEG covered whiskers.
The WAXD study confirmed that cellulose whiskers
remained as crystallites after swelling/separation in
DMAc/LiCl.
This was a first step to develop a new processing method
for cellulose whiskers nanocomposites which can later on
be used in larger scale production. The color on the sam-
ples was changed from transparent yellow to light brown
which indicates thermal degradation. The color change
and decreased mechanical properties indicates that the
DMAc/LiCl is not suitable as swelling/separation agent
for CNW if high temperature processing is used. The next
step in our work will be to optimize the compounding pro-
cess, use a feeding medium which do not cause degarada-
2783
tion of cellulose nanowhiskers or the PLA in high
temperature processing
Acknowledgements
The authors thank Cargill Dow LLC, Minneapolis,
USA for supplied Nature WorksTM PLA polymer and Asahi
Kasei, Tokyo, Japan for supplied microcrystalline cellu-
lose. We also thank Dr. Bjørn Steinar Tanem for the trans-
mission electron microscopy work.
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