Composites Science and Technology 69 (2009) 1293–1297

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Composites Science and Technology

journal homepage: www.elsevier.com/locate/compscitech

Production of microfibrillated cellulose (MFC)-reinforced polylactic acid (PLA)

nanocomposites from sheets obtained by a papermaking-like process
Antonio Norio Nakagaito a,*, Akihiro Fujimura b, Toshiaki Sakai b, Yoshiaki Hama b, Hiroyuki Yano a
a
Research Institute for Sustainable Humanosphere, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan
b
Awa Paper Mfg. Co. Ltd., 3-10-18 Minami-yaso-cho, Tokushima-shi, Tokushima 770-0005, Japan

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

Article history: The fabrication of cellulose nanofiber-reinforced composites has been so far problematic due to difficul-
Received 6 November 2008 ties in obtaining good dispersion of hydrophilic cellulose fibers in a hydrophobic polymer matrix. A new
Received in revised form 5 February 2009 manufacturing process similar to papermaking, which enables the production of thin sheets made of uni-
Accepted 4 March 2009
formly dispersed microfibrillated cellulose (MFC) with polylactic acid (PLA) fibers was devised, and the
Available online 13 March 2009
composites were obtained by compression molding of the stacked sheets. The process is suitable for
adoption at an industrial scale owing to the high yields and fast dewatering times. The measurement
Keywords:
of tensile properties revealed that the modulus, strength, and strain at fracture increased linearly with
A. Nano composites
A. Polymer–matrix composites (PMCs)
the MFC content. The improvement in toughness was considered one of the key benefits brought by
B. Mechanical properties MFC reinforcement.
A. Microfibrillated cellulose (MFC) Ó 2009 Elsevier Ltd. All rights reserved.
A. Polylactic acid (PLA)

1. Introduction approaches like plasticization, block copolymerization, blending

The increasing pressure on manufacturers by new environmen-
tal and waste management policies, consumers demand and also
the escalating oil price, is steering the trends of composite technol-
ogy away from traditional materials. The majority of composites
currently available on the market aim long term durability, relying
on nondegradable polymers such as epoxies and polyurethane
reinforced with fibers like graphite, aramid, and glass. But from
now the tendency is to use ‘green’ composites in substitution for
ordinary plastics in consumer products in order to gain in perfor-
mance while reducing weight and cost [1].
Polylactic acid is a versatile polymer derived from lactic acid
and is made from completely renewable resources like sugar beets
and sugarcanes or even corn, wheat, and other starch-rich prod-
ucts. As such, PLA is an attractive sustainable alternative to petro-
leum-based plastics since it can be processed using the same
machinery. It can be molded, vacuum formed, blown or even ex-
truded as easily as conventional plastics. Among its many potential
uses, PLA already has found applications in textile and medical
fields and also in the packaging industry. Besides, PLA is in princi-
ple compostable under certain conditions, that is, in the presence
of the right triggers the material can be degraded into harmless
natural compounds. Nonetheless, the inherent brittleness of PLA
has been the main obstacle to expand its commercial use. Many
* Corresponding author. Tel.: +81 774 38 3657.
E-mail addresses: nakagaito@rish.kyoto-u.ac.jp, norio@rocketmail.com (A.N.
Nakagaito).
with tougher polymers or rubber have been proposed but all led
to significant decreases in modulus and strength of the toughened
PLA [2].
Plant fibers are long regarded as being promising candidates for
replacing conventional reinforcing fibers (e.g. glass fibers) in com-
posites for semi-structural and even structural applications. The
availability of inexpensive plant fibers everywhere in the world
has contributed to their use as reinforcement in ‘greener’ compos-
ites. The non-abrasiveness to the processing equipment, the possi-
bility to be incinerated and still keep the CO2 neutrality are
recognized as being the main advantages as well [1]. Among the var-
ious plant derived fibers, there is a particular cellulose morphology
known as microfibrillated cellulose or MFC. This is a form of ex-
panded high-volume cellulose, moderately degraded and greatly
expanded in surface area, obtained through a homogenization pro-
cess. Initially, a pulp fiber slurry is treated by several passes through
a disk refiner and subsequently introduced into a device called high-
pressure homogenizer, where the slurry is pumped at high-pressure
through a spring-loaded valve assembly. The valve opens and closes
in a reciprocating motion, subjecting the cellulose to a large
pressure drop with shearing and impact forces. The slurry is reintro-
duced in the device many times. This combination of repeated
mechanical forces promotes fibrillation of the cellulose fibers and
ultimately a high degree of microfibrillation. Cellulose fibers are
split and unraveled to expose smaller fibrils and microfibrils, the lat-
ter having diameters in the range of 10–100 nm [3,4]. This cellulose
morphology was initially intended to be used in food, cosmetics, and
medical products.

0266-3538/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2009.03.004
1294 A.N. Nakagaito et al. / Composites Science and Technology 69 (2009) 1293–1297

MFC has a great potential as reinforcing medium in composites,
as demonstrated by earlier studies [5–8]. The reinforcement by cel-
lulose nanofibers instead of micro-sized fibers is recognized as
being more effective due to interactions between the nano-sized
elements that make up a percolated network connected by hydro-
gen bonds or entanglements [9], once a good dispersion in the ma-
trix is achieved. More specifically, MFC delivers enhanced
toughness to the composites compared to pulp fibers [5]. Never-
theless, the adequate dispersion of hydrophilic cellulosic fibers in
a matrix of mostly hydrophobic polymers is a critical aspect to
be addressed, which is especially difficult in the case of nanofibers.
The aim of this study was to establish a straightforward process
to produce MFC/PLA nanocomposites by obtaining homogeneously
dispersed MFC/PLA sheets from aqueous suspensions followed by
compression molding. The method is similar to papermaking, with
reduced dewatering time, and it is simple enough to be readily
applicable at an industrial scale. The reinforcement attained by
the incorporation of MFC resulted in better mechanical properties
over neat PLA, especially regarding the enhancement in toughness.
platinum to avoid specimen charging. The thickness of the coating
was approximately 2 nm.
2.4. Tensile test
Samples were cut into rectangular pieces about 0.3 mm thick,
4 mm wide, and 35–50 mm long, dried at 40 °C under vacuum
for 8 h, and subjected to tensile test using an Instron 3365 univer-
sal materials testing machine at a strain rate of 1 mm/min. To pre-
vent damage at the gripping points, the ends of each specimen
were covered with aluminum and clasped with serrated chucks.
The widths and thicknesses were measured at different points
spaced 5 mm from each other along the specimens. Since the spec-
imens were not hourglass-shaped but ribbon-shaped, the cross
sectional areas corresponding to the actual fracture sites were con-
sidered to calculate the tensile modulus and strength. The speci-
men gage lengths were measured with a caliper for each sample
upon gripping.
2.5. Dynamic mechanical analysis (DMA)

2. Experimental Dynamic mechanical properties were measured using a Rheovi-

bron DDV 25FD (Orientec A&D Co. Ltd., Japan) by the force vibra-
2.1. Materials tion method in tensile mode. Samples about 0.3 mm thick were
cut into approximately 4.5 mm  30 mm rectangular pieces and
The reinforcing nanofibers consisted of commercially available dried at 40 °C under vacuum for 8 h. Measurements were per-
MFC, tradename Celish KY-100G produced by Daicel Chemical formed at a heating rate of 1.5 °C/min, with the span set to
Industries, Ltd. The semi-crystalline PLA was Terramac PL01 from 21 mm, a preload of 5 g, and at a frequency of 1 Hz.
Unitika Fibers Ltd. in fiber form with a diameter of 10–15 lm,
length of 3.5 mm, melt temperature of 170 °C, and a glass transi- 3. Results and discussion
tion temperature of 57 °C.
The production of the MFC/PLA sheets was carried out by a
2.2. Composite preparation papermaking-like process. The yields and drainage times are pre-
sented in Table 2. The process delivered very low loss especially
An aqueous suspension containing 3 wt% of a mixture of PLA considering that the wire mesh alone would not be able to hold
and MFC was prepared by first mixing MFC with water using a the nano-sized MFC fibrils. The micro-sized PLA fibers seem to
Waring blender for 30 s and subsequently adding PLA fibers and have acted as an additional sieve for the MFC, which have been
mixing for another 10 s. The PLA to MFC ratio was adjusted to de- trapped by sticking to the surface of the PLA fibers during the sheet
liver the desired MFC content to the composites. A high molecular forming, as can be observed by the SEM images in Fig. 1. The pro-
weight polymer flocculant polyacrylamide (PAM), 1 wt% relative to cess delivered high yields, retaining most of the tiny MFC fibrils in
the oven dry weight of MFC, was added as a drainage aid. Following the dewatered sheets. Hydrophobic PLA fibers also contributed to
the thorough dispersion of fibers (PLA and MFC), the suspension the fast dewatering delivering reduced drainage times. As seen in
was dewatered in a sieve consisting of a metal wire mesh following Table 2, almost all sheets were sieved in less than about half a min-
a papermaking process in accordance to JIS P 8209. The suspen-
sions with MFC contents up to 70 wt% were sieved with a 70 mesh
(212 lm opening) sieve whereas for the 90 wt% MFC content sus-
pension, a finer 400 mesh (37 lm opening) was selected. The Table 1
Compressing pressures and temperatures applied in the fabrication of MFC/PLA
formed square sheets 25 cm by 25 cm were sandwiched between
composites for different MFC contents.
blotting paper and dried at 98 °C for 15 min under a load of
MFC fiber content (wt%) 90 70 50 30 20 10
26 kg. The final dried sheets had a basis weight of approximately
Compressing pressure (MPa) 30 10 3 2 1
50 g/m2. Compressing temperature (°C) 185 180
The MFC/PLA sheets were further dried at 105 °C for 1 h prior to
composite making to completely remove absorbed moisture.
Sheets were stacked in eight layers and sandwiched between two
stainless steel plates. In the hot press, the sheets/plates set was
pre-heated at 180 °C without pressure for the first 3 min, and com- Table 2
Parameters of MFC/PLA sheet forming for different MFC contents.
pressing pressures and temperatures depicted in Table 1 were ap-
plied for another 3 min. The heater was turned off and the heating MFC fiber 90 70 50 30 20 10
content
plates were cooled down by circulating water before the samples
(wt%)
were taken out. All samples were annealed at 105 °C for 1 h. Yield (%) 98 88 89 99.6 99.1 103.1 96.5
Drainage time 63 min 100 Two layers 37 16 13.1 13.6
2.3. Scanning electron microscopy (SEM) (s) combined
19 s/layer
Wire mesh 400 mesh 70 mesh (212 lm)a
MFC/PLA sheets were examined using a field emission scanning
(37 lm)a
electron microscope, model JSM-6700F (JEOL Ltd.). The accelerat-
a
ing voltage was set to 1 kV, and samples were coated with Sieve mesh designation and aperture sizes according to JIS Z8801-1.
 A.N. Nakagaito et al. / Composites Science and Technology 69 (2009) 1293–1297 1295

sure evidence that the papermaking-like process delivered levels

of fiber dispersion that translates in improved mechanical proper-
ties. The increase in stiffness of the composites with increasing
MFC load holds true even at high temperatures, as seen in Fig. 3.
The storage modulus above the glass transition temperature
(Tg = 57 °C) is increased as the fiber content of the composites
raises. At a fiber content of 70 and 90 wt%, the storage modulus
is sustained up to 250 °C while the composites with lower fiber
contents have the modulus dropped at temperatures starting at
150 °C due to the melting of PLA. The percolated cellulosic fibril
web formed at higher MFC contents acted as a load bearing frame-
work and was able to maintain the stiffness of the samples even
after the melting of the matrix.
The tensile strength against MFC content is shown in Fig. 4.
Similar to the Young’s modulus, the ultimate strength of the com-
posites increased linearly with the fiber content. The strength gain
at a fiber content of 70 wt% was almost three times higher com-
pared to the composite at 10 wt% MFC load. The improvement rate
of tensile strength being higher than that of the tensile modulus,
which was almost two times at the same MFC loads, is explained
by the increase in elongation up to fracture of the composites.
The strain at fracture also evolved linearly with the fiber content,
as seen in Fig. 5. It should be noted that the crystallized neat PLA
after annealing was extremely brittle so that the tensile test could
not be performed. According to reports describing PLA reinforced
with natural cellulosic fibers, the toughness of the composites is
decreased as the fibers are added to the matrix [12–18]. This is
likely caused by agglomerations of fibers as the dispersion be-
comes difficult to achieve especially at higher fiber contents. None-
theless, the present process seems to deliver good nanofiber
dispersion which translates in enhanced reinforcement with
increasing MFC contents. Notably at high fiber loads, the good
dispersion of the fibrils might lead to a percolated network of

16
14
12
E (GPa)

10
8
6
4
2
0
0 20 40 60 80 100
MFC (wt%)

Fig. 2. Tensile modulus of MFC/PLA composites as a function of MFC fiber content.

Fig. 1. Scanning electron micrographs of a MFC/PLA sheet containing 70 wt% MFC.
The network of tiny MFC fibrils is uniformly adhered to the thick PLA fibers. Arrows
point to PLA fibers.

1.E+05

ute, except the 90 wt% MFC sheet that took 1 h. The 70 wt% MFC
sheet demanded a slightly longer time in excess of 1 min, but by 1.E+04 90 wt%
E' (MPa)

splitting the sheets in two layers obtained separately and com-

bined into one, the time required for dewatering could be reduced 70 wt%
to just 19 s. The process exhibits two highly desirable attributes
1.E+03
from the industrial viewpoint, increased yield and speedy drainage
50 wt%
of water. 30 wt%
20 wt%
The tensile Young’s moduli of MFC/PLA composites as a function 10 wt%
of MFC contents are presented in Fig. 2. The modulus increased lin- 1.E+02
0 50 100 150 200 250
early as the reinforcing cellulosic fibrils were added to the PLA, o
Temperature ( C)
from about 5 GPa at a fiber content of 10 wt% to almost twice as
high at values around 9 GPa, at an MFC content of 70 wt%. The pro- Fig. 3. Temperature dependence of the storage modulus of MFC/PLA composites.
gressive increase of Young’s modulus even at high MFC loads is a Percentages indicate MFC fiber contents.
1296 A.N. Nakagaito et al. / Composites Science and Technology 69 (2009) 1293–1297
200
180
160
140
σ (MPa)
120
100
80
60
40
20
0 10 wt%
0 20 40 60 80 100
MFC (wt%)
Fig. 4. Tensile strength of MFC/PLA composites as a function of MFC fiber content.
0.04
0.035
Strain at fracture
0.03
0.025
0.02
0.015
0.01
0.005
0
0 20 40 60 80 100
MFC (wt%)
Fig. 5. Strain at fracture of MFC/PLA composites as a function of MFC fiber content.
cellulose fibrils that slows down the propagation of cracks during
fracture [5]. The enhancements in toughness of the composites
with the addition of MFC are quite definite if analyzed through
the stress–strain curves presented in Fig. 6, the increases in both
modulus and strain at fracture resulted in improvements in ulti-
mate strength of the composites.
Cellulose nanofibers have a Young’s modulus close to that of a
perfect cellulose crystal, 138 GPa [19], and considering that the
strength of a single kraft pulp fiber can reach a tensile strength
of 1.7 GPa [20], the estimated tensile strength lays well beyond
2 GPa, figures comparable to aramid fibers. In addition, according
to early studies concerning cellulose-based nanocomposites, the
unusual reinforcement effect obtained by nano-sized elements is
attributable to a formation of a rigid network of nanofibers con-
nected by hydrogen bonds [21] and also by mutual entanglements
[9]. According to Dalmas et al. [22], interactions by hydrogen bonds
are limited in the case of compression molded composites because
the viscosity of the melted polymer hinders the nanofibers rear-
rangements, hence the network might be primarily based on
entanglements. In the present case, as the suspension of MFC and
PLA is formed into dried sheets prior to molding, part of the hydro-
gen bonds might be preserved, especially at high fiber contents.
Yet, the percolation phenomenon may be a major advantage of
nanofibers over micro-sized pulp fibers.
The numerous studies on composites based on PLA and cellu-
losic nanofibers reported so far have succeeded in reinforcing
the polymer at relatively low fiber contents. Many of the attempts
with fibers [10–17,25,26] and nanofibers [18,23,24] relied on
twin-screw extrusion, an established compounding process in
the plastics industry, albeit with limited success particularly at
high fiber loads. This would be likely due to the limited amount
of polymer to completely cover the surface of fibers in the micro-
composites, whereas the difficulties in dispersing cellulosic nanof-
ibers in the polymer melt would be a predominant factor in the
case of nanocomposites. In general, the Young’s modulus of com-
posites increased in relation to the neat PLA, however, high fiber
200
90 wt%
180
160
Stress (MPa)
140
120 70 wt%
100
50 wt%
80
60 30 wt%
40
20
20 wt%
0
0 0.01 0.02 0.03 0.04
Strain
Fig. 6. Typical stress–strain curves of MFC/PLA composites at different MFC fiber
contents. Percentages indicate MFC fiber contents.
contents led to the formation of fiber agglomerations that com-
promised the ultimate strength of composites, especially in the
case of nanofibers. The only exception was when high-tenacity ra-
yon was used as reinforcement, which resulted in increased
strength of the composites [25,26], although rayon is a regener-
ated man-made cellulose. More recently Iwatake et al. [7] pro-
posed a quite unconventional approach by dissolving PLA in an
organic solvent mixing it with MFC previously dispersed in the
same organic medium. The ultimate reinforcement was attained
at MFC contents up to 10 wt%, higher MFC loads however, reduced
toughness and strength. Again, the decrease in mechanical prop-
erties was attributed to the flocculation of hydrophilic cellulosic
fibrils. The advantage of the present method lies in the fact that
since the mixing of MFC and PLA fibers is entirely carried through
in aqueous suspension, hydrophilic MFC fibrils and hydrophobic
PLA fibers could be uniformly dispersed. Besides, this new method
is much closer to an industrial process with immediate potential
to be realized.
4. Conclusions
A new process to produce MFC/PLA composites by compression
molding of sheets made of uniformly dispersed MFC and PLA fibers
by a procedure similar to papermaking was developed. The method
delivered high yields and reduced dewatering times and could be
easily adopted by the industry. Good dispersions were obtained
even at high MFC contents up to 90 wt% and as a result the tensile
modulus, strength and strain at fracture of the composites in-
creased linearly as a function of MFC content. The modulus was
doubled and the strength was tripled as the MFC content increased
from 10 to 70 wt%.
Acknowledgements
The authors would like to express gratitude to Dr. K. Abe, Kyoto
University for the SEM observations. This research was supported
by a Grant-in-Aid for Research and Development for Regional Inno-
vation Consortium (Nos. 17S5018, 2006.9–2007.3) from the Minis-
try of Economy, Trade and Industry, Japan.
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