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Natural fibres as reinforcement in polylactic


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Article in Composites Science and Technology · July 2003


DOI: 10.1016/S0266-3538(03)00103-9

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Composites Science and Technology 63 (2003) 1317–1324
www.elsevier.com/locate/compscitech

Natural fibres as reinforcement in polylactic acid (PLA) composites


K. Oksmana,*, M. Skrifvarsb, J.-F. Selinc
a
Department of Machine Design and Materials Technology, NTNU, Norwegian University of Science and Technology, Rich. Birkelands vei 2,
N-7491 Trondheim, Norway
b
SICOMP AB, POB 271, SE-94126 Piteå, Sweden
c
Fortum Oyj, POB 310, FIN-06101 Porvoo, Finland

Accepted 21 February 2003

Abstract
The focus in this work has been to study if natural fibres can be used as reinforcement in polymers based on renewable raw
materials. The materials have been flax fibres and polylactic acid (PLA). PLA is a thermoplastic polymer made from lactic acid and
has mainly been used for biodegradable products, such as plastic bags and planting cups, but in principle PLA can also be used as a
matrix material in composites. Because of the brittle nature of PLA triacetin was tested as plasticizer for PLA and PLA/flax com-
posites in order to improve the impact properties. The studied composite materials were manufactured with a twin-screw extruder
having a flax fibre content of 30 and 40 wt.%. The extruded compound was compression moulded to test samples. The processing
and material properties have been studied and compared to the more commonly used polypropylene flax fibre composites (PP/flax).
Preliminary results show that the mechanical properties of PLA and flax fibre composites are promising. The composite strength is
about 50% better compared to similar PP/flax fibre composites, which are used today in many automotive panels. The addition of
plasticizer does not show any positive effect on the impact strength of the composites. The study of interfacial adhesion shows that
adhesion needs to be improved to optimise the mechanical properties of the PLA/flax composites. The PLA/flax composites did not
show any difficulties in the extrusion and compression moulding processes and they can be processed in a similar way as PP based
composites.
# 2003 Elsevier Science Ltd. All rights reserved.
Keywords: PLA; Flax; Renewable raw materials; Composites; Extrusion; B. Mechanical properties; B. Microstructure; DMTA

1. Introduction The long-term properties of renewable materials are


also very important especially if the products are not
The growing environmental awareness and new rules single use applications.
and regulations are forcing the industries to seek more Natural fibres have many advantages compared to
ecologically friendly materials for their products. For synthetic fibres, for example low weight, and they are
example automotive applications based on natural recyclable and biodegradable. They are also renewable
fibres with polypropylene as matrix material are very and have relatively high strength and stiffness and cause
common today. Less work has been done to study no skin irritations [1–8]. On the other hand there are
composites with matrices, which originate from renew- also some disadvantages: moisture uptake, quality var-
able raw materials. There are many different polymers iations and low thermal stability. Many investigations
of renewable materials: for example polylactic acid, cel- have been made on the potential of the natural fibres as
lulose esters, poly hydroxyl butyrates, starch and lignin reinforcements for composites and in several cases the
based plastics. The problems with these polymers have results have shown that the natural fibre composites
been poor commercial availability, poor processability, own good stiffness but the composites do not reach the
low toughness, high price and low moisture stability. same level of strength as glass fibre composites [1–8].
The manufacturing methods of natural fibre thermo-
* Corresponding author. Tel.: +47-73-59-38-26; fax: +47-73-59-
plastic composites have been modified lay-up/press
41-29. moulding (film stacking method), pultrusion, extrusion
E-mail address: kristiina.oksman@immtek.ntnu.no (K. Oksman). and injection moulding [4–8].
0266-3538/03/$ - see front matter # 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0266-3538(03)00103-9
1318 K. Oksman et al. / Composites Science and Technology 63 (2003) 1317–1324

While many studies have been made on the potential 2. Materials and methods
of natural fibres just a few investigations are made on
the possibilities to use renewable polymers as matrix 2.1. Materials
for such fibres [9–13]. The studied biopolymers have
been soy-oil based epoxy, starch, polycaprolactone
(PCL), polyhydroxybutyrate (PHB), modified cellulose,  Matrix: PolyL-lactic acid (PLA), POLLAIT from
acetic acid, polylactic acid (PLA) and polyester amide Fortum was used. The MFI for PLA is between 1
[9–13]. and 2 g/10 min (190  C, 2.16 kg), which is lower
Polylactic acid polymers or polylactides are polyesters than for the used PP.
of lactic acid, and these polymers have recently been  Matrix (ref): Polypropylene (PP), from Adstiff
introduced commercially for products where biode- 770 ADXP, Montell polyolefins. This is a PP
gradability is wanted. Polylactic acid is a versatile poly- with specific high MFI, 45 g/10 min (230  C, 2.16
mer made from renewable agricultural raw materials, kg). It is a suitable matrix for extrusion of com-
which are fermented to lactic acid. The lactic acid is posite materials.
then via a cyclic dilactone, lactide, ring opening poly-  Additive: Triacetin, glycerol triacetate ester, from
merised to the wanted polylactic acid. The polymer is Sigma-Aldrich, was used as plasticizer for PLA.
modified by certain means, which enhance the tempera- It has good compatibility with the polymer, and
ture stability of the polymer and reduce the residual increases the elongation of the plastic from less
monomer content. The resulting polylactic acid can be than 10% to more than 250%.
processed similarly as polyolefines and other thermo-  Reinforcements: Enzyme retted flax fibres in the
plastics although the thermal stability could be better. form of long heckled fibres were connected
Reinforcing with fibres is one possibility to enhance together by hand, called ‘‘hand made roving’’.
thermal stability. Polylactide polymers are stiff and The appearance of used fibres can be seen in
brittle materials, and it is therefore necessary to use Fig. 1.
plasticizers to improve the elongation and impact
properties. The polylactide is fully biodegradable. The Table 1 shows the properties of used materials. PLA
degradation occurs by hydrolysis to lactic acid, which has better mechanical properties compared to PP while
is metabolised by micro-organisms to water and car- PP has higher MFI and lower density. The flax fibres
bon monoxide. By composting together with other have superior mechanical properties compared to PP
biomass the biodegradation occurs within two weeks, and PLA, which can be expected to result in good rein-
and the material has fully disappeared within 3–4 forcing effect for both polymers.
weeks [14]. Various formulations of studied materials are shown in
There are several promising markets for biode- Table 2, totally 12 different formulations were studied.
gradable polymers such as polylactide. Plastic bags
for household bio waste, barriers for sanitary pro- 2.2. Methods
ducts and diapers, planting cups, disposable cups
and plates are some typical applications. To date no 2.2.1. Compounding of composite materials
commercial large-scale production of polylactide The composite materials were manufactured using a
exists, but this is likely to change in the near future. twin-screw extruder (Coperion Werner & Pfleiderer
The starting material, lactic acid, will also need new
capacity. Commercial markets for biodegradable
polymers are expected to increase substantially in the
coming years.
The aim of this study was to make an initial
investigation how PLA will act as matrix material for
natural fibre composites. As PLA can be processed in
nearly the same way as polypropylene, it should be
possible to prepare flax reinforced composites by
extrusion. The mechanical properties of the compo-
sites were studied according to the tensile testing.
Further, the thermal properties were studied with
dynamic mechanical thermal analysis (DMTA), the
morphology was studied with scanning electron micro-
scopy (SEM) and the possible degradation of PLA dur-
ing extrusion was determined by gel permeation
chromatography (GPC). Fig. 1. Hand made flax fibre roving.
K. Oksman et al. / Composites Science and Technology 63 (2003) 1317–1324 1319

Table 1
Material properties of used raw materials

Materials Flexural-modulus Tensile strength Elongation to break MFI (g/10min) Density


(GPa) (MPa) (%) (2.16 kg, 190  C) (g/cm3)

PP 1.6 30 – 45 0.9
PLAa 3.4 60 8 1–2 1.26
Flax fibres 70–80 600–1000 1–2 – 1.5
a
Data from the manufacturer.

Table 2 Table 3
Compositions of different materials Processing settings for extrusion

Materials Matrix Flax fibres Triacetin Material PP/flax PLA/flax


(wt.%) (wt.%) (wt.%)
Speed (rpm) 250 250
PP 100 – – Torque (%) 31–41
PP/flax 70 30 – Vacuum vent. Yes Yes
PP/flax 60 40 – Temp. profile (C )
PLA 100 – – Zone 1 180 180
PLA/flax 70 30 – (PP, PLA, plastizer)
PLA/flax 60 40 – Zone 2 – –
PLA/triacetin 95 – 5 Zone 3 180 180
PLA/triacetin 90 – 10 Zone 4 (Flax fibres) 170 170
PLA/triacetin 85 – 15 Zone 5 175 175
PLA/triacetin/flax 55 40 5 Zone 6 180 180
PLA/triacetin/flax 50 40 10 Zone 7 – –
PLA/triacetin/flax 45 40 15 Zone 8 185 185
Zone 9 190 190
Zone 10 – –
Zone 11 200 200
ZSK 25 WLE). The flax fibre content was 30 and 40 Total output (kg/h) 16
wt.%. The fibres were fed into the side extruder and the
fibre content in the composite was calculated according
to feeding speed and the weight of the roving per meter. 2.2.5. GPC
The processing parameters are shown in Table 3. The Number and weight average molecular weights before
liquid triacetin plasticizer was pumped into the extru- and after the extrusion of the PLA were determined by
der. gel permeation chromatography on a Waters GPC sys-
tem with Styragel columns (105, 104, 103 and 500 Å) and
2.2.2. Compression moulding a refractive index detector. Chloroform was used as
Test samples for mechanical testing were compression effluent, and the analysis was done at room temperature.
moulded with a conventional compression moulding A universal calibration was used for the calculation of
press (Fjellman Press Mariestad AB) with a maximum the molecular weights, using Mark–Houwink constants
press capacity of 3100 tons. The mould temperature was for PLA and polystyrene, which was used as standard.
50  C and the pressure was about 70 MPa.
2.2.6. DMTA
2.2.3. Mechanical testing Dynamical mechanical thermal analysis (DMTA,
The tensile testing was performed according to Rheometric Scientific Mk III) was performed to initially
ASTM 3039 standard for tensile testing on an Instron. investigate if the addition of the flax fibres will improve
Impact testing was performed according to ISO 179 the thermal properties, such as maximum use tempera-
unnotched Charpy standard for fibre reinforced com- ture of PLA. Four materials, PLA, and PLA/flax, PLA/
posite materials. At least 10 specimens were tested for triacetin and PLA/flax/triacetin, were tested to find the
every material. maximum use temperature for the use and also to see
possible interaction effects between PLA matrix and flax
2.2.4. Electron microscopy fibres. DMTA was run in the dual cantilever bending
Fractured surfaces of the materials were studied mode and the typical sample dimensions were: thickness
with a CamScan scanning electron microscope (SEM) 1–2 mm, length 25 mm and width 4 mm. The tempera-
with an acceleration voltage of 30 kV. The sample ture interval was from room temperature, about 25  C,
surfaces were sputter coated with gold to avoid to 180  C with a heating rate of 1.5  C/min and using a
charging. frequency of 1 Hz.
1320 K. Oksman et al. / Composites Science and Technology 63 (2003) 1317–1324

3. Results

3.1. Mechanical testing

The mechanical properties of PLA/flax composites


were compared to PP/flax. Table 4 shows the summary
of the results. Generally, the pure PLA has better
mechanical properties than pure PP.
Fig. 2 shows the tensile stress and Fig. 3 the stiffness
of the tested materials. The pure PLA has a tensile
strength of 50 MPa and a modulus of 3.4 GPa com-
pared to 28 MPa and 1.3 GPa of pure PP. The addition
of flax fibres will not improve the tensile strength, which
is an indication of poor adhesion between the flax fibres Fig. 2. Tensile stress of PLA/flax composite compared to PP/flax.
and the matrix. The stress is not transferred from the
matrix to the stronger fibres.
The addition of flax will increase the modulus but the
higher fibre content will not improve the modulus in the
PLA composites as it will for PP composites. A possible
explanation of this can be the fibre orientation. The test
samples are compression moulded and the fibres can be
orientated differently from one sample to another.
Cyras et al. [10] have studied starch/PCL/sisal fibre
composites and reported a tensile modulus of 0.7 GPa
and a maximum strength of 14.4 MPa with a 30 wt.%
sisal fibre content. These values are very low compared
to our PLA/flax modulus 8.3 GPa and the strength 53
MPa. A research group at DLR in Germany lead by
Riedel [11,12] have studied different biocomposites and
reported very high mechanical properties of composites Fig. 3. Tensile modulus of PLA/flax composites compared with PP/
they studied. They have used Bioceta, Sconacell and flax.
PLA as matrix and unspecified natural fibre mats as
reinforcements and reached mechanical properties near The results show that the tensile stress is decreased
by glass fibre mat reinforced plastics. with increased triacetin content and this trend was even
Because of the brittle nature of PLA, triacetin was more visible in PLA/flax composites. The addition of
used to plasticize the pure PLA and for the PLA/flax triacetin showed a positive effect on the elongation to
composites. Triacetin has previously been used for break for pure PLA and PLA/flax composites, which
plasticizing of pure PLA with good results. Usually the was expected because of the softening effect. The highest
triacetin content is 12–15%, lower amounts do not give triacetin addition (15%) clearly shows a negative effect
effects. In this work with addition of fibres we also for PLA/flax composites, both the stress and stiffness
wanted to test lower amounts. The fibre content was are strongly decreased (see also Figs. 4 and 5).
held constant during this test, 40 wt.%. Table 5 shows a Fig. 5 shows how the stiffness of PLA and PLA/flax
summary of the mechanical properties of plasticized composites is affected by addition of triacetin. The
PLA and PLA/flax composites. stiffness of PLA/flax composites is strongly decreased

Table 4
The mechanical properties of PP/flax and PLA/flax composites

Materials Elongation to break (%) S.D. Max. Stress (MPa) S.D. E-modulus (GPa) S.D.

PP – – 30 – 1.6 –
PP/30% flax 2.7 1.5 29 4.2 5 0.4
PP/40% flax 1.5 0.8 29 3.1 7.6 0.9
PLA 2 0.2 50 2.4 3.4 0.1
PLA/30% flax 1.0 0.2 53 3.1 8.3 0.6
PLA/40% flax 0.9 0.2 44 7.2 7.3 0.5
K. Oksman et al. / Composites Science and Technology 63 (2003) 1317–1324 1321

Table 5
Mechanical testing of plasticized PLA with and without flax fibres

Materials Elongation to break (%) S.D. Max. stress (MPa) S.D. E-modulus (GPa) S.D.

PLA 2.0 0.2 50.3 2.4 3.4 0.1


PLA/5% Tri 2.2 0.2 41.7 3.4 3.0 0.2
PLA/10% Tri 1.8 0.2 43.6 1.6 3.4 0.2
PLA/15% Tri 2.6 0.1 37.2 1.6 2.6 0.2
PLA/40% flax 0.9 0.2 44.1 7.2 7.3 0.5
PLA/5% Tri/40% flax 1.4 0.3 43.2 2.6 7.3 0.4
PLA/10% Tri/40% flax 1.1 0.5 29.5 4.0 5.4 1.0
PLA/15% Tri/40% flax 2.3 1.8 16.6 4.7 2.4 0.4

Fig. 6. The effect of triacetin and 40% flax fibres on the unnotched
Fig. 4. The tensile stress of PLA with 5%, 10% and 15% triacetin Charpy impact strength of PLA.
content and 40% flax fibres.

content does not show any positive effect on Charpy


impact strength of the composites. Notice that the
standard deviation was increased with increased triace-
tin content. The residual moisture content in the flax
fibres had most likely a negative effect on the triacetin /
PLA /fibre system.

3.2. Electron microscopy

Fig. 7 shows the fracture surface of the PLA/flax


composite. It is possible to see that there are many fibre
pull-outs and that the fibre surfaces are clean which
indicates poor adhesion between the fibres and the PLA
matrix. The fibres are also orientated (which can be seen
in Fig. 7b).
Fig. 5. The effect of triacetin and 40% flax fibres on the tensile
Further, Fig. 7 shows that the flax fibres are in the
modulus of PLA.
form of single fibres and that indicates that the fibres
have been separated during the extrusion process. The
with the triacetin content while the triacetin did not fibres are also very well dispersed in the PLA matrix.
affect the stiffness of pure PLA in the same level. Good dispersion of single fibres and fibre orientation
Fig. 6 shows how the impact properties of PLA and should result in very high mechanical properties.
PLA/flax composites are affected by the addition of
triacetin. It can be seen that the addition of triacetin did 3.3. GPC
not affect the impact properties of the PLA/flax com-
posites at all as expected. The addition of 5% triacetin The GPC analysis showed that the weight average
in PLA shows the best impact strength. Higher triacetin molecular weight was 97 000 g/mol for the pure PLA.
1322 K. Oksman et al. / Composites Science and Technology 63 (2003) 1317–1324

occur at temperatures around 80–100  C. Fig. 8 shows


dynamic modulus and tan delta curves of the PLA and
PLA/flax composites. It is possible to see in Fig. 8a that
thermal properties of PLA are increased with the incor-
poration of flax fibres. The softening temperature is
increased from about 50  C for pure PLA to 60  C with
flax fibres and it is further increased if the composite is
crystallized. The composite will soften after 60  C but
the modulus will start to increase again around 80  C
which is a typical effect of cold crystallisation [15]. The
curve of the crystallized sample (PLA/flax II) shows
very good thermal properties. Fig. 8b shows tan delta
for PLA and PLA/flax composites and PLA/flax II
(cold crystallised). The tan delta peak is not changed
due to addition of flax but it is very much affected by
the crystallisation. The peak broadens and is also very
low compared to uncrystallised sample.
Fig. 9 shows PLA and PLA/flax with 10 wt.% triace-
tin plasticizer. Fig. 9a shows that the plasticizer has
decreased the thermal properties of PLA which was
even expected because of the plasticizing effect. The
addition of fibres and crystallisation will increase the
softening temperature. In Fig. 9b tan delta curves are
shown, the addition of triacetin will decrease the tan
delta peak from 63 to 55  C for PLA but the addition of

Fig. 7. Fractured surface of PLA/flax composites: (a) detailed picture,


(b) overview.

After extrusion with flax fibres, a slightly lower number


average molecular weight was recorded, 80 000 g/mol.
The GPC also showed that the molecular weight dis-
tribution was unimodal, and that no low molecular
weight fraction was present. It could therefore be con-
cluded that the PLA matrix does not degrade chemically
during the processing.

3.4. DMTA

Dynamic mechanical tests were run to characterize


the composites. PLA can be semi-crystallic material but Fig. 8. DMTA runs for PLA and PLA with flax fibres: (a) dynamic
it is usually amorphous because the crystallisation will modulus, (b) tan delta.
K. Oksman et al. / Composites Science and Technology 63 (2003) 1317–1324 1323

The study of interfacial adhesion, which is a well-


known problem for natural fibres and synthetic poly-
mers, also shows that adhesion needs to be improved to
optimise the mechanical properties of the PLA/flax
composites. The microscopy study of the composite
microstructure showed poor adhesion between the fibres
and PLA matrix. The flax fibres were well dispersed in
the PLA and separated to single fibres due to the com-
pounding process. The thermal properties of the PLA,
which are a drawback for PLA, were improved with an
addition of flax fibres.
Triacetin plasticizer did not improve the composite
impact properties, it rather had a negative effect on
mechanical and impact properties. The results of
mechanical testing indicated that triacetin will change
the fibre structure making the fibres more brittle
because all mechanical properties were strongly
decreased by the use of triacetin.
The GPC analysis shows that the PLA was not
degraded due to the compounding process and incor-
poration of flax fibres.
The possibility to use conventional manufacturing
processes is a very important factor for industrial use of
renewable materials. In this case PLA/flax composites
did not show any difficulties in the extrusion and com-
pression moulding processes and they can be processed
in a similar way as PP based composites.
Fig. 9. DMTA run for PLA/flax composites with 10% triacetin: (a)
dynamic modulus, (b) tan delta.
Acknowledgements
triacetin resulted in increased tan delta temperature for the
composites. Tan delta was increased from 55  C to 70  C This work was funded by Vinnova, The Swedish
which indicates some kind of interaction effect between the Agency for Innovation Systems. Runar Långström,
fibres and PLA due to the triacetin. It is possible that tria- SICOMP AB, is gratefully acknowledged for perform-
cetin will act as a compatibilizer for the PLA/flax system. ing the composite manufacturing and mechanical test-
Further, the peak is moved to the higher temperatures and ing and Maaria Seläntaus, Fortum Oil and Gas, is
also broadens for cold crystallised sample. gratefully acknowledged for doing the GPC analysis.

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