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Abstract
The paper is focusses on the study of the thermal and mechanical behaviour of reinforced agro-materials. Various formulations based on
plasticized starch matrix have been carried out, varying matrix formulation, filler content, fibres length and nature. Cellulose and
lignocellulose fibres, which show unequal surface tensions, have been tested. After extrusion and injection moulding, the properties of these
wheat starch-based biocomposites are analysed. Mechanical properties (tensile tests), thermo-mechanical properties (DMTA) and thermal
degradation (TGA) are analysed. DMTA analysis shows important variations of main relaxation temperature, which can be linked both,
to interactions resulting in a decrease of starch chain mobility and to a regular reinforcing effect. These results are consistent with the static
mechanical behaviour, which vary according to the filler content (up to 30 wt%), fibre nature (cellulose vs. lignocellulose) and fibre length
(from 60 mm to 1 mm). Besides, we have shown that the addition of cellulose fillers improves the thermal resistance of these biocomposites.
Finally, we have tested the impact of the addition of biodegradable polyesters into these composites without significant effect on the postprocessing stability.
q 2004 Elsevier Ltd. All rights reserved.
Keywords: Composite; Plasticized starch; Cellulose fibres; Mechanical properties
1. Introduction
Ecological concerns have resulted in a renewed interest
in natural and compostable materials, and therefore issues
such as biodegradability and environmental safety are
becoming important. Tailoring new products within a
perspective of sustainable development or eco-design, is a
philosophy that is applied to more and more materials. It is
the reason why material components such as natural
fibres, biodegradable polymers can be considered as
interestingenvironmentally safealternatives for the
development of new biodegradable composites.
Biocomposites (biodegradable composites) consist of
biodegradable polymers as the matrix material and
biodegradable fillers, usually biofibres (e.g. lignocellulose
fibres). Since both components are biodegradable, the
composite as the integral part is also expected to be
biodegradable (Mohanty, Misra, & Hinrichsen, 2000c).
* Corresponding author. Tel.: 33-3902-42707; fax: 33-3902-42716.
E-mail address: averousl@ecpm.u-strasbg.fr (L. Averous).
0144-8617/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbpol.2003.11.015
112
2. Experimental
2.1. Materials
2.1.1. Fillers
Natural cellulose fibres from leafwood are supplied by
Omya Rettenmier (JRS-Arbocel, Germany). Different
semi-crystalline cellulose microfibres with increasing
lengths are tested. The fibres are like ribbons, with an
average diameter close to 20 mg, determined by image
analysis (Fig. 2a, and below). Initial average lengths are
respectively 60 (SF), 300 (MF) and 900 (LF) microns. Initial
shape ratios (length/diameter) are respectively 3, 15 and 45.
Cellulose content is greater than 99.5%. Residue on ignition
at 850 8C during 4 h is less than 0.3%. In a previous paper,
Amash and Zugenmaier (2000) have presented some
113
Fig. 2. Images from LF (a) and PPF fibres, obtained by optic microscopy. Scale 100 mg.
114
Table 1
Main materials characteristics
Density (g/ml)
Melting point, in 8C (DSC)
Glass transition, in 8C (DSC)
Cristallinity, in %
Modulusa, in MPa
Elongation at breaka, in %
Max. tensile stressa, in MPa
Biodegradationb (Mineralization in %)
Surface tensionc s sd sp ; in mJ m22
Dispersive component sd ; in mJ m22
Polar component sp ; in mJ m22
a
b
c
TPS1
TPS2
1.11
65
261
67
190 (6)
.500
14.2 (1.4)
100
52
41
11
1.07
112
229
33
262 (12)
420 (59)
17.2 (5.2)
100
59
37
22
1.37
None
8
None
87 (10)
124 (3)
3.6 (0.1)
100
42
23
19
1.34
None
220
None
12 (1)
60 (5)
1.4 (0.3)
100
32
20
12
According to NF 51-035 1983. Standard deviations given in bracket. TPS materials are tested 4 weeks after injection.
At 60 days in controlled composting according to ASTM 5336 (Bastioli, 1998).
Determinations from contact angles measurements of probes liquids.
115
Table 2
Composites: (a) TPS1-based formulations (b) TPS2-based formulations
TPS1-based composites
Filler (wt%)
Polyester (wt%)
0, 15 or 30
0, 10 or 25
4, 8, 12 or 16
MF
LF
PPF
4, 8, 12 or 16
10 or 20
10 or 20
Fig. 4. Rheological TPS2 behaviours: storage and loss modulus, tangent delta vs. temperature.
116
Table 3
DMTA results
wt%
SF
MF
LF
PPF
0
8
12
8
12
10
20
10
20
a Transition
b Transition
Ta (8C)
Height at Ta
Tb (8C)
Height at Tb
3 (1)
6(1)
9 (1)
7 (1)
12 (1)
7 (1)
15 (1)
12 (1)
18 (1)
0.27 (0.01)
0.26 (0.01)
0.27 (0.01)
0.24 (0.01)
0.22 (0.01)
0.23 (0.01)
0.23 (0.01)
0.21 (0.01)
0.22 (0.01)
266 (1)
264 (1)
263 (1)
264 (1)
262 (1)
nd
nd
nd
nd
0.30 (0.01)
0.28 (0.01)
0.27(0.01)
0.28 (0.01)
0.26 (0.01)
nd
nd
nd
nd
nd not determined.
Fig. 5. TPS2/SF composites with different filler contents. Variations of loss and storage modulus vs. temperature.
117
118
scomposite
1 2 vf
expB vf
smatrix
1 2:5vf
B l Af K1 K2
Table 4
Mechanical results (Tensile tests)
Type of fibres
Modulus
ratio
Elongation at
break ratio
Maximum
strength
ratio
SF
MF
SF
MF
SF
5.4
2.6
LF
3.4
9.9
6.0
5.0
PPF
4.0
10.8
0.22
0.68
LF
0.48
0.34
0.17
0.52
PPF
0.42
0.25
2.2
1.6
LF
2.6
5.4
3.0
2.4
PPF
2.0
3.6
4sdFibre sdTPS
sdFibre sdTPS
4spFibre spTPS
spFibre spTPS
Table 5
Surface tension results
Lignocellulose
Cellulose
33 (2)
15 (2)
48 (2)
39 (2)
22 (2)
61 (2)
119
Fig. 10. Thermograms: Mass fraction (%) vs. temperature. TG of neat TPS2, or LF and PPF- TPS2 composites.
120
Table 6
TGA results
TPS2
TPS2/10 wt% LF
TPS2/20 wt% LF
TPS2/10 wt% PPF
TPS2/20 wt% PPF
LF Fibres
PPF Fibres
Degradation temperature
(Max DTG peak)
332 (1)
335 (1)
336 (1)
335 (1)
339 (1)
362 (2)
370 (2)
36.3
28.3
33.0
33.5
33.2
3.5
7.1
4. Conclusion
Table 7
Post-processing ageing results. Ratios: Modulus at 6 weeks/Modulus at
2 weeks
Systems studied
Without polyester
PEA
PCL
TPS1
TPS1/15 wt% SF
TPS1/15 wt% MF
TPS1/15 wt% LF
TPS1/30 wt% LF
TPS1 25 wt% polyester
TPS1/15% MF 10 wt% polyester
TPS1/15% MF 25 wt% polyester
2.15
1.19
1.08
1.07
1.07
2.21
1.35
1.33
2.01
1.35
1.31
Acknowledgements
This work is funded by EuropolAgro (AlternovalReims, France) through a research program devoted to the
development of new compostable packaging materials
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