The The ““greengreen”” challenge : challenge : PLAPLA ((nano)compositesnano)composites for for ""durable" applications ?durable" applications ?M. Murariu, L. Bonnaud, K. K. BerlierBerlier, , A–L Dechief, Y. Paint, A. Gallos1, G. Fontaine1, A. Doumbia2, M. Ferreira2,
C. Campagne2, S. Bourbigot1, , E. Devaux2 and Ph. Dubois
Laboratory of Polymeric and Composite Materials, Center of Innovation and Research in Materials & Polymers (CIRMAP), Materia Nova Research Center & University of Mons, 20 Place du Parc, 7000 - Mons, Belgium
1 - Ecole Nationale Supérieure de Chimie de Lille (ENSCL), Villeneuve d’Ascq Cedex, France2 - Ecole Nationale Supérieure des Arts et Industries Textiles (ENSAIT) Roubaix, France
PolylactidePolylactide ((PLAPLA)) is currently receiving considerable attention for conventional utilization such as
biodegradable packaging materials as well as production of textile fibers, and surprisingly enough, as
(nano)composites for technical applications. For a great number of “durable” applications new
customized PLA grades with improved properties are required. Like an expression of the high interest
for PLA utilization in engineering applicationsengineering applications, the aim of some R & D projects (e.g., NANOLAC –
INTERREG IV) and of this communication, is to propose new PLA (nano)composites designed with
desired end-use performances such as rigidity, improved tensile strength, or flame retardant properties.
Authors thank the Wallonia Region, Nord-Pas de Calais Region and European Community for the financial support in the frame of the IINTERREG – MABIOLAC & NANOLAC projects.
They thank all collaborators for helpful discussions and to all suppliers of raw materials.
This work was also supported by the European Commission and FEDER program (Materia
Nova) and “OPTI²MAT” program of excellence, by the Interuniversity Attraction Pole program of
the Belgian Federal Science Policy Office (PAI 6/27) and by FNRS-FRFC.
PLAPLA microcompositesmicrocomposites for for ““durabledurable”” utilizationutilization : : addition into addition into PLAPLA of selected additives of selected additives
and and CaSOCaSO44 (AII form), a by(AII form), a by--product issued from lactic acid production process. product issued from lactic acid production process.
PLAPLA--HNTHNT nanocompositesnanocomposites : potentially interesting for mechanical applications as : potentially interesting for mechanical applications as
stronger, lighter and less expensive new materials.stronger, lighter and less expensive new materials.
Addition of carbon Addition of carbon nanofillersnanofillers into into PLAPLA is leading to is leading to nanocompositesnanocomposites very promising for very promising for
utilization in engineering applications utilization in engineering applications (multifunctional properties).(multifunctional properties).
INTERREG efface les frontièresUnion Européenne –Fonds Européen de Développement Régional
References1. Dubois Ph, Murariu M, TheThe ““greengreen”” challengechallenge: JEC Compos. Mag. 2008, 45, 66– 69. 2. Dubois Ph, Murariu M, Alexandre M, Degée Ph, Bourbigot S, Devaux E. et al, WO 095874 A1 (2008)3. Murariu M, Bonnaud L, Yoann P, Fontaine G, Bourbigot S, Dubois Ph., Pol. Deg. Stab. 2010; 95(3):374-381.
Conclusions & Acknowledgements
PLAPLA ((nano)compositesnano)composites for technical applicationsfor technical applications
Introduction
Potential utilization in Potential utilization in
electronic electronic applications
Category V0 (UL-94V)
for PLA-AII-MP composites (3.1 mm)
To obtain V0 classification the composites filled with (15-30)% AII must contain ≈≈≈≈ 25% MP
(ASTM 638, v=1mm/min, specimens type V).
Les Fonds EuropLes Fonds Europééens de Dens de Dééveloppement Rveloppement Réégional et la Rgional et la Réégion Wallonne investissent dans votre avenirgion Wallonne investissent dans votre avenir
PLA + nano- and microcharges
NANOLAC project : PLA from“disposable” to “durable” applications
PLA-1% NTC
1. PLA + microfillers
HIGH TENSILE STRENGTH :HIGH TENSILE STRENGTH :
The best tensile properties (e.g. stress at break ≈ 55 MPa) for PLA- 40% AII (silane) composites.
CaSO4 (anhydrite II)
as microfillerExcellent filler dispersion
PLA-40% AIILactic acid (lactide)
Gypsum- (by-product)
(1) PLA
(2) AII (CaSO4)
(3) Additives (silanes, clays,
impact modifiers, plasticizers…)
500°C
Fermentation
HIGH TENSILE STRENGTH :
PLA- Halloysite nanotubes
SPECIFIC FIRE PROPERTIESSPECIFIC FIRE PROPERTIES : : PLAPLA-- (clays, (clays, CNTsCNTs, , EGEG……))
2700
2000
2500
2800
0
10
20
30
40
50
60
70
0% 3% 6% 12%
Content of halloysite (wt-%)
Ma
x.
ten
sil
e s
tre
ng
th,
MP
a
1600
2100
2600
3100
Yo
un
g's
mo
du
lus
, M
Pa
Max. tensile strength Young's modulus
PLA - 6% EG (MB way)
GrapheneGraphene layerslayers
1.0 x 103PLA – 6% EG
Volume resistivity, Ώcm
1.1 x 100PLA – 3% EG- 3% CNT
1.6 x 100PLA – 4% EG- 2% CNT
2.5 x 100PLA – 5% EG- 1% CNT
Mean
Sample
(%- by weight)
1.0 x 103PLA – 6% EG
Volume resistivity, Ώcm
1.1 x 100PLA – 3% EG- 3% CNT
1.6 x 100PLA – 4% EG- 2% CNT
2.5 x 100PLA – 5% EG- 1% CNT
Mean
Sample
(%- by weight)
PLA- 4% EG- 2% CNT
hybrid nanocomposites
ELECTRICAL PROPERTIES :ELECTRICAL PROPERTIES : PLAPLA –– ( ( CNTsCNTs, , EGEG, , EGEG--CNTsCNTs……))
PLA- 3% C30B
0
50
100
150
200
250
300
350
400
0 100 200 300 400 500 600 700
Time (s)
RH
R (
kW
/m²)
PLA
PLA- 6% EG
PLA- 9% EG
PLA-12% EG:Decrease of pHRR of above 50%
Neat PLA(0% EG)
12% EG
6% EG
*Cloisite 30B (C30B): organo-modified clay
Rate of heat release (RHR):
PLA vs. PLA-EG nanocomposites
Impact or fire Impact or fire
retardancyretardancy as as
tailored propertiestailored properties
Specimens (3 x 12 x 30 mm3)
2. PLA + nanofillers
HalloysiteHalloysite nanotubesnanotubes
PLAPLA + + HalloysiteHalloysite nanotubesnanotubes ((HNTHNT), ),
expanded graphite (expanded graphite (EGEG), clays, ), clays,
carbon carbon nanotubesnanotubes ((CNTCNT))……
(Source: NaturalNano, Inc. (USA)
PLAPLA-- AIIAII-- melamine phosphate (MP)