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)