See discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/266951909 “Green” PLA nanocomposites designed with special end-use properties (PowerPoint Presentation) Conference Paper · May 2012 DOI: 10.13140/2.1.2504.4480 CITATIONS READS 0 188 7 authors , including: Marius Murariu Awa Doumbia Materia Nova Materials R&D Centre Laboratoires Urgo, Dijon, France 198 PUBLICATIONS 3,039 CITATIONS 12 PUBLICATIONS 220 CITATIONS SEE PROFILE SEE PROFILE Some of the authors of this publication are also working on these related projects: Sustainable multifunctional polymeric and (nano)composite materials SUSMAT View project European Project AMBIO View project All content following this page was uploaded by Marius Murariu on 16 October 2014. The user has requested enhancement of the downloaded file.
“Green” PLA na nano noco compo mposite sites de design signed ed with sp with spec ecial ial en end-use use pr prop oper erties ties Dr Dr. . Che Chem. . Eng. Eng. Marius Marius MURAR MURARIU IU (Prof. Philippe DUBOIS) Center of Innovation and Research in MAterials & Polymers (CIRMAP), Laboratory of Polymeric and Composite Materials , Materia Nova Research Center, Mons & University of Mons, Belgium Académie Universitaire Wallonie-Bruxelles 1 BiPoCo 2012
“Green” PLA na nano noco compo mposite sites de design signed ed with sp with spec ecial ial en end-use use pr prop oper erties ties (1) M. Murariu, A.-L. Dechief, L. Bonnaud, Ph. Dubois (2) A. Doumbia, M. Ferreira, C. Campagne, E. Devaux 1 Materia Nova Research Center & University of Mons, Avenue Copernic 1, Mons 7000, Belgium 2 Ecole Nationale Supérieure des Arts et Industries Textiles, Roubaix Cedex1, 59056, France Follo ollowi wing ng th the e co coll llabo boration tion INT INTERR ERREG EG, NANOL ANOLAC C pr projec oject 2 Union Eu Européenne – Fonds Eu Européen de Dé Développeme ment Ré Régional INTE TERR RREG EG efface les frontières
Presentation outline • INTRODUCTION: Biopolymers & PLA… • Pathways to PLA - ZnO nanocomposites designed for production of films and fibers • CONCLUSIONS & ... further works
Intr Introd oduc uction tion: : Ev Evolution olution of of mar markets f ets for or biop bioplastics lastics European Bioplastics association: Adapted, source: BCC Inc. Global production capacity will 3500 ktonnes double from 2010 to 2015 3000 3230 Europe Global market 2500 2000 Number of worldwide patents 1500 per year linked to PLA 1000 754 500 572 175 0 2010 2015 Year 41.4% compound annual growth rate for bioplastics from 2010 through 2015 In short time ˃ 400 patents/ year ! (source: BCC Research; Bioplastics: Technologies and Global Markets (PLS050A) – Sept. 2010) (source: Michel Biron, SpecialChem - May 10, 2011 )
LAST TENDENCIES: From packaging & fibers to PLA products for technical applications PLA grades with improved properties are required: impact & high tensile strength, PLA LA nan nanoco ocomposites mposites : : high HDT & long term durability, crystallization… a a grea eat pot potent ential ial 5
PL PLA can A can be be suc succe cess ssfull fully y mo modified dified wi with th va variou rious s na nano nofil filler lers to s to ob obtain tain co compe mpeti titi tive e pr prop oper erti ties es Various types of nanoscale materials Our top of nanofillers: 1D : Organo modified clays, graphite derivatives (expanded and exfoliated graphite)… 2D : CNTs, cellulose nanowhiskers, Halloysite, Sepiolite … 3D : Ag, POSS, SiO 2 , CaCO 3, AlO (OH)… ZnO (A.P. Kumar et al./ Progress in Polymer Science 34 ( 2009 ) 479 – 515 ) PLA is sensitive to shear, hydrolysis, thermo-oxidative degradation … Some nanofillers & their treatment can lead to PLA degradation
PATHWA THWAYS S TO O PLA PLA - ZnO ZnO NANO ANOCOMP COMPOS OSITE ITES S DESIG DESIGNE NED D FOR FOR PR PRODUCTION ODUCTION OF OF FILMS FILMS AND AND FIBERS FIBERS WITH WITH SPECIAL SPECIAL END END-USE USE PR PROPER OPERTIES TIES Sta State of te of t the Ar he Art t : ZnO nanofillers mixed with different polymers (PA 6, epoxy and acrylic resins, PMMA, PS...): antibacterial function, intensive ultraviolet absorption, other characteristic features. .. (Gaur MS, et al., J. Appl. Polym. Sci. 2010 ;118:2833-40; Agrawal M, et al., Macromol. Chem. Phys. 2010 ;211:1925-32) PLA-ZnO nanocomposites, no relevant information The catalytic depolymerization ability of Zn-based products (ZnO) : the main reason explaining the lack of studies concerning the PLA-ZnO nanocomposites. (Murariu M, Doumbia A, Devaux E, Dubois Ph. et al., ( Abe, H et al., Biomacromolecules 2004 , 5 : 1606-14 ) Biomacromolecules 2011 , 12 : 1762 – 71)
Transesterification (a) and “unzipping” depolymerization (b) reactions of PLA in presence of Zn compounds (adapted from Abe, H et al.,. Biomacromolecules 2004 , 5 : 1606-14 ) O CH 3 O CH 3 O CH 3 O CH 3 O CH 3 O CH 3 PLLA O C CH O C CH O C CH O Zn PLLA O C CH O C CH O C CH O Zn Zn O CH C O CH C O CH C O PLLA CH 3 O CH 3 O CH 3 O CH 3 O O CH C O O CH 3 C CH O CH 3 PLLA O C CH O O CH 3 Zn PLLA O C CH O Zn a a b + b O CH 3 O CH 3 O CH 3 O CH 3 O CH 3 O CH 3 PLLA O C CH O C CH O C CH O C CH O C CH O Zn PLLA O C CH O Zn + CH 3 O O CH C C CH O O CH 3 ZnO as well as other Zn compounds have been successfully utilized as effective catalysts for lactide polymerization and also in “unzipping” depolymerization of PLA and lactic acid oligomers (OLA). (Xiao-Gang Yang et al., Polymer Bulletin 2008 , 61: 177 – 88) 8
Examples to illustrate the application of anti-bacterial products Antibacterial fibers Water Treatment , Purifications Electronics, washing machines, refrigerators, Health Care Industry air conditioners & purifiers, vacuum cleaners… Electronics & Communications Textile & Clothing Industry Painting Industry Agriculture Cosmetic Industry Soft Drinks Industry Shoes Industry Aerospace Industry Consumer Products Packaging Industry Automotive Industry Military And Government Services
Ma Mater terials ials Pol oly(L,L y(L,L-lact lactide ide) ) (PLA) (PLA) - “ Na Natu tureW eWor orks ks ” PLA1 (grade for films/ 4032D) : M n(PLA) = 88 500; M w / M n =1.8; D-isomer: <2 %. PLA2 (grade for fibers*/ 6201D) : M n(PLA) = 55 000; M w / M n =1.9; D-isomer: 1.4 %. Ultranox 626A (U626): Bis (2,4-di-t-butylphenyl) Pentaerythritol Diphosphite ZnO, rod-like nanoparticles : Umicore Zinc Chemicals Zano 20 : Bulk density: 280 g/l, Specific surface area BET : 25 - 35 m 2 /g (noted as ZnO). Zano 20 Plus : surface treated with triethoxy caprylylsilane , bulk density: 360 g/l, loss on drying at 105°C (2h): max. 1%; ZnO content: 96.2 ± 0.5%; (noted as ZnO(s)). “Rods” of ZnO(s) ( length up to 100 nm, ZnO diameter of ~15-30 nm) * PLA 6202D (D-isomer ≈ 2%), spinning grade was also used for up- scaling in production of fibers 10 %- for all compositions will refer to weight percentage.
To make PLA less susceptible to the catalytic action of ZnO surface treatments with selected additives I. Stearates as coating agents II. II . Sil Silanes anes Triethoxy caprylyl silane: especially suitable for the treatment of metal oxides (ZnO), very stable coating. I. Surface coating of ZnO with up I. 3% of selected stearates (Zn or Mg) does not lead to some improvements of properties: low tensile strength or breakable plates after compression molding. (source: www.koboproducts.com) ZnO vs. ZnO(s) in PLA-ZnO nanocomposites PLA1- 2% ZnO (treated with Mg stearate)
Melt-blending at small scale with Brabender kneaders: 190-200 C (3 min premixing/30rpm, 7 min mixing/70rpm) All components are dried before melt-blending PLA was dried overnight at 80 C (vacuum) PLA PLA + + To compression molding na nano nofil filler ler + + additiv ad ditives* es* Testing Plates for realization of Additional processing by specimens by cutting injection molding U626 was used in preferred percentage of 0.3 wt-% 12
The modification of molecular parameters (M n (a) and PI (b)) of PLA1 and PLA2 with different loadings of surface-treated or untreated ZnO The surface-coating of ZnO allows for limiting the decrease of PLA molecular weights (more evident in the case of PLA2) Even in presence of surface-treated ZnO(s) it is not possible to completely avoid the degradation of the polyester matrix.
Recommend
More recommend
