[en] Polyamide-6 nanocomposites were prepared from a new phosphonium organoclay obtained at pilot scale in supercritical carbon dioxide (scCO2) and a commercially available ammonium modified-silicate. The composites were homogenised by twin-screw extrusion, then specimens for testing were prepared by injection moulding. The clay content of the composites was varied from 0 to 7 vol% in 7 steps. The clays were characterised in detail; they differed in their surface coverage and gallery structure, while their particle size was similar and their surface energy differed only slightly. X-ray diffraction, electronic microscopy and rheology were used for the characterisation of composite structure. Different gallery structure of the clays led to dissimilar extent of exfoliation. The phosphonium organoclay exfoliated better in PA than the silicate treated with the ammonium salt in spite of its smaller surface coverage. The nanocomposites showed the usual complex structure: besides individual platelets and intercalated stacks, large particles were also present and the development of a silicate network could be shown at large clay contents. Quantitative determination of the extent of reinforcement revealed two determining factors: contact surface and strength of interaction. The first increases with exfoliation, but the latter decreases as an effect of organophilisation. The extent of exfoliation was also estimated quantitatively, and the calculation confirmed the results of qualitative evaluation showing larger extent of exfoliation for the scCO2-prepared phosphonium clay.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Naveau, Elodie ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Dominkovics, Zita; Budapest University of Technology and Economics and Institute of Materials Science and Environmental Chemistry, Chemical Research Center, Hungarian Academy of Sciences > Laboratory of Plastics and Rubber Technology
Detrembleur, Christophe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Christine ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Hári, József; Budapest University of Technology and Economics and Institute of Materials Science and Environmental Chemistry, Chemical Research Center, Hungarian Academy of Sciences > Laboratory of Plastics and Rubber Technology
Renner, Károly; Budapest University of Technology and Economics and Institute of Materials Science and Environmental Chemistry, Chemical Research Center, Hungarian Academy of Sciences > Laboratory of Plastics and Rubber Technology
Alexandre, Michaël ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Pukánszky, Béla; Budapest University of Technology and Economics and Institute of Materials Science and Environmental Chemistry, Chemical Research Center, Hungarian Academy of Sciences > Laboratory of Plastics and Rubber Technology
Language :
English
Title :
Effect of clay modification on the structure and mechanical properties of polyamide-6 nanocomposites
The "Région Wallonne" in the frame of the FINECLAY project
Funders :
BELSPO - Service Public Fédéral de Programmation Politique scientifique F.R.S.-FNRS - Fonds de la Recherche Scientifique Région wallonne The National Scientific Research Fund of Hungary
Y. Fukushima Swelling behavior of montmorillonite by polyamide 6 Clay Mineral 23 1 1988 27
A. Usuki, M. Kawasumi, Y. Kojima, Y. Fukushima, A. Okada, and T. Kurauchi Synthesis of nylon 6-clay hybrid J Mater Res 8 5 1993 1179 1184
M. Kawasumi, N. Hasegawa, M. Kato, A. Usuki, and A. Okada Preparation and mechanical properties of polypropylene clay hybrids Macromolecules 30 20 1997 6333 6338
R.A. Vaia, and W. Liu X-ray powder diffraction of polymer/layered silicate nanocomposites: model and practice J Polym Sci Part B Polym Phys 40 15 2002 1590 1600
D. Kaempfer, R. Thomann, and R. Mülhaupt Melt compounding of syndiotactic polypropylene nanocomposites containing organophilic layered silicates and in situ formed core/shell nanoparticles Polymer 43 10 2002 2909 2916
N. Hasegawa, and A. Usuki Silicate layer exfoliation in polyolefin/clay nanocomposites based on maleic anhydride modified polyolefins and organophilic clay J Appl Polym Sci 93 1 2004 464 470
H.R. Dennis, D.L. Hunter, D. Chang, S. Kim, J.L. White, and J.W. Cho Effect of melt processing conditions on the extent of exfoliation in organoclay-based nanocomposites Polymer 42 23 2001 9513 9522
P.C. LeBaron, Z. Wang, and T.J. Pinnavaia Polymer-layered silicate nanocomposites: an overview Appl Clay Sci 15 1-2 1999 11 29
M. Alexandre, and P. Dubois Polymer-layered silicate nanocomposites: preparation, properties and uses of a new class of materials Mater Sci Eng 28 1-2 2000 1 63
L. Százdi, B. Pukánszky Jr., G.J. Vancsó, and B. Pukánszky Quantitative estimation of the reinforcing effect of layered silicates in PP nanocomposites Polymer 47 13 2006 4638 4648
L. Százdi, A. Pozsgay, and B. Pukánszky Factors and processes influencing the reinforcing effect of layered silicates in polymer nanocomposites Eur Polymer J 43 2 2007 345 359
Ábrányi Á, Százdi L, Pukánszky B, Jr., Vancsó GJ, Pukánszky B. Formation and detection of clay network structure in poly(propylene)/layered silicate nanocomposites. Macromol Mater Eng 2006:27(2):132-135.
L. Százdi, Á. Ábrányi, B. Pukánszky Jr., G.J. Vancsó, and B. Pukánszky Morphology characterization of PP/clay nanocomposites across the length scales of the structural architecture Macromol Mater Eng 291 7 2006 858 868
K. Renner, S. Henning, J. Móczó, M.S. Yang, H.J. Choi, and B. Pukánszky Micromechanical deformation processes in PA/layered silicate nanocomposites: correlation of structure and properties Polym Eng Sci 2007 8 2007 1235 1245
E. Picard, H. Gauthier, J.F. Gérard, and E. Espuche Influence of the intercalated cations on the surface energy of montmorillonites: consequences for the morphology and gas barrier properties of polyethylene/montmorillonites nanocomposites J Colloid Interf Sci 307 2 2007 364 376
F.G. Ramos Filho, T.J.A. Mélo, M.S. Rabello, and S.M.L. Silva Thermal stability of nanocomposites based on polypropylene and bentonite Polym Degrad Stab 89 3 2005 383 392
C.O. Rohlmann, M.F. Horst, L.M. Quinzani, and M.D. Failla Comparative analysis of nanocomposites based on polypropylene and different montmorillonites Eur Polymer J 44 9 2008 2749 2760
T.D. Fornes, P.J. Yoon, D.L. Hunter, H. Keskkula, and D.R. Paul Effect of organoclay structure on nylon 6 nanocomposite morphology and properties Polymer 43 22 2002 5915 5933
R.A. Vaia, and E.P. Giannelis Lattice model of polymer melt intercalation in organically-modified layered silicates Macromolecules 30 25 1997 7990 7999
H. Ishida, S. Campbell, and J. Blackwell General approach to nanocomposites preparation Chem Mater 12 5 2000 1260 1267
P. Reichert, H. Nitz, S. Klinke, R. Brandsch, R. Thomann, and R. Mülhaupt Poly(propylene)/organoclay nanocomposite formation: influence of compatibilizer functionality and organoclay modification Macromol Mater Eng 275 2000 8 17
F. Bertini, M. Canetti, G. Audisio, G. Costa, and L. Falqui Characterization and thermal degradation of polypropylene-montmorillonite nanocomposites Polym Degrad Stab 91 3 2006 600 605
F. Chavarria, K. Nairn, P. White, A.J. Hill, D.L. Hunter, and D.R. Paul Morphology and properties of nanocomposites from organoclays with reduced cation exchange capacity J Appl Polym Sci 105 5 2007 2910 2924
H. Dennis Nanocomposites: the importance of processing Plast Eng 57 1 2001 56
D. García-López, S. López-Quintana, I. Gobernado-Mitre, J.C. Merino, and J.M. Pastor Study of melt compounding conditions and characterization of polyamide 6/metallocene ethylene- polypropylene-diene copolymer/maleated ethylene-polypropylene-diene copolymer blends reinforced with layered silicates Polym Eng Sci 47 7 2007 1033 1039
E. Naveau, C. Calberg, C. Detrembleur, S. Bourbigot, C. Jérôme, and M. Alexandre Supercritical CO2 as an efficient medium for layered silicate organomodification: preparation of thermally stable organoclays and dispersion in polyamide 6 Polymer 50 6 2009 1438 1446
T.D. Fornes, P.J. Yoon, H. Keskkula, and D.R. Paul Nylon 6 nanocomposites: the effect of matrix molecular weight Polymer 42 25 2001 09929 09940
Y. Kojima, A. Usuki, M. Kawasumi, Y. Fukushima, A. Okada, and T. Kurauchi Mechanical properties of nylon-6 clay hybrid J Mater Res 8 5 1993 1185 1189
Naveau E, Calberg C, Detrembleur C, Jérôme C, Alexandre M. Applied Clay Science. submitted.
B.K.G. Theng The Chemistry of Clay-Organic Reactions 1974 Wiley New York
F. Kádár, L. Százdi, E. Fekete, and B. Pukánszky Surface characteristics of layered silicates: influence on the properties of clay/polymer nanocomposites Langmuir 22 18 2006 7848 7854
P. Reichert, B. Hoffmann, T. Bock, R. Thomann, R. Mülhaupt, and C. Friedrich Morphological stability of poly(propylene) nanocomposites Macromol Rapid Commun 22 7 2001 519 523
A.B. Morgan, and J.W. Gilman Characterization of polymer-layered silicate (clay) nanocomposites by transmission electron microscopy and X-ray diffraction: a comparative study J Appl Polym Sci 87 8 2003 1329 1338
R. Wagener, and T.J.G. Reisinger A rheological method to compare the degree of exfoliation of nanocomposites Polymer 44 24 2003 7513 7518
W. Lertwimolnun, and B. Vergnes Influence of compatibilizer and processing conditions on the dispersion of nanoclay in a polypropylene matrix Polymer 46 10 2005 3462 3471
Jain S. Nano-scale events with macroscopic events in PP/silica nanocomposites. Eindhoven, 2005. p. 31-47.
H.E. Miltner, G.V. Assche, A. Pozsgay, B. Pukánszky, and B.V. Mele Restricted chain segment mobility in poly(amide) 6/clay nanocomposites evidenced by quasi-isothermal crystallization Polymer 47 3 2006 826 835
T.D. Fornes, and D.R. Paul Modeling properties of nylon 6/clay nanocomposites using composite theories Polymer 44 17 2003 4993 5013
Pukánszky B, Turcsányi B, Tüdós F. Effect of interfacial interaction on the tensile yield stress of polymer composites. Elsevier, 1988. p. 467-477.
B. Turcsányi, B. Pukánszky, and F. Tüdós Composition dependence of tensile yield stress in filled polymers J Mater Sci Lett 7 2 1988 160 162
J. Móczó, E. Fekete, and B. Pukánszky Acid-base interactions and interphase formation in particulate-filled polymers J Adhes 78 10 2002 861 875
G. Vörös, E. Fekete, and B. Pukánszky An interphase with changing properties and the mechanism of deformation in particulate-filled polymers J Adhes 64 1 1997 229
