Comparison of polylactide/nano-sized calcium carbonate and polylactide/montmorillonite composites: Reinforcing effects and toughening mechanisms

Abstract Semicrystalline polylactide (PLA) exhibits high tensile strength and modulus but very low strain-at-break and toughness. In this study, PLA nanocomposites with nano-sized precipitated calcium carbonate (NPCC) and organically modified montmorillonite (MMT) clay were prepared by melt extrusion. Morphologies, tensile mechanical properties, dynamic mechanical and rheological properties, polymer–nanoparticle interactions, and toughening mechanisms of the PLA/NPCC and PLA/MMT nanocomposites were compared. MMT and NPCC showed significantly different effects on the strength, modulus and elongation of the PLA nanocomposites. Different toughening mechanisms were first elucidated for the two types of nanocomposites based on the evidence from both macroscopic and microscopic observations. Under uniaxial tension, large quantities of microvoids were created in both PLA nanocomposites. The microvoids in PLA/NPCC caused massive crazing, while in PLA/MMT they resulted in shear yielding, particularly in the nanocomposite with 2.5 wt% MMT. The MMT stacks and platelets were found to be located between the microvoids in the extended specimens and prevented them from collapsing and coalescing.

[1]  T. Kotaka,et al.  Biaxial Flow-Induced Alignment of Silicate Layers in Polypropylene/Clay Nanocomposite Foam , 2001 .

[2]  M. Cakmak,et al.  Superstructural hierarchy developed in coupled high shear/high thermal gradient conditions of injection molding in nylon 6 nanocomposites , 2004 .

[3]  P. Maiti,et al.  New Polylactide/Layered Silicate Nanocomposites: Role of Organoclays , 2002 .

[4]  J. Sarasua,et al.  Crystallization and melting behavior of polylactides , 1998 .

[5]  M. Pluta Morphology and properties of polylactide modified by thermal treatment, filling with layered silicates and plasticization , 2004 .

[6]  Y. Konishi,et al.  Structural hierarchy developed in injection molding of nylon 6/clay/carbon black nanocomposites , 2005 .

[7]  Snyder,et al.  Geometrical percolation threshold of overlapping ellipsoids. , 1995, Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics.

[8]  A. Kinloch Mechanics and mechanisms of fracture of thermosetting epoxy polymers , 1985 .

[9]  M. Wolcott,et al.  Study of biodegradable polylactide/poly(butylene adipate-co-terephthalate) blends. , 2006, Biomacromolecules.

[10]  A. Argon,et al.  Toughenability of Nylon-6 with CaCO3 filler particles: new findings and general principles , 2001 .

[11]  M. Cakmak,et al.  Structural Gradients in Injection Molded PPS , 1990 .

[12]  R. J. Gaymans,et al.  Rigid particle toughening of aliphatic polyketone , 2006 .

[13]  Jung-Ki Park,et al.  Effect of P(lLA‐co‐εCL) on the compatibility and crystallization behavior of PCL/PLLA blends , 2000 .

[14]  Thomas J. Pinnavaia,et al.  Nanolayer Reinforcement of Elastomeric Polyurethane , 1998 .

[15]  M. Cakmak,et al.  Amplification effect of platelet type nanoparticles on the orientation behavior of injection molded nylon 6 composites , 2003 .

[16]  Mario Malinconico,et al.  Poly (D,L-lactic acid)/poly (∈-caprolactone) blend membranes: preparation and morphological characterisation , 2000 .

[17]  T. Pinnavaia,et al.  Clay-Reinforced Epoxy Nanocomposites , 1994 .

[18]  Jie Yin,et al.  Preparation and properties of hybrids of organo-soluble polyimide and montmorillonite with various chemical surface modification methods , 1999 .

[19]  D. Pochan,et al.  Poly (l-Lactic Acid)/Layered Silicate Nanocomposite: Fabrication, Characterization, and Properties , 2003 .

[20]  Toshio Kurauchi,et al.  Mechanical properties of nylon 6-clay hybrid , 1993 .

[21]  T. D. Fornes,et al.  Nylon 6 nanocomposites: the effect of matrix molecular weight , 2001 .

[22]  Vlachos,et al.  Nanoscopic-confinement effects on local dynamics , 2000, Physical review letters.

[23]  S. Ray,et al.  New polylactide/layered silicate nanocomposites. 3. High-performance biodegradable materials , 2003 .

[24]  M. Malinconico,et al.  Immiscible Poly(L-lactide)/Poly(ε-caprolactone) Blends: Influence of the Addition of a Poly(L-lactide)-Poly(oxyethylene) Block Copolymer on Thermal Behavior and Morphology , 2004 .

[25]  M. Cakmak,et al.  Hierarchical structural gradients in injection moulded poly(ethylene naphthalene-2,6-dicarboxylate) parts , 1994 .

[26]  M. G. Volpe,et al.  Compatibilized poly(ε-caprolactone)/poly(L-lactide) blends for biomedical uses , 1999 .

[27]  Emmanuel P. Giannelis,et al.  Structure and Dynamics of Polymer-Layered Silicate Nanocomposites , 1996 .

[28]  Y. Lam,et al.  Strengthening acrylonitrile-butadiene-styrene (ABS) with nano-sized and micron-sized calcium carbonate , 2005 .

[29]  Robert E. Cohen,et al.  Toughness mechanism in semi-crystalline polymer blends: II. High-density polyethylene toughened with calcium carbonate filler particles , 1999 .

[30]  Thomas J. Pinnavaia,et al.  Hybrid Organic−Inorganic Nanocomposites: Exfoliation of Magadiite Nanolayers in an Elastomeric Epoxy Polymer , 1998 .

[31]  S. Ray,et al.  New Polylactide/Layered Silicate Nanocomposites. 1. Preparation, Characterization, and Properties , 2002 .

[32]  John C. Halpin,et al.  Primer on Composite Materials Analysis , 1984 .

[33]  Jin-Hae Chang,et al.  Poly(lactic acid) nanocomposites with various organoclays. I. Thermomechanical properties, morphology, and gas permeability , 2003 .

[34]  J. Huetink,et al.  Toughening of polypropylene with calcium carbonate particles , 2001 .

[35]  T. D. Fornes,et al.  Modeling properties of nylon 6/clay nanocomposites using composite theories , 2003 .

[36]  David P. Ziegler,et al.  Influence of montmorillonite layered silicate on plasticized poly(l-lactide) blown films , 2005 .

[37]  Ramanan Krishnamoorti,et al.  Linear Viscoelasticity of Disordered Polystyrene−Polyisoprene Block Copolymer Based Layered-Silicate Nanocomposites , 2000 .

[38]  P. Dubois,et al.  Polymer-layered silicate nanocomposites: preparation, properties and uses of a new class of materials , 2000 .

[39]  Y. Lam,et al.  The influence of fatty acid coating on the rheological and mechanical properties of thermoplastic polyurethane (TPU)/nano-sized precipitated calcium carbonate (NPCC) composites , 2006 .

[40]  Suprakas Sinha Ray,et al.  POLYMER/LAYERED SILICATE NANOCOMPOSITES: A REVIEW FROM PREPARATION TO PROCESSING , 2003 .

[41]  M. Cakmak,et al.  Structural gradients developed in injection-molded syndiotactic polystyrene (sPS) , 1996 .

[42]  E. Giannelis,et al.  Poly(lactic acid) nanocomposites: comparison of their properties with montmorillonite and synthetic mica (II) , 2003 .

[43]  A. Argon,et al.  Toughenability of polymers , 2003 .