Abstract
Rheological analysis was used to understand the structure–property relations of polymer nano-composites based on ethylene vinyl acetate. Two geometrically different nano-particles (sphere of CaCO3 and platelet of montmorillonite) having the same energetic attractions with ethylene vinyl acetate were studied for concentrations between 2.5 and 15 wt%. Three phenomena were studied: the appearance of a solid-like behavior in the linear viscoelastic domain, the limits of linear viscoelasticity, and the presence of stress overshoot in step shear tests. In particular, stress overshoot was investigated based on the tube concept of polymeric chains. Also, differences related to nano-particle geometry (platelet vs. spherical) were investigated based on a filler-network mechanism. Due to higher physical contacting probability, platelet particles can better interact and create a network structure, which dominates the rheological response. On the other hand, although spherical particles can limit the motion of polymeric chains under flow, a strong physical network was not formed. For platelets, scaling behavior was well described by fractal model which considers direct aggregation, and such scaling was not observed for spherical particles. The filler-network mechanism was validated by image analysis.
Similar content being viewed by others
References
Akcora P, Kumar SK, Garciía Sakai V, Li Y, Benicewicz BC, Schadler LS (2010) Segmental dynamics in PMMA-grafted nanoparticle composites. Macromolecules 43:8275–8281
Akcora P, Kumar SK, Moll J, Lewis S, Schadler LS, Li Y, Benicewicz BC, Sandy A, Narayanan S, Ilavsky J, Thiyagarajan P, Colby RH, Douglas JF (2009) “Gel-like” mechanical reinforcement in polymer nanocomposite melts. Macromolecules 43:1003–1010
Anderson BJ, Zukoski CF (2009) Rheology and microstructure of entangled polymer nanocomposite melts. Macromolecules 42:8370–8384
Anderson BJ, Zukoski CF (2010) Rheology and microstructure of polymer nanocomposite melts: variation of polymer segment-surface interaction. Langmuir 26:8709–8720
Bogoslovov RB, Roland CM, Ellis AR, Randall AM, Robertson CG (2008) Effect of silica nanoparticles on the local segmental dynamics in poly(vinyl acetate). Macromolecules 41:1289–1296
Cassagnau P (2003) Payne effect and shear elasticity of silica-filled polymers in concentrated solutions and in molten state. Polymer 44:2455–2462
Cassagnau P (2008) Melt rheology of organoclay and fumed silica nanocomposites. Polymer 49:2183–2196
Chatterjee T, Krishnamoorti R (2008) Steady shear response of carbon nanotube networks dispersed in poly(ethylene oxide). Macromolecules 41:5333–5338
Chen B, Evans JRG (2006) Nominal and effective volume fractions in polymer–clay nanocomposites. Macromolecules 39:1790–1796
Chen DTN, Chen K, Hough LA, Islam MF, Yodh AG (2010) Rheology of carbon nanotube networks during gelation. Macromolecules 43:2048–2053
Chevigny C, Dalmas F, Di Cola E, Gigmes D, Bertin D, Boué Fo, Jestin J (2010) Polymer-grafted-nanoparticles nanocomposites: dispersion, grafted chain conformation, and rheological behavior. Macromolecules 44:122–133
Ci L, Suhr J, Pushparaj V, Zhang X, Ajayan PM (2008) Continuous carbon nanotube reinforced composites. Nano Lett 8:2762–2766
Doi M, Edwards SF (1989) The theory of polymer dynamics. Clarendon, New York
Du F, Scogna RC, Zhou W, Brand S, Fischer JE, Winey KI (2004) Nanotube networks in polymer nanocomposites: rheology and electrical conductivity. Macromolecules 37:9048–9055
Durmus A, Kasgoz A, Macosko CW (2007) Linear low density polyethylene (LLDPE)/clay nanocomposites. Part I: structural characterization and quantifying clay dispersion by melt rheology. Polymer 48:4492–4502
Dykes LMC, Torkelson JM, Burghardt WR (2012) Shear-induced orientation in well-exfoliated polystyrene/clay nanocomposites. Macromolecules 45:1622–1630
Galgali G, Ramesh C, Lele A (2001) A rheological study on the kinetics of hybrid formation in polypropylene nanocomposites. Macromolecules 34:852–858
Goel V, Chatterjee T, Bombalski L, Yurekli K, Matyjaszewski K, Krishnamoorti R (2006) Viscoelastic properties of silica-grafted poly(styrene–acrylonitrile) nanocomposites. J Polym Sci, Part B, Polym Phys 44:2014–2023
Groot RD, Agterof WGM (1995) Dynamic viscoelastic modulus of associative polymer networks: off-lattice simulations, theory and comparison to experiments. Macromolecules 28:6284–6295
Harton SE, Kumar SK, Yang H, Koga T, Hicks K, Lee H, Mijovic J, Liu M, Vallery RS, Gidley DW (2010) Immobilized polymer layers on spherical nanoparticles. Macromolecules 43:3415–3421
Heinrich G, Klüppel M (2002) Recent advances in the theory of filler networking in elastomers. In: Arora M (ed) Filled elastomers drug delivery systems. Springer, Berlin, pp 1–44
Inoue T, Uematsu T, Yamashita Y, Osaki K (2002a) Significance of the longest rouse relaxation time in the stress relaxation process at large deformation of entangled polymer solutions. Macromolecules 35:4718–4724
Inoue T, Yamashita Y, Osaki K (2002b) Viscoelasticity of an entangled polymer solution with special attention on a characteristic time for nonlinear behavior. Macromolecules 35:1770–1775
Isichenko MB (1992) Percolation, statistical topography, and transport in random media. Rev Mod Phys 64:961–1043
Jancar J, Douglas JF, Starr FW, Kumar SK, Cassagnau P, Lesser AJ, Sternstein SS, Buehler MJ (2010) Current issues in research on structure–property relationships in polymer nanocomposites. Polymer 51:3321–3343
Jouault N, Vallat P, Dalmas F, Said Sr, Jestin J, Bouè Fo (2009) Well-dispersed fractal aggregates as filler in polymer-silica nanocomposites: long-range effects in rheology. Macromolecules 42:2031–2040
Kalfus J, Jancar J (2007) Immobilization of polyvinylacetate macromolecules on hydroxyapatite nanoparticles. Polymer 48:3935–3937
Kalfus J, Jancar J (2008) Reinforcing mechanisms in amorphous polymer nano-composites. Compos Sci Technol 68:3444–3447
Koo JH (2006) Polymer nanocomposites—processing, characterization, and applications. McGraw-Hill, New York
Krishnamoorti R, Giannelis EP (1997) Rheology of end-tethered polymer layered silicate nanocomposites. Macromolecules 30:4097–4102
Krishnamoorti R, Yurekli K (2001) Rheology of polymer layered silicate nanocomposites. Curr Opin Colloid Interface Sci 6:464–470
Lee KM, Han CD (2003) Rheology of organoclay nanocomposites: effects of polymer matrix/organoclay compatibility and the gallery distance of organoclay. Macromolecules 36:7165–7178
Letwimolnun W, Vergnes B, Ausias G, Carreau PJ (2007) Stress overshoots of organoclay nanocomposites in transient shear flow. J Non-Newton Fluid Mech 141:167–179
Lin CW, Huang LC, Ma CCM, Yang ACM, Lin CJ, Lin LJ (2008) Nanoplastic flows of glassy polymer chains interacting with multiwalled carbon nanotubes in nanocomposites. Macromolecules 41:4978–4988
Litvinov VM, Spiess HW (1991) 2H NMR study of molecular motions in polydimethylsiloxane and its mixtures with aerosils. Makromol Chem 192:3005–3019
Mahi H, Rodrigue D (2012) Linear and non-linear viscoelastic properties of ethylene vinyl acetate/nano-crystalline cellulose composites. Rheol Acta 51:127–142
Manitiu M, Horsch S, Gulari E, Kannan RM (2009) Role of polymer-clay interactions and nano-clay dispersion on the viscoelastic response of supercritical CO2 dispersed polyvinylmethylether (PVME)-clay nanocomposites. Polymer 50:3786–3796
Mansoutre S, Colombet P, Van Damme H (1999) Water retention and granular rheological behavior of fresh C3S paste as a function of concentration. Cement Concrete Rec 29:1441–1453
Mobuchon C, Carreau P, Heuzey M-C (2007) Effect of flow history on the structure of a non-polar polymer/clay nanocomposite model system. Rheol Acta 46:1045–1056
Mohraz A, Solomon MJ (2005) Orientation and rupture of fractal colloidal gels during start-up of steady shear flow. J Rheol 49:657–681
Mu M, Winey KI (2007) Improved load transfer in nanotube/polymer composites with increased polymer molecular weight. J Phys Chem C 111:17923–17927
Muthukumar M (1989) Screening effect on viscoelasticity near the gel point. Macromolecules 22:4656–4658
Nagase Y, Okada K (1986) Heterogeneous behavior after yielding of solid suspensions. J Rheol 30:1123–1142
Nusser K, Schneider GJ, Richter D (2011) Microscopic origin of the terminal relaxation time in polymer nanocomposites: an experimental precedent. Soft Matter 7:7988–7991
Osaki K, Inoue T, Uematsu T, Yamashita Y (2001) Evaluation methods of the longest Rouse relaxation time of an entangled polymer in a semidilute solution. J Polym Sci, Part B, Polym Phys 39:1704–1712
Paul DR, Robeson LM (2008) Polymer nanotechnology: nanocomposites. Polymer 49:3187–3204
Pearson D, Herbolzheimer E, Grizzuti N, Marrucci G (1991) Transient behavior of entangled polymers at high shear rates. J Polym Sci, Part B, Polym Phys 29:1589–1597
Prince E, Rouse J (1953) A theory of the linear viscoelastic properties of dilute solutions of coiling polymers. J Chem Phys 21:1272–1280
Pujari S, Rahatekar SS, Gilman JW, Koziol KK, Windle AH, Burghardt WR (2009) Orientation dynamics in multiwalled carbon nanotube dispersions under shear flow. J Chem Phys 130:214903
Ren J, Silva AS, Krishnamoorti R (2000) Linear viscoelasticity of disordered polystyrene-polyisoprene block copolymer based layered-silicate nanocomposites. Macromolecules 33:3739–3746
Ren J, Krishnamoorti R (2003) Nonlinear viscoelastic properties of layered-silicate-based intercalated nanocomposites. Macromolecules 36:4443–4451
Robertson CG, Roland CM (2008) Glass transition and interfacial segmental dynamics in polymer-particle composites. Rubber Chem Technol 81:506–522
Rueb CJ, Zukoski CF (1997) Viscoelastic properties of colloidal gels. J Rheol 41:197–218
Sarvestani AS (2008) Modeling the solid-like behavior of entangled polymer nanocomposites at low frequency regimes. Eur Polym J 44:263–269
Shih W-H, Shih WY, Kim S-I, Liu J, Aksay IA (1990) Scaling behavior of the elastic properties of colloidal gels. Phys Rev A 42:4772–4779
Solomon MJ, Almusallam AS, Seefeldt KF, Somwangthanaroj A, Varadan P (2001) Rheology of polypropylene/clay hybrid materials. Macromolecules 34:1864–1872
Song Y, Zheng Q (2010) Linear viscoelasticity of polymer melts filled with nano-sized fillers. Polymer 51:3262–3268
Sternstein SS, Zhu A-J (2002) Reinforcement mechanism of nanofilled polymer melts as elucidated by nonlinear viscoelastic behavior. Macromolecules 35:7262–7273
Utracki LA, Sepehr M, Carreau PJ (2010) Rheology of polymers with nanofillers. In: Utracki LA, Jamieson AM (eds) Polymer physics: from suspensions to nanocomposites and beyond. Wiley, Hoboken, pp 639–708
Vermant J, Ceccia S, Dolgovskij MK, Maffettone PL, Macosko CW (2007) Quantifying dispersion of layered nanocomposites via melt rheology. J Rheol 51:429–450
Whittle M, Dickinson E (1997) Stress overshoot in a model particle gel. J Chem Phys 107:10191–10200
Winter HH, Chambon F (1986) Analysis of linear viscoelasticity of a crosslinking polymer at the gel point. J Rheol 30:367–382
Yziquel F, Carreau PJ, Tanguy PA (1999) Non-linear viscoelastic behavior of fumed silica suspensions. Rheol Acta 38:14–25
Zhang Q, Archer LA (2002) Poly(ethylene oxide)/silica nanocomposites: structure and rheology. Langmuir 18:10435–10442
Zheng X, Xu Q (2010) Comparison study of morphology and crystallization behavior of polyethylene and poly(ethylene oxide) on single-walled carbon nanotubes. J Phys Chem 114:9435–9444
Zhu Z, Thompson T, Wang S-Q, von Meerwall ED, Halasa A (2005) Investigating linear and nonlinear viscoelastic behavior using model silica-particle-filled polybutadiene. Macromolecules 38:8816–8824
Acknowledgements
The authors acknowledge the financial support of Natural Sciences and Research Council of Canada and the Quebec Ministry for Economic Development, Innovation and Exportation for this work. Financial support from the ArboraNano Center of Excellence is also acknowledged. Special thanks go to Specialty Minerals, Inc. for the CaCO3 and Southern Clay Products, Inc. for the nano-clay samples. Finally, Prof. Maria Cornelia Iliuta and Mrs. Sanaz Mosagedh Sedghi are acknowledged for the contact angle measurements.
Author information
Authors and Affiliations
Electronic Supplementary Material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Hassanabadi, H.M., Rodrigue, D. Relationships between linear and nonlinear shear response of polymer nano-composites. Rheol Acta 51, 991–1005 (2012). https://doi.org/10.1007/s00397-012-0655-5
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00397-012-0655-5