Abstract
The present work attempts at a relative deduction of correlations between structure-reinforcement and chain dynamics in Laponite- and graphene oxide (GO)-dispersed epoxy nanocomposites. The fillers were reasonably well dispersed in the epoxy matrix as revealed by wide-angle X-ray diffraction, transmission electron microscopy and small-angle X-ray scattering studies. The scattering from the nanocomposites exhibited power-law behaviour at low q region with fractal dimensions, implying presence of platelets and tactoids of varying thicknesses. A comprehensive study on the thermomechanical properties of the nanocomposites was made in terms of tensile, dynamic mechanical analysis and flexural and fracture toughness measurements. The studies revealed simultaneous reinforcement as well as toughening effects in the nanocomposites; ~42 and ~34 % increases in flexural strength and mode I fracture toughness (K IC), respectively, with 0.1 wt% GO; and ~25 and ~20 % enhancements in flexural modulus and K IC with 0.1 and 0.3 wt% Laponite, respectively. A unique phenomenon of bimodal distribution of glass transition temperatures was observed as two overlapped peaks in terms of Gaussian contributions in the tan δ versus temperature profiles of the nanocomposites (from dynamic mechanical analysis) and derivative of reversible heat capacity with respect to temperature, dC p,rev/dT versus temperature profiles (from modulated differential scanning calorimetric measurements); as against a single symmetric profile for the unfilled matrix. We attempt to understand the nanofiller-induced alteration in the primary relaxation mechanisms as well as notable reinforcement and toughening effects by invoking the filler/polymer interactions, filler dispersion and fractographic investigations.
Similar content being viewed by others
References
Alexandre M, Dubois P (2000) Polymer-layered silicate nanocomposites: preparation, properties and uses of a new class of materials. Mater Sci Eng R 28:1–63
Ray SS, Okamoto M (2003) Polymer/layered silicate nanocomposites: a review from preparation to processing. Prog Polym Sci 28:1539–1641
Kuilla T, Bhadra S, Yao D, Kim NH, Bose S, Lee JH (2010) Recent advances in graphene based polymer composites. Prog Polym Sci 35:1350–1375
Kim H, Abdala AA, Macosko CW (2010) Graphene/polymer nanocomposites. Macromolecules 43:6515–6530
Zhu J, Kim J, Peng H, Margrave JL, Khabashesku VN, Barrera EV (2003) Improving the dispersion and integration of single-walled carbon nanotubes in epoxy composites through functionalization. Nano Lett 3:1107–1113
Yang H, Shan C, Li F, Zhang Q, Han D, Niu L (2009) Convenient preparation of tunably loaded chemically converted graphene oxide/epoxy resin nanocomposites from graphene oxide sheets through two-phase extraction. J Mater Chem 19:8856–8860
Donato RK, Donato KZ, Schrekker HS, Matejka L (2012) Tunable reinforcement of epoxy-silica nanocomposites with ionic liquids. J Mater Chem 22:9939–9948
Bortz DR, Heras EG, Martin GI (2012) Impressive fatigue life and fracture toughness improvements in graphene oxide/epoxy composites. Macromolecules 45:238–245
Fang M, Zhang Z, Li J, Zhang H, Lu H, Yang Y (2010) Constructing hierarchically structured interphases for strong and tough epoxy nanocomposites by amine-rich graphene surfaces. J Mater Chem 20:9635–9643
Weiping L, Hoa VS, Pugh M (2005) Fracture toughness and water uptake of high-performance epoxy/nanoclay nanocomposites. Comp Sci Technol 65:2364–2373
Lan T, Kaviratna DP, Pinnavaia JT (1995) Mechanism of clay tactoid exfoliation in epoxy-clay nanocomposites. Chem Mater 7:2144–2150
Park JH, Jana SC (2003) Mechanism of exfoliation of nanoclay particles in epoxy-clay nanocomposites. Macromolecules 36:2758–2768
Rafiee MA, Rafiee J, Wang Z, Song H, Yu ZZ, Koratkar N (2009) Enhanced mechanical properties of nanocomposites at low graphene content. ACS Nano 3:3884–3890
Gojny HF, Wichmann HGM, Fiedler B, Schulte K (2005) Influence of different carbon nanotubes on the mechanical properties of epoxy matrix composites–a comparative study. Comp Sci Technol 65:2300–2313
Yasmin A, Luo JJ, Daniel MI (2006) Processing of expanded graphite reinforced polymer nanocomposites. Comp Sci Technol 66:1182–1189
Tie L, Pinnavaia JT (1994) Clay-reinforced epoxy nanocomposites. Chem Mater 6:2216–2219
Lipinska M, Hutchinson MJ (2012) Elastomeric epoxy nanocomposites: nanostructure and properties. Comp Sci Technol 72:640–646
Wang Z, Thomas JP (1998) Hybrid organic-inorganic nanocomposites: exfoliation of magadiite nanolayers in an elastomeric epoxy polymer. Chem Mater 10:1820–1826
Isil I, Yilmazer U, Bayram G (2003) Impact modified epoxy/montmorillonite nanocomposites: synthesis and characterisation. Polymer 44:6371–6377
Zaman I, Le HQ, Kuan CH, Kawashima N, Lee L, Gerson A, Ma J (2011) Interface-tuned epoxy/clay nanocomposites. Polymer 52:497–504
Yasmin A, Abot LJ, Daniel MI (2003) Processing of clay/epoxy nanocomposites by shear mixing. Scr Mater 49:81–86
Launey ME, Ritchie RO (2009) On the fracture toughness of advanced materials. Adv Mater 21:2103–2110
Liu W, Hoa VS, Pugh M (2005) Organoclay-modified high performance epoxy nanocomposites. Comp Sci Technol 65:307–316
Domun N, Hadavinia H, Zhang T, Sainsbury T, Liaghat GH, Vahid S (2015) Improving the fracture toughness and the strength of epoxy using nanomaterials—a review of the current status. Nanoscale 7:10294–10329
Liao YH, Marietta TO, Liang Z, Zhang C, Wang B (2004) Investigation of the dispersion process of SWNTs/SC-15 epoxy resin nanocomposites. Mater Sci Eng A 385:175–181
Tak GK, Sue HJ. Preparation and mechanical properties of epoxy-clay nanocomposites. ACS Spring Meeting, 2000 (San Francisco, USA)
McIntyre S, Kaltzakorta I, Liggat JJ, Pethrick RA, Rhoney I (2005) Influence of the epoxy structure on the physical properties of epoxy resin nanocomposites. Ind Eng Chem Res 44:8573–8579
Khare KS, Khare R (2013) Effect of carbon nanotube dispersion on glass transition in cross-linked epoxy-carbon nanotube nanocomposites: role of interfacial interactions. J Phys Chem B 117:7444–7454
Allaoui A, El Bounia NE (2009) How carbon nanotubes affect the cure kinetics and glass transition temperature of their epoxy composites?–a review. Expr Polym Lett 3:588–594
Gonzalez DJ, Gonzalez M, Anson CA, Diez PMA, Gomez AM, Martinez MT (2011) Effect of various aminated single-walled carbon nanotubes on the epoxy cross-linking reactions. J Phys Chem C 115:7238–7248
Chakraborty AK, Plyhm T, Barbezat M, Necola A, Terras GP (2011) Carbon nanotube (CNT)–epoxy nanocomposites: a systematic investigation of CNT dispersion. J Nanopart Res 13:6493–6506
Wang S, Liang Z, Liu T, Wang B, Zhang C (2006) Effective amino-functionalization of carbon nanotubes for reinforcing epoxy polymer composites. Nanotechnology 17:1551
Wang S, Liang Z, Gonnet P, Liao YH, Wang B, Zhang C (2007) Effect of nanotube functionalization on the coefficient of thermal expansion of nanocomposites. Adv Funct Mater 17:87–92
Putz WK, Palmeri JM, Cohn BR, Andrews R, Brinson CL (2008) Effect of cross-link density on interphase creation in polymer nanocomposites. Macromolecules 41:6752–6756
Sun L, Warren GL, O’Reilly JY, Everett WN, Lee SM, Davis D, Lagoudas D, Sue HJ (2008) Mechanical properties of surface-functionalized SWNT/epoxy composites. Carbon 46:320–328
Natarajan B, Li Y, Deng H, Brinson LC, Schadler LS (2013) Effect of interfacial energetics on dispersion and glass transition temperature in polymer nanocomposites. Macromolecules 46:2833–2841
Patro TU, Wagner HD (2011) Layer-by-layer assembled PVA/laponite multilayer free-standing films and their mechanical and thermal properties. Nanotechnology 22:455706
Ruggerone R, Plummer JGC, Herrera NN, Lami BE, Manson EJA (2009) Highly filled polystyrene-laponite nanocomposites prepared by emulsion polymerization. Eur Polym J 45:621–629
Stankovich S, Dikin DA, Dommett GH, Kohlhaas KM, Zimney EJ, Stach EA, Ruoff RS (2006) Graphene-based composite materials. Nature 442:282–286
Hummers JWS, Offeman RE (1958) Preparation of Graphene Oxide. J Am Chem Soc 80:1339
Kaya ED (2006) Development of layered silicate/epoxy nanocomposites. PhD Dissertation, Izmir Institute of Technology
Young RJ, Kinloch IA, Gong L, Novoselov KS (2012) The mechanics of Graphene Nanocomposites: a Review. Comp Sci Technol 72:1459–1476
Martin JE, Hurd AJ (1987) Scattering from fractals. J Appl Crystallogr 20:61–78
Hurd AJ, Schaefer DW, Smith DM, Ross SB, Le MA, Spooner S (1989) Surface areas of fractally rough particles studied by scattering. Phys Rev B 39:9742
Karlsson C, Best AS, Swenson J, Kohlbrecher J, Borjesson L (2005) A SANS study of 3PEG-LiClO4-TiO2 nanocomposite polymer electrolytes. Macromolecules 38:6666–6671
Schaefer DW, Justice RS (2007) How nano are nanocomposites? Macromolecules 40:8501–8517
Miller SG, Bauer JL, Maryanski MJ, Heimann PJ, Barlow JP, Gosau JM, Allred RE (2010) Characterization of epoxy functionalized graphite nanoparticles and the physical properties of epoxy matrix nanocomposites. Comp Sci Technol 70:1120–1125
Lee C, Wei X, Kysar JW, Hone J (2008) Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321:385–388
Chen B, Evans JRG (2006) Elastic moduli of clay platelets. Scr Mater 54:1581–1585
Auad ML, Nutt SR, Pettarin V, Frontini PM (2007) Synthesis and properties of epoxy-phenolic clay nanocomposites. Exp Polym Lett 1:629–639
Rath SK, Aswal VK, Sharma C, Joshi K, Patri M, Harikrishnan G, Khakhar DV (2014) Mechanistic origins of multi-scale reinforcements in segmented polyurethane-clay nanocomposites. Polymer 55:5198–5210
Sargsyan A, Tonoyan A, Davtyan S, Schick C (2007) The amount of immobilized polymer in PMMA SiO2 nanocomposites determined from calorimetric data. Eur Polym J 43:3113–3127
Kourkoutsaki T, Logakis E, Kroutilova I, Matejka L, Nedbal J, Pissis P (2009) Polymer dynamics in rubbery epoxy networks/polyhedral oligomeric silsesquioxanes nanocomposites. J Appl Polym Sci 113:2569–2582
Krzeminski M, Molinari M, Troyon M, Coqueret X (2010) Characterization by atomic force microscopy of the nanoheterogeneities produced by the radiation-induced cross-linking polymerization of aromatic diacrylates. Macromolecules 43:8121–8127
Krzeminski M, Molinari M, Troyon M, Coqueret X (2010) Calorimetric characterization of the heterogeneities produced by the radiation-induced cross-linking polymerization of aromatic diacrylates. Macromolecules 43:3757–3763
Kong X, Narine SS (2008) Physical Properties of Sequential Interpenetrating Polymer Networks Produced from Canola Oil-Based Polyurethane and Poly(methyl methacrylate). Biomacromolecules 9:1424–1433
Rath SK, Chavan JG, Sasane S, Srivastava A, Patri M, Samui AB, Chakraborty BC, Sawant SN (2009) Coatings of PDMS-modified epoxy via urethane linkage: segmental correlation length, phase morphology, thermomechanical and surface behaviour. Prog Org Coat 65:366–374
Patil PN, Rath SK, Sharma SK, Sudarshan K, Maheshwari P, Patri M, Praveen S, Khandelwal P, Pujari PK (2013) Free volumes and structural relaxations in diglycidyl ether of bisphenol-A based epoxy–polyether amine networks. Soft Matter 9:3589–3599
Jin J, Song M, Yao KJ (2006) A MTDSC analysis of phase transition in polyurethane–organoclay nanocomposites. Thermochim Acta 447:202–208
Rath SK, Patri M, Khakhar DV (2012) Structure–thermomechanical property correlation of moisture cured poly(urethane-urea)/clay nanocomposite coatings. Prog Org Coat 75:264–273
Zaman I, Phan TT, Kuan HC, Meng Q, La LTB, Luong L, Youssf O, Ma J (2011) Epoxy/graphene platelets nanocomposites with two levels of interface strength. Polymer 52:1603–1611
Qiu J, Wang S (2010) Enhancing polymer performance through graphene sheets. J Appl Polym Sci 119:3670–3674
Acknowledgement
TUP would like to thankfully acknowledge lab facilities and financial support from DIAT (DIAT/F/MATE/4845/TUP) and the funding from DST under Fast Track Project for Young Scientist (SB/FT/CS-043/2012). The funding from DRDO–DIAT program on nanomaterials by ER-IPR, DRDO is thankfully acknowledged.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Chouhan, D.K., Rath, S.K., Kumar, A. et al. Structure-reinforcement correlation and chain dynamics in graphene oxide and Laponite-filled epoxy nanocomposites. J Mater Sci 50, 7458–7472 (2015). https://doi.org/10.1007/s10853-015-9305-5
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10853-015-9305-5