Review on the Preparation, Structure and Property Relation of Clay-Based Polymer Nanocomposites

  • David, Jr. P. Peñaloza Chemistry Department, College of Science, De La Salle University, Manila
Keywords: clay-polymer nanocomposite, montmorillonite, exfoliation, clay modification


Clay-based polymer nanocomposites have attracted considerable interest in recent years because of the intermarriage between organic and clay components at nanoscale measurement offers prospect of new and enhanced properties. Resulting nanomaterials are of practical importance in applications that require exceptional mechanical properties, remarkable thermal stability, and good barrier properties. This review paper highlights the benefits we can derive from the preparation of these nanomaterials.


Advincula R. Polymer Brushes by Anionic and Cationic Surface-Initiated Polymerization (SIP). In: Surface-Initiated Polymerization I. Berlin/Heidelberg: Springer-Verlag; p. 107–36.

Akat H, Tasdelen MA, Prez F Du, Yagci Y. Synthesis and characterization of polymer/clay nanocomposites by intercalated chain transfer agent. Eur Polym J. 2008 Jul;44(7):1949–54.

Akelah A, Rehab A, Selim A, Agag T. Synthesis and application of organophilic polystyrene-montmorillonite supported onium salts in organic reactions. J Mol Catal. 1994 Dec;94(3):311–22.

Al-Esaimi MM. Reaction catalyzed by montmorillonite: Polymerization of methyl methacrylate. J Appl Polym Sci. 1997 Apr 11;64(2):367–72.

Alexandre M. Polyethylene-layered silicate nanocomposites prepared by the polymerization-filling technique: synthesis and mechanical properties. Polymer. 2002;43(8):2123–32.

Alexandre M, Beyer G, Henrist C, Cloots R, Rulmont A, Jérôme R, et al. “One-Pot” Preparation of Polymer/Clay Nanocomposites Starting from Na + Montmorillonite. 1. Melt Intercalation of Ethylene−Vinyl Acetate Copolymer. Chem Mater. 2001 Nov;13(11):3830–2.

Alexandre M, Dubois P. Polymer-layered silicate nanocomposites: preparation, properties and uses of a new class of materials. Mater Sci Eng R Reports. 2000 Jun;28(1–2):1–63.

Aranda P, Ruiz-Hitzky E. Poly(ethylene oxide)-silicate intercalation materials. Chem Mater. 1992 Nov;4(6):1395–403.

Balazs AC, Singh C, Zhulina E. Modeling the Interactions between Polymers and Clay Surfaces through Self-Consistent Field Theory. Macromolecules. 1998 Nov;31(23):8370–81.

Bergaya F, Detellier C, Lambert J-F, Lagaly G. Introduction to Clay–Polymer Nanocomposites (CPN). In 2013. p. 655–77.

Biasci L, Aglietto M, Ruggeri G, Ciardelli F. Functionalization of montmorillonite by methyl methacrylate polymers containing side-chain ammonium cations. Polymer. 1994 Jul;35(15):3296–304.

Bledzki A. Composites reinforced with cellulose based fibres. Prog Polym Sci. 1999 May;24(2):221–74.

Chen G, Chen X, Lin Z, Ye W, Yao K. Preparation and properties of PMMA/clay nanocomposite. J Mater Sci Lett. 1999;18(21):1761–3.

Chen K, Guo B, Luo J. Quaternized carboxymethyl chitosan/organic montmorillonite nanocomposite as a novel cosmetic ingredient against skin aging. Carbohydr Polym. 2017 Oct;173:100–6.

Cho J., Paul D. Nylon 6 nanocomposites by melt compounding. Polymer. 2001 Feb;42(3):1083–94.

Colonna M, Berti C, Binassi E, Fiorini M, Karanam S, Brunelle DJ. Nanocomposite of montmorillonite with telechelic sulfonated poly(butylene terephthalate): Effect of ionic groups on clay dispersion, mechanical and thermal properties. Eur Polym J. 2010 May;46(5):918–27.

Crétois R, Follain N, Dargent E, Soulestin J, Bourbigot S, Marais S, et al. Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) based nanocomposites: influence of the microstructure on the barrier properties. Phys Chem Chem Phys. 2015;17(17):11313–23.

Cui Y, Kumar S, Rao Kona B, van Houcke D. Gas barrier properties of polymer/clay nanocomposites. RSC Adv. 2015;5(78):63669–90.

Decker C, Keller L, Zahouily K, Benfarhi S. Synthesis of nanocomposite polymers by UV-radiation curing. Polymer. 2005 Aug;46(17):6640–8.

Doh JG, Cho I. Synthesis and properties of polystyrene-organoammonium montmorillonite hybrid. Polym Bull. 1998 Nov 16;41(5):511–8.

Eichhorn SJ, Baillie CA, Zafeiropoulos N, Mwaikambo LY, Ansell MP, Dufresne A, et al. Review: Current international research into cellulosic fibres and composites. J Mater Sci. 2001 May;36(9):2107–31.

Fischer HR, Gielgens LH, Koster TPM. Nanocomposites from polymers and layered minerals. Acta Polym. 1999 Apr 1;50(4):122–6.

Fornes T., Yoon P., Hunter D., Keskkula H, Paul D. Effect of organoclay structure on nylon 6 nanocomposite morphology and properties. Polymer. 2002 Jan;43(22):5915–33.

Forte C, Geppi M, Giamberini S, Ruggeri G, Veracini CA, Mendez B. Structure determination of clay/methyl methacrylate copolymer interlayer complexes by means of 13C solid state n.m.r. Polymer. 1998;39(12):2651–6.

Fu X, Qutubuddin S. Polymer–clay nanocomposites: exfoliation of organophilic montmorillonite nanolayers in polystyrene. Polymer. 2001 Jan;42(2):807–13.

Giannelis EP. Polymer Layered Silicate Nanocomposites. Adv Mater. 1996 Jan;8(1):29–35.

Giroto AS, de Campos A, Pereira EI, Ribeiro TS, Marconcini JM, Ribeiro C. Photoprotective effect of starch/montmorillonite composites on ultraviolet-induced degradation of herbicides. React Funct Polym. 2015 Aug;93:156–62.

Goldstein AN, editor. Handbook of nanophase materials. Vol. 32, Materials Research Bulletin. New York: Marcel Dekker, Inc.; 1997. 1723 p.

Hajibeygi M, Shabanian M, Khodaei-Tehrani M. New heat resistant nanocomposites reinforced silicate nanolayers containing triazine rings based on polyamide: Synthesis, characterization, and flame retardancy study. Polym Compos. 2016 Jan;37(1):188–98.

Hasegawa N, Okamoto H, Kato M, Usuki A, Sato N. Nylon 6/Na–montmorillonite nanocomposites prepared by compounding Nylon 6 with Na–montmorillonite slurry. Polymer. 2003 May;44(10):2933–7.

Hasegawa N, Okamoto H, Kawasumi M, Kato M, Tsukigase A, Usuki A. Polyolefin-clay hybrids based on modified polyolefins and organophilic clay. Macromol Mater Eng. 2000 Aug 1;280–281(1):76–9.

Hedenberg P, Gatenholm P. Conversion of plastic/cellulose waste into composites. I. Model of the interphase. J Appl Polym Sci. 1995 May 9;56(6):641–51.

Ho DL, Glinka CJ. Effects of solvent solubility parameters on organoclay dispersions. Chem Mater. 2003;15(6):1309–12.

Hoang T, Wei C, Yang Y. Tribological Study on Clay and CNF Epoxy Glass Fiber Composited Materials. In: Proceedings of the 14th IFToMM World Congress. 2015. p. 521–6.

Hong SI, Rhim JW. Preparation and properties of melt-intercalated linear low density polyethylene/clay nanocomposite films prepared by blow extrusion. LWT - Food Sci Technol. 2012;48(1):43–51.

Horsch S, Serhatkulu G, Gulari E, Kannan RM. Supercritical CO2 dispersion of nano-clays and clay/polymer nanocomposites. Polymer. 2006;47(21):7485–96.

Huang X, Brittain WJ. Synthesis and characterization of PMMA nanocomposites by suspension and emulsion polymerization. Macromolecules. 2001;34(10):3255–60.

Jeon HG, Jung H-T, Lee SW, Hudson SD. Morphology of polymer/silicate nanocomposites High density polyethylene and a nitrile copolymer. Polym Bull. 1998;41(1):107–13.

Jin Y-H, Park H-J, Im S-S, Kwak S-Y, Kwak S. Polyethylene/Clay Nanocomposite by In-Situ Exfoliation of Montmorillonite During Ziegler-Natta Polymerization of Ethylene. Macromol Rapid Commun. 2002 Jan 1;23(2):135–40.

Kawasumi M. The discovery of polymer-clay hybrids. J Polym Sci Part A Polym Chem. 2004;42(4):819–24.

Khandal D, Pollet E, Avérous L. Elaboration and behavior of poly(3-hydroxybutyrate-co-4-hydroxybutyrate)- nano-biocomposites based on montmorillonite or sepiolite nanoclays. Eur Polym J. 2016;81:64–76.

Kim S, Palomino AM. Factors influencing the synthesis of tunable clay-polymer nanocomposites using bentonite and polyacrylamide. Appl Clay Sci. 2011;51(4):491–8.

Kojima Y, Usuki A, Kawasumi M, Okada A, Kurauchi T, Kamigaito O, et al. Fine-Structure of Nylon-6-Clay Hybrid. J Polym Sci Part B-Polymer Phys. 1994;32(4):625–30.

Kornmann X, Lindberg H, Berglund L a. Synthesis of epoxy – clay nanocomposites : influence of the nature of the clay on structure. Polymer. 2001;42(4):1303–10.

Lambert JF, Bergaya F. Smectite-polymer nanocomposites. Dev Clay Sci. 2013;5:679–706.

Lan T, Kaviratna PD, Pinnavaia TJ. Mechanism of Clay Tactoid Exfoliation in Epoxy-Clay Nanocomposites. Chem Mater. 1995;7(11):2144–50.

Lee DC, Jang LW. Characterization of epoxy-clay hybrid composite prepared by emulsion polymerization. J Appl Polym Sci. 1998;68(12):1997–2005.

Lee DC, Jang LW. Preparation and Characterization of PMMA-Clay Hybrid Composite by Emulsion Polymerization. J Appl Polym Sci. 1996;61:1117–22.

Li H, Ren W, Zhu J, Xu S, Wang J. Rheology and Processing of Laponite/Polymer Nanocomposites. In: Rheology and Processing of Polymer Nanocomposites. Hoboken, NJ, USA: John Wiley & Sons, Inc.; 2016. p. 383–404.

Liu L, Qi Z, Zhu X. Studies on nylon 6/clay nanocomposites by melt‐intercalation process. J Appl Polym Sci. 1999;71(7):1133–8.

Majka TM, Leszczyńska A, Pielichowski K. Thermal stability and degradation of polymer nanocomposites. Polym Nanocomposites Electr Therm Prop. 2016;167–90.

Marchante V, Beltrán M. Montmorillonite Polyethylene Nanocomposites. Polyethyl Based Blends, Compos Nanocomposities. 2015;257–80.

Marques MDF V, Fernandes RM. Influence of Polypropylene Reaction Time on the Clay Exfoliation Process by In Situ Polymerization. J Nanosci Nanotechnol. 2017 Jul 1;17(7):5095–103.

Martino L, Guigo N, van Berkel JG, Sbirrazzuoli N. Influence of organically modified montmorillonite and sepiolite clays on the physical properties of bio-based poly(ethylene 2,5-furandicarboxylate). Compos Part B Eng. 2017;110:96–105.

Mattausch H. Properties and applications of nanoclay composites. Polym Nanoclay Compos. 2015;127–55.

Meier LP, Shelden RA, Caseri WR, Suter ’ UW. Polymerization of Styrene with Initiator Ionically Bound to High Surface Area Mica: Grafting via an Unexpected Mechanism. Macromolecules. 1994;27:1637–42.

Messersmith PB, Giannelis EP. Synthesis and Barrier Properties of Poly(e-Caprolactone)-Layered Silicate Nanocomposites. J Polym Sci A Polym Chem. 1995;33:1047–57.

Moet AS, Akelah A. Polymer-clay nanocomposites: polystyrene grafted onto montmorillonite interlayers. Mater Lett. 1993;18(1–2):97–102.

Moustafa H, Duquesne S, Haidar B, Vallat MF. Influence of the degree of exfoliation of an organoclay on the flame-retardant properties of cross-linked ethylene-co-Propylene-co-diene monomer-g-Maleic anhydride-based composites. Polym Compos. 2017;38(5):966–73.

Nese A, Sen S, Tasdelen MA, Nugay N, Yagci Y. Clay-PMMA nanocomposites by photoinitiated radical polymerization using intercalated phenacyl pyridinium salt initiators. Macromol Chem Phys. 2006;207(9):820–6.

Noh MW, Lee DC. Synthesis and characterization of PS-clay nanocomposite by emulsion polymerization. Polym Bull. 1999;42(5):619–26.

O. K. Synthesis of nylon 6-clay hybrid. J Mater Res. 1993;8(5):1179.

Ogasa T, Takahashi J, Kemmochi K. Polymer-based composite materials in general industrial fields. Adv Compos Mater. 1995;4(3):221–35.

Ogawa M, Kuroda K. Preparation of Inorganic-Organic Nanocomposites through Intercalation of Organoammonium Ions into Layered Silicates. Bull Chem Soc Jpn. 1997;70(11):2593–618.

Okada A, Usuki A. Twenty Years of Polymer-Clay Nanocomposites. Macromol Mater Eng. 2006 Dec 8;291(12):1449–76.

Okada A, Usuki A. The chemistry of polymer-clay hybrids. Mater Sci Eng C. 1995;3(2):109–15.

Okada A, Usuki A. Twenty years of polymer-clay nanocomposites. Macromol Mater Eng. 2006;291(12):1449–76.

Okamoto M, Morita S, Kim YH, Kotaka T, Tateyama H. Synthesis and structure of smectic clay/poly(methyl methacrylate) and clay/polystyrene nanocomposites via in situ intercalative polymerization. Polymer. 2000;41(10):3887–90.

Osman AF, Tuty TF, Rakibuddin M, Hashim F, Tuan Johari SAT, Ananthakrishnan R, et al. Pre-dispersed organo-montmorillonite (organo-MMT) nanofiller: Morphology, cytocompatibility and impact on flexibility, toughness and biostability of biomedical ethyl vinyl acetate (EVA) copolymer. Mater Sci Eng C. 2017;74:194–206.

Penaloza DP, Sandberg DJ, Giotto MV, Seery TAP. An exfoliated clay-poly(norbornene) nanocomposite prepared by metal-mediated surface-initiated polymerization. Polym Eng Sci. 2015;55(10).

Pramanik M, Srivastava SK, Samantaray BK, Bhowmick a. K. EVA/clay nanocomposite by solution blending: Effect of aluminosilicate layers on mechanical and thermal properties. Macromol Res. 2003;11(4):260–6.

Ramesh S, Punithamurthy K. The effect of organoclay on thermal and mechanical behaviours of thermoplastic polyurethane nanocomposites. Dig J Nanomater Biostructures. 2017;12(2):331–8.

Ray SS, Okamoto K, Okamoto M. Structure-property relationship in biodegradable poly(butylene succinate)/layered silicate nanocomposites. Macromolecules. 2003;36(7):2355–67.

Rong MZ, Zhang MQ, Liu Y, Yang GC, Zeng HM. The effect of fiber treatment on the mechanical properties of unidirectional sisal-reinforced epoxy composites. Compos Sci Technol. 2001 Aug;61(10):1437–47.

Schauberger JG, Riess G, Kern W. Preparation of UV reactive montmorillonite and characterization of its nanocomposites with poly(vinyl alcohol). J Appl Polym Sci. 2013;130(1):665–72.

Shakoor A, Rizvi TZ, Hina M. Charge transport mechanism in intercalated polypyrrole aluminum-pillared montmorillonite clay nanocomposites. J Appl Polym Sci. 2012;124(4):3434–9.

Shori S, Chen X, Peralta M, Gao H, Zur Loye HC, Ploehn HJ. Effect of interfacial pretreatment on the properties of montmorillonite/poly(vinyl alcohol) nanocomposites. J Appl Polym Sci. 2015;132(18).

Sinha Ray S, Okamoto M. Polymer/layered silicate nanocomposites: A review from preparation to processing. Prog Polym Sci. 2003;28(11):1539–641.

Song EH, Kang BH, Kim TY, Lee HJ, Park YW, Kim YC, et al. Highly oriented gold/nanoclay-polymer nanocomposites for flexible gas barrier films. ACS Appl Mater Interfaces. 2015;7(8):4778–83.

Souza PMS, Corroqué NA, Morales AR, Marin-Morales MA, Mei LHI. PLA and Organoclays Nanocomposites: Degradation Process and Evaluation of ecotoxicity Using Allium cepa as Test Organism. J Polym Environ. 2013;21(4):1052–63.

Spoljaric S, Salminen A, Dang Luong N, Lahtinen P, Vartiainen J, Tammelin T, et al. Nanofibrillated cellulose, poly(vinyl alcohol), montmorillonite clay hybrid nanocomposites with superior barrier and thermomechanical properties. Polym Compos. 2014;35(6):1117–31.

Strawhecker KE, Manias E. Structure and Properties of Poly(vinyl alcohol)/Na+ Montmorillonite Nanocomposites. Chem Mater. 2000;12:2943–9.

Swaminathan G, Shivakumar K. Thermomechanical and fracture properties of exfoliated nanoclay nanocomposites. J Reinf Plast Compos. 2011;30(3):256–68.

Szymczyk A, Paszkiewicz S, Roslaniec Z. Influence of intercalated organoclay on the phase structure and physical properties of PTT-PTMO block copolymers. Polym Bull. 2013;70(5):1575–90.

Tjong SC. Structural and mechanical properties of polymer nanocomposites. 2006 Aug;53:73–197.

Triantou MI, Tarantili PA, Andreopoulos AG. Melt processing and property testing of a model system of plastics contained in waste from electrical and electronic equipment. Waste Manag Res. 2015;33(5):453–9.

Tseng CR, Wu JY, Lee HY, Chang FC. Preparation and characterization of polystyrene-clay nanocomposites by free-radical polymerization. J Appl Polym Sci. 2002;85(7):1370–7.

Unuabonah EI, Taubert A. Clay-polymer nanocomposites (CPNs): Adsorbents of the future for water treatment. Appl Clay Sci. 2014;99:83–92.

Usuki A, Koiwai A, Kojima Y, Kawasumi M, Okada A, Kurauchi T, et al. Interaction of Nylon-6 Clay Surface and Mechanical-Properties of Nylon-6 Clay Hybrid. J Appl Polym Sci. 1995;55(1):119–23.

Usuki A, Hasegawa N, Kato M. Polymer-Clay Nanocomposites. Adv Polym Sci. 2005;179:135–95.

Usuki A, Kawasumi M, Kojima Y, Okada A, Kurauchi T. Synthesis and Properties of Diamine-Modified Nylon 6-Clay Hybrid. Kobunshi Ronbunshu. 1995;52(7):440–4.

Usuki A, Kawasumi M, Kojima Y, Okada A, Kurauchi T, Kamigaito O. Swelling behavior of montmorillonite cation exchanged for ω-amino acids by ε-caprolactam. J Mater Res. 1993;8(5):1174–8.

Vaia RA, Vasudevan S, Krawiec W, Scanlon LG, Giannelis EP. New polymer electrolyte nanocomposites: Melt intercalation of poly(ethylene oxide) in mica-type silicates. Adv Mater. 1995;7(2):154–6.

Vaia RA, Giannelis EP. Lattice Model of Polymer Melt Intercalation in Organically-Modified Layered Silicates. Am Chem Soc. 1997;9297(95):7990–9.

Vaia RA, Giannelis EP. Polymer Melt Intercalation in Organically-Modified Layered Silicates: Model Predictions and Experiment. Macromolecules. 1997;30(25):8000–9.

Vaia R a, Ishii H, Giannelis EP. Synthesis and Properties of Two-Dimensional Nanostructures by Direct Intercalation of Polymer Melts in Layered Silicates. Chem Mater. 1993;5(16):1694–6.

Valandro SR, Poli AL, Neumann MG, Schmitt CC. Organomontmorillonite/poly(methyl methacrylate) nanocomposites prepared by in situ photopolymerization. Effect of the organoclay on the photooxidative degradation. Appl Clay Sci. 2013;85(1):19–24.

Venugopal G, Veetil JC, Raghavan N, Singh V, Kumar A, Mukkannan A. Nano-dynamic mechanical and thermal responses of single-walled carbon nanotubes reinforced polymer nanocomposite thinfilms. J Alloys Compd. 2016;688:454–9.

Vuluga Z, Panaitescu DM, Sanporean CG, Radovici C, Gabor R, Nicolae CA, et al. The effect of polystyrene blocks content and of type of elastomer blocks on the properties of block copolymer/layered silicate nanocomposites. J Alloys Compd. 2014;616:569–76.

Wang MS, Pinnavaia TJ. Clay-Polymer Nanocomposites Formed from Acidic Derivatives of Montmorillonite and an Epoxy Resin. Chem Mater. 1994;6(4):468–74.

Weimer MW, Chen H, Giannelis EP, Sogah DY. Direct synthesis of dispersed nanocomposites by in situ living free radical polymerization using a silicate-anchored initiator. J Am Chem Soc. 1999;121(7):1615–6.

Wu J, Lerner MM. Structural, thermal, and electrical characterization of layered nanocomposites derived from sodium-montmorillonite and polyethers. Chem Mater. 1993;5(6):835–8.

Yano K, Usuki A, Okada A. Synthesis and properties of polyimide-clay hybrid films. J Polym Sci Part A Polym Chem. 1997 Aug;35(11):2289–94.

Yano K, Usuki A, Okada A, Kurauchi T, Kamigaito O. Synthesis and properties of polyimide-clay hybrid. J Polym Sci Part A Polym Chem. 1993;31(10):2493–8.

Yenice Z, Tasdelen MA, Oral A, Guler C, Yagci Y. Poly(styrene-b-tetrahydrofuran)/clay nanocomposites by mechanistic transformation. J Polym Sci Part A Polym Chem. 2009;47(8):2190–7.

Zhang J, Gupta RK, Wilkie CA. Controlled silylation of montmorillonite and its polyethylene nanocomposites. Polymer. 2006;47(13):4537–43.

Zhang Y, Yang JH, Ellis TS, Shi J. Crystal structures and their effects on the properties of polyamide 12/clay and polyamide 6-polyamide 66/clay nanocomposites. J Appl Polym Sci. 2006;100(6):4782–94.

Zhou Q, Fan X, Xia C, Mays J, Advincula R. Living anionic surface initiated polymerization (SIP) of styrene clay surfaces. Chem Mater. 2001;13(8):2465–7.

Zhulina E, Singh C, Balazs AC. Attraction between surfaces in a polymer melt containing telechelic chains: Guidelines for controlling the surface separation in intercalated polymer-clay composites. Langmuir. 1999;15(11):3935–43.

Ziadeh M, Weiss S, Fischer B, Förster S, Altstädt V, Müller AHE, et al. Towards completely miscible PMMA nanocomposites reinforced by shear-stiff, nano-mica. J Colloid Interface Sci. 2014;425:143–51.

How to Cite
Peñaloza, D. J. P. (2017). Review on the Preparation, Structure and Property Relation of Clay-Based Polymer Nanocomposites. KIMIKA, 28(1), 44-56.
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