Abstract
In this chapter we focus on the barrier properties of nanocomposite of biodegradable polyesters with layered inorganic fillers. First of all, to better understand the influence of the lamellar inorganic fillers on the permeability, the theory of permeation and the barrier models so far developed for polymer nanocomposites are reviewed. Afterwards the barrier properties of the most important biodegradable polyesters filled with inorganic lamellar solids, such as Polylactic acid (PLA), Polycaprolactone (PCL), Polyhydroxbutyrate (PHB), and Polybutylenesuccinate (PBS) are reviewed and the outstanding results enlightened. As a general trend, the best improvement of barrier properties is related to the exfoliation of clay platelets into the polymeric matrix, and this in turn is dependent on the chemical structure of the clay, the organic modification, the filler concentration and the processing procedure to prepare the composite. Where possible, all these parameters were reported and correlated with the final properties. Also the contrasting effect of clays on the two parameters determining the water permeability, that is sorption and diffusion, is reported in many cases.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Kaplan DL (1998) Biopolymers from renewable resources. Springer, New York
Fakirov S, Bhattacharya D (2007) Engineering biopolymers: homopolymers, Blends and Composites. Hanser Gardner Pubns, Munchen
Van de Velde K, Kiekens P (2002) Biopolymers: overview of several properties and consequences on their applications. Polym Testing 21:433–442
Bordes P, Pollet E, Averous L (2009) Nano-biocomposites: biodegradable polyester/nanoclay systems. Prog Polym Sci 34(2):125–155
Pan P, Inoue Y (2009) Polymorphism and isomorphism in biodegradable polyesters. Prog Polym Sci 34(7):605–640
Siracusa V, Rocculi P, Romani S, Dalla Rosa M (2008) Biodegradable polymers for food packaging: a review. Trends Food Sci Technol 19(12):634–643
Alexandre M, Dubois P (2000) Polymer-layered silicate nanocomposites preparation, properties and uses of a new class of materials. Mater Sci Eng 28:1–11
Sinha Ray S, Okamoto M (2003) Polymer/layered silicate nanocomposites: a review from preparation to processing. Prog Polym Sci 28:1539–1641
Bharadwaj RK (2001) Modeling the barrier properties of polymer-layered silicate nanocomposites. Macromolecules 34:9189–9192
Sorrentino A, Tortora M, Vittoria V (2006) Diffusion behaviour in polymer-clay nanocomposites. J Polym Sci B Polym Phys 44(2):265–274
Oya A, Kurokawa Y, Yasuda H (2000) Factors controlling mechanical properties of clay mineral/polypropylene nanocomposites. J Mater Sci 35:1045–1050
Picard E, Vermogen A, Gérard JF, Espuche E (2008) Influence of the compatibilizer polarity and molar mass on the morphology and the gas barrier properties of polyethylene/clay nanocomposites. J Polym Sci B Polym Phys 46(23):2593–2604
Durmus A, Woo M, Kasgoz A, Macosko CW, Tsapatsis M (2007) Intercalated linear low density polyethylene (LLDPE)/clay nanocomposites prepared with oxidized polyethylene as a new type compatibilizer: structural, mechanical and barrier properties. Eur Polym J 43(9):3737–3749
Giannelis EP (1996) Polymer layered silicate nanocomposites. Adv Mater 8(1):29–35
Vieth WR (1991) Diffusion in and through polymers: principles and applications. Hanser, New York
Lucian AL, Orlando JR (2009) The nanoscience and technology of renewable biomaterials. Wiley, Chichester
Frisch HL, Rogers CE (1966) Transport in polymers. J Polym Sci C 12:297–315
Cussler EL (1997) Diffusion: mass transfer in fluid systems. Cambridge University Press, New York
Frisch HL (1980) Sorption and transport in glassy polymers: a review. Polym Eng Sci 20(1):2–13
Peterlin A (1975) Dependence of diffusive transport on the morphology of crystalline polymers. J Macromol Sci Phys B11(1):57–87
Comyn J (1985) Polymer permeability. Elsevier Appl Sci, London
Vieth WR, Amini MA (1974) In: Hopfenberg HB (ed) Permeability of plastic films and coatings. Plenum Press, London
Soney CG, Sabu T (2001) Transport phenomena through polymeric systems. Prog Polym Sci 26(6):985–1017
Hedenqvist M, Gedde UW (1996) Diffusion of small-molecule penetrants in semicrystalline polymers. Prog Polym Sci 21(2):299–333
Shastri R, Roehrs HC, Brown CN, Dollinger SE (1990) Permeability of competitive oxygen-barrier resins: orientability and effect of orientation. In: Barrier polymers and structures ACS symposium series, vol. 423, pp 239–251, ISBN: 9780841212794 Chap. 12
Tabatabaei SH, Carreau PJ, Ajji A (2008) Microporous membranes obtained from polypropylene blend films by stretching. J Membr Sci 325(2):772–782
Sorrentino A, Gorrasi G, Tortora M, Vittoria V (2006) Barrier properties of polymer/clay nanocomposites. In: Mai Y-W, Yu Z-Z (eds.) Polymer nanocomposites, “Woodhead Publishing Ltd”, Cambridge, pp 273–292 Chap. 11
Neilsen LE (1967) Models for the permeability of filled polymers. J Macromol Sci (Chem) A1(5):929–942
Fredrickson GH, Bicerano J (1999) Barrier properties of oriented disk composites. J Chem Phys 110:2181–2188
Lape NK, Nuxoll EE, Cussler EL (2004) Polydisperse flakes in barrier films. J Membr Sci 236:29–37
Lim L-T, Auras R, Rubino M (2008) Processing technologies for poly(lactic acid). Prog Polym Sci 33(8):820–852
Garlotta D (2001) A literature review of poly(lactic acid). J Polym Environ 9(2):63–84
Sinha Ray S, Yamada K, Ogami A, Okamoto M, Ueda K (2002) New polylactide/layered silicate nanocomposite: nanoscale control over multiple properties. Macromol Rapid Commun 23(16):943–947
Ozkoc G, Kemaloglu S, Quaedflieg M (2010) Production of poly(lactic acid)/organoclay nanocomposite scaffolds by microcompounding and polymer/particle leaching. Polym Compos 31(4):674–683
Sinha Ray S, Okamoto K, Yamada K, Okamoto M (2002) Novel porous ceramic material via burning of polylactide/layered silicate nanocomposite. Nano Lett 2(4):423–425
Sinha Ray S, Yamada K, Okamoto M, Fujimoto Y, Ogami A, Ueda K (2003) New polylactide/layered silicate nanocomposites. 5. Designing of materials with desired properties. Polymer 44(21):6633–6646
Sinha Ray S, Yamada K, Okamoto M, Ueda K (2002) Polylactide-layered silicate nanocomposite: a novel biodegradable material. Nano Lett 2(10):1093–1096
Pluta M, Galeski A, Alexandre M, Paul M-A, Dubois P (2002) Polylactide/montmorillonite nanocomposites and microcomposites prepared by melt blending: structure and some physical properties. J Appl Polym Sci 86(6):1497–1506
Balakrishnan H, Hassan A, Wahit M-U, Yussuf AA, Razak SBA (2010) Novel toughened polylactic acid nanocomposite: mechanical, thermal and morphological properties. Mater Des 31(7):3289–3298
Rhim J-W, Hong S-I, Ha C-S (2009) Tensile, water vapor barrier and antimicrobial properties of PLA/nanoclay composite films. LWT–Food. Sci Technol 42(2):612–617
Cava D, Cabedo L, Gimenez E, Gavara R, Lagaron JM (2006) The effect of ethylene content on the interaction between ethylene-vinyl alcohol copolymers and water: (I) Application of FT-IR spectroscopy to determine transport properties and interactions in food packaging films. Polym Testing 25(2):254–261
Sinha Ray S, Yamada K, Okamoto M, Ogami A, Ueda K (2003) New polylactide/layered silicate nanocomposites. 3. high-performance biodegradable materials. Chem Mater 15(7):1456–1465
Maiti P, Yamada K, Okamoto M, Ueda K, Okamoto K (2002) New polylactide/layered silicate nanocomposites: role of organoclays. Chem Mater 14(11):4654–4661
Chowdhury SR (2008) Some important aspects in designing high molecular weight poly(L-lactic acid)—clay nanocomposites with desired properties. Polym Int 57(12):1326–1332
Chang J-H, An YU, Sur GS (2003) Poly(lactic acid) nanocomposites with various organoclays. I. Thermomechanical properties, morphology, and gas permeability. J Polym Sci B Polym Phys 41(1):94–103
Thellen C, Orroth C, Froio D, Ziegler D, Lucciarini J, Farrell R, D’Souza NA, Ratto JA (2005) Influence of montmorillonite layered silicate on plasticized poly(L-lactide) blown films. Polymer 46(25):11716–11727
Ogata N, Jimenez G, Kawai H, Ogihara T (1997) Structure and thermal/mechanical properties of poly(l-lactide)-clay blend. J Polym Sci B Polym Phys 35(2):389–396
Plackett D, Sodergard A (2005) Polylactide-based biocomposites. In: Mohanty AK, Misra M, Drzal LT (eds) Natural fibers, biopolymers, and biocomposites. CRC Press, Boca Raton, pp 579–598
Petersson L, Oksman K (2006) Biopolymer based nanocomposites: comparing layered silicates and microcrystalline cellulose as nanoreinforcement. Compos Sci Technol 66(13):2187–2196
Sinha Ray S, Maiti P, Okamoto M, Yamada K, Ueda K (2002) New polylactide/layered silicate nanocomposites. 1. Preparation, characterization, and properties. macromolecules 35(8):3104–3110
Pandey JK, Kumar AP, Misra M, Mohanty AK, Drzal LT, Singh RP (2005) Recent advances in biodegradable nanocomposites. J Nanosci Nanotechnol 5(4):497–526
Koh HC, Park JS, Jeong MA, Hwang HY, Hong YT, Ha SY, Nam SY (2008) Preparation and gas permeation properties of biodegradable polymer/layered silicate nanocomposite membranes. Desalination 233(1–3):201–209
Park H-M, Ha C-S (2010) Barrier properties biodegradable nanocomposites. Barrier properties of polymer clay nanocomposites, pp 231–256
Cabedo L, Feijoo JL, Villanueva MP, Lagaron JM, Giménez E (2006) Optimization of biodegradable nanocomposites based on PLA/PCL blends for food packaging applications. Macromol Symp 233:191–197
Yano K, Usuki A, Okada A (1997) Synthesis and properties of polyimide-clay hybrid films. J Polym Sci A Polym Chem 35(11):2289–2294
Holmes PA (1985) Applications of PHB—a microbially produced biodegradable thermoplastic. Phys Technol 16(1):32–36
Pouton CW, Akhtar S (1996) Biosynthetic polyhydroxyalkanoates and their potential in drug delivery. Adv Drug Deliv Rev 18(2):133–162
Byrom D (1993) The synthesis and biodegradation of polyhydroxyalkanoates from bacteria. Int Biodeterior Biodegradation 31(3):199–208
Inoue Y, Yoshie N (1992) Structure and physical properties of bacterially synthesized polyesters. Prog Polym Sci 17(4):571–610
Doi Y (1995) Microbial synthesis, physical properties, and biodegradability of polyhydroxyalkanoates. Macromol Symp 98:585–599
Verhoogt H, Ramsay BA, Favis BD (1994) Polymer blends containing poly(3-hydroxyalkanoate)s. Polymer 35(24):5155–5169
Miguel O, Egiburu JL, Iruin JJ (2001) Blends of bacterial poly(3-hydroxybutyrate) with synthetic poly(3-hydroxybutyrate) and poly(epichlorohydrin): transport properties of carbon dioxide and water vapor. P Polym 42(3):953–962
Abe H, Matsubara I, Doi Y, (1995) Physical properties and enzymic degradability of polymer blends of bacterial Poly[(R)-3-hydroxybutyrate] and Poly[(R,S)-3-hydroxybutyrate] stereoisomers. Macromolecules 28(4):844–853
Gonzalez A, Iriarte M, Iriondo PJ, Iruin JJ (2002) Miscibility and carbon dioxide transport properties of blends of bacterial poly(3-hydroxybutyrate) and a poly(vinylidene chloride-co-acrylonitrile) copolymer. Polymer 43(23):6205–6211
Pankova YN, Shchegolikhin AN, Iordanskii AL, Zhulkina AL, Ol’khov AA, Zaikov GE (2010) The characterization of novel biodegradable blends based on polyhydroxybutyrate: the role of water transport. J Mol Liq 156:65–69
Modi S, Koelling K, Vodovotz Y (2011) Assessment of PHB with varying hydroxyvalerate content for potential packaging applications. Eur Polymer J 47:179–186
Lagaron JM, Catala R, Gavara R (2004) Structural characteristics defining high barrier properties in polymeric materials. Mater Sci Technol 20(1):1–7
Lagaron JM, Cabedo L, Cava D, Feijoo JL, Gavara R, Gimenez E (2005) Improving packaged food quality and safety. Part 2: Nanocomposites. Food Addit Contam 22(10):994–998
Sanchez-Garcia MD, Gimenez E, Lagaron JM (2008) Morphology and barrier properties of nanobiocomposites of poly(3-hydroxybutyrate) and layered silicates. J Appl Polym Sci 108(5):2787–2801
Song J, Ren M, Song C, Wang S, Zhang H, Mo Z (2004) The effect of 60Co y-rays on the crystal structure, melting and crystallization behavior of poly(butylene succinate). Polym Int 53(11):1773–1779
Fujimaki T, Harigaya N (1993) Development of biodegradable plastics Bionolle. Seikei Kako 5(1):36–41
Ishioka D (2002) Biopolymers, polyesters III. applications and commercial products, vol. 4. Wiley-VCH Verlag Gmbh, Weinheim, p 275
Nikolic MS, Djonlagic J (2001) Synthesis and characterization of biodegradable poly(butylene succinate-co-butylene adipate)s. Polym Degrad Stab 74(2):263–270
Fujimaki T (1998) Processability and properties of aliphatic polyesters, “Bionolle”, synthesized by polycondensation reaction. Polym Degrad Stab 59(1–3):209–214
Werpy T, Frye J, Holladay J (2006) Succinic acid e a model building block for chemical synthesis from renewable resources. In: Kamm JB, Gruber PR, Kam M (eds) Biorefineries e industrial processess and products: status quo and future directions, vol 1. WileyeVCH, Weinheim
Song H, Lee SY (2006) Production of succinic acid by bacterial fermentation. Enzym Microb Technol 39(3):352–361
Dornburg V, Hermann BG, Patel MK (2008) Scenario projections for future market potentials of biobased bulk chemicals. Environ Sci Technol 42(7):2261–2267
Caesar B (2008) Industrial biotechnology: more than just ethanol—factors driving industry growth. Ind Biotechnol 4(1):50–54
Huang X, Li C, Zheng L, Zhang D, Guan G, Xiao Y (2009) Synthesis, characterization and properties of biodegradable poly(butylene succinate)-block-poly(propylene glycol) segmented copolyesters. Polym Int 58(8):893–899
Papageorgiou GZ, Bikiaris DN (2005) Crystallization and melting behavior of three biodegradable poly(alkylene succinates). comp study Polym 46(26):12081–12092
Liu Y, Ranucci E, Lindblad MS, Albertsson A-C (2001) New biodegradable polymers from renewable sources: polyester-carbonates based on 1,3-propylene-co-1,4-cyclohexanedimethylene succinate. J Polym Sci A Polym Chem 39(14):2508–2519
Shih YF, Wang TY, Jeng RJ, Wu JY, Wuu DS (2008) Crosslinked and uncross-linked biodegradable nanocomposites. I. Nonisothermal crystallization kinetics and gas permeability. J Appl Polym Sci 110(2):1068–1079
Phua YJ, Chow WS, Ishak ZAM (2011) Poly(butylene succinate)/Organo-montmorillonite nanocomposites: effects of the organoclay content on mechanical, thermal, and moisture absorption properties. J Thermoplast Compos Mater 24(1):133–151
Zenga J-B, Jiao L, Li Y-D, Srinivasan M, Li T, Wanga Y-Z (2011) Bio-based blends of starch and poly(butylene succinate) with improved miscibility, mechanical properties, and reduced water absorption. Carbohydr Polym 83:762–768
Dean K, Yu L, Bateman S, Wu DY (2007) Gelatinized starch/biodegradable polyester blends: processing, morphology, and properties. J Appl Polym Sci 103(2):802–811
John J, Mani R, Bhattacharya M (2002) Evaluation of compatibility and properties of biodegradable polyester blends. J Polym Sci A Polym Chem 40(12):2003–2014
Okamoto K, Sinha Ray S, Okamoto M (2003) New poly(butylene succinate)/layered silicate nanocomposites. Part II. Effect of organically modified layered silicates on structure, properties, melt rheology, and biodegradability. J Polym Sci B Polym Phys 41(24):3160–3172
Chen G-X, Kim H-S, Yoon J-S (2007) Synthesis and characterization of poly(butylene succinate)/epoxy group functionalized organoclay. Polym Int 56(9):1159–1165
Chen G-X, Yoon J-S (2005) Nonisothermal crystallization kinetics of poly(butylene succinate) composites with a twice functionalized organoclay. J Polym Sci B Polym Phys 43(7):817–826
Chen G-X, Kim E-S, Yoon J-S (2005) Poly(butylene succinate)/twice functionalized organoclay nanocomposites: preparation, characterization, and properties. J Appl Polym Sci 98(4):1727–1732
Messersmith PB, Giannelis EP (1995) Synthesis and barrier properties of poly(ε-Capro1actone)-layered silicate nanocomposites. J Polym Sci A Polym Chem 33:1047–1057
Gorrasi G, Tortora M, Vittoria V, Pollet E, Lepoittevin B, Alexandre M, Dubois P (2003) Vapor barrier properties of polycaprolactone montmorillonite nanocomposites: effect of clay dispersion. Polymer 44:2271–2279
Gorrasi G, Tortora M, Vittoria V, Pollet E, Alexandre M, Dubois P (2004) Physical properties of poly(ε-caprolactone) layered silicate nanocomposites prepared by controlled grafting polymerization. J Polym Sci B Polym Phys 42:1466–1475
Gain O, Espuche E, Pollet E, Alexandre M, Dubois P (2005) Gas barrier properties of poly(ε-caprolactone)/clay nanocomposites: influence of the morphology and polymer/clay interactions. J Polym Sci B Polym Phys 43:205–214
Di Y, Iannace S, Sanguigno L, Nicolais L (2005) Barrier and mechanical properties of poly(caprolactone)/orgnoclay nanocomposites. Macromol Symp 228:115–124
Cava D, Giménez E, Gavara R, Lagaron JM (2006) Comparative performance and barrier properties of biodegradable thermoplastics and nano bio composites versus PET for food packaging applications. J Plast Film Sheeting 22(4):265–274
Sanchez-Garcia MD, Ocio MJ, Gimenez E, Lagaron JM (2008) Novel Polycaprolactone nanocomposites containing thymol of interest in antimicrobial film and coating applications. J Plast Film Sheeting 24:3–4
Shafiei Sabet S, Katbab AA (2009) Interfacially Compatibilized Poly(lactic acid) and Poly(lactic acid)/Polycaprolactone/Organoclay nanocomposites with improved biodegradability and barrier properties: effects of the compatibilizer structural parameters and feeding route. J Appl Polym Sci 111:1954–1963
Vertuccio L, Gorrasi G, Sorrentino A, Vittoria V (2009) Nano clay reinforced PCL/starch blends obtained by high energy ball milling. Carbohydr Polym 75:172–179
Benali S, Olivier A, Brocorens P, Bonnaud L, Alexandre M, Bourbigot S, Espuche E, Gouanve F, Lazzaroni R, Dubois P (2008) Fire and gas barrier properties of poly(styrene-co-acrylonitrile) nanocomposites using polycaprolactone/clay nanohybrid based-masterbatch. Adv Mater Sci Eng Article ID 394235, p 11 doi:10.1155/2008/394235
Sorrentino A, Gorrasi G, Tortora M, Vittoria V, Costantino U, Marmottini F, Padella F (2005) Incorporation of Mg-Al hydrotalcite into a biodegradabile poly(ε-caprolactone) by high energy ball milling. Polymer 46:1601–1608
Bugatti V, Costantino U, Gorrasi G, Nocchetti M, Tammaro L, Vittoria V (2010) Nano-hybrids incorporation into poly(e-caprolactone) for multifunctional applications: mechanical and barrier properties. Eur Polymer J 46:418–427
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2012 Springer-Verlag London
About this chapter
Cite this chapter
Sorrentino, A., Gorrasi, G., Vittoria, V. (2012). Permeability in Clay/Polyesters Nano-Biocomposites. In: Avérous, L., Pollet, E. (eds) Environmental Silicate Nano-Biocomposites. Green Energy and Technology. Springer, London. https://doi.org/10.1007/978-1-4471-4108-2_9
Download citation
DOI: https://doi.org/10.1007/978-1-4471-4108-2_9
Published:
Publisher Name: Springer, London
Print ISBN: 978-1-4471-4101-3
Online ISBN: 978-1-4471-4108-2
eBook Packages: EngineeringEngineering (R0)