Abstract
Green nanocomposite films were elaborated from cellulose acetate (CA), three clay types as nanofillers, namely natural montmorillonite (Na-MMT) and organo-modified MMT with gelatin (Ge-MMT) or chitosan (Cs-MMT) and in the presence or absence of triethyl citrate (TEC) as an eco-friendly plasticizer, using solvent-casting method. The formation of the organoclays was confirmed by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The nanoclay dispersion within CA matrix was investigated by XRD analysis together with transmission electron microscopy (TEM). For unplasticized nano-hybrids, it was observed intercalated/exfoliated structures with a small clay tactoïds remaining, although a more aggregated structure was obtained in the presence of unmodified MMT. The plasticized nano-hybrids exhibited mainly intercalated/aggregated structure, while some exfoliated layers were much labeled in the presence of Ge-MMT nanoclay. Glass transition (T g) and melting (T m) temperatures of CA, as attested by differential scanning calorimetry (DSC) analysis, were slightly affected by clay addition. Besides, the thermal stabilities and water vapor barriers properties of CA-based nano-hybrids were enhanced by increasing clay loading, while the optical clarity, assessed by UV–visible spectroscopy, was rather decreased. Better nanocomposite properties were reached in the presence of Ge-MMT at 5 wt%. The clay impact on CA biodegradation was also studied by gravimetric, scanning electron microscopy (SEM) and TGA methods. The results highlighted a retarding effect of nanoclays, except for Ge-MMT that showed a catalytic role.
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References
Reddy MM, Vivekanandhan S, Misra M, Bhatia SK, Mohanty AK (2013) Biobased plastics and bionanocomposites: current status and future opportunities. Prog Polym Sci 38:1653–1689
Kaiser MR, Anuar HB, Samat NB, Abdul Razak SB (2013) Effect of processing routes on the mechanical, thermal and morphological properties of PLA-based hybrid biocomposite. Iran Polym J 22:123–131
Ojijo V, Ray SS (2014) Nano-biocomposites based on synthetic aliphatic polyesters and nanoclay. Prog Mater Sci 62:1–57
Rhim JW, Park HM, Ha CS (2013) Bio-nanocomposites for food packaging applications. Prog Polym Sci 38:1629–1652
Okamoto M, John B (2013) Synthetic biopolymer nanocomposites for tissue engineering scaffolds. Prog Polym Sci 38:1487–1503
Rusli H, Gandasasmita S, Amran MB (2013) Cellulose acetate-silica fume membrane: characterization and application for separation of starch and maltose. Iran Polym J 22:335–340
El Badawi N, Ramadan AR, Esawi AMK, El-Morsi M (2014) Novel carbon nanotube-cellulose acetate nanocomposite membranes for water filtration applications. Desalination 344:79–85
Yoshioka M, Takabe K, Sugiyama J, Nishio Y (2006) Newly developed nanocomposites from cellulose acetate/layered silicate/poly (e-caprolactone): synthesis and morphological characterization. J Wood Sci 52:121–127
Nejad MH, Ganster J, Bohn A, Pinnow M, Volkert B (2009) Bio-based nanocomposites of cellulose acetate and nanoclay with superior mechanical properties. Macromol Symp 280:123–129
Rodríguez FJ, Coloma A, Galotto MJ, Guarda A, Bruna JE (2012) Effect of organoclay content and molecular weight on cellulose acetate nanocomposites properties. Polym Degrad Stabil 97:1996–2001
Park HM, Liang X, Mohanty AK, Misra M, Drzal LT (2004) Effect of compatibilizer on nanostructure of the biodegradable cellulose acetate/organoclay nanocomposites. Macromolecules 37:9076–9082
Wibowo A, Misra M, Park HM, Drzal LT, Schalek R, Mohanty AK (2006) Biodegradable nanocomposites from cellulose acetate: mechanical, morphological, and thermal properties. Comp Part A A37:1428–1433
Park HM, Mohanty AK, Drzal LT, Lee E, Mielewski DF, Misra M (2006) Effect of sequential mixing and compounding conditions on cellulose acetate/layered silicate nanocomposites. J Polym Environ 14:27–35
Romero RB, Leite CAP, Gonçalves MC (2009) The effect of the solvent on the morphology of cellulose acetate/montmorillonite nanocomposites. Polymer 50:161–170
De Lima JA, Pinotti CA, Felisberti MI, Gonçalves MC (2012) Morphology and mechanical properties of nanocomposites of cellulose acetate and organic montmorillonite prepared with different plasticizers. J Appl Polym Sci 124:4628–4635
Zhang W, Liang Y, Luo W, Fang Y (2003) Effects of clay-modifying agents on the morphology and properties of poly(methyl methacrylate)/clay nanocomposites synthesized via γ-ray irradiation polymerization. J Polym Sci Pol Chem 41:321–325
Lin FH, Chen CH, Change WTK, Kuo TF (2006) Modified montmorillonite as vector for gene delivery. Biomaterials 27:3333–3338
Ratinac KR, Gilbert RG, Ye L, Jones AS, Ringer SP (2006) The effects of processing and organoclay properties on structure of poly(methyl methacrylate)-clay nanocomposites. Polymer 47:6337–6361
Chiu YC, Huang LN, Vang CM, Huang JF (1990) Determination of cation exchange capacity of clay minerals by potentiometric titration using divalent cation electrodes. Colloid Surf 46:327–337
Silverstein RM, Bassler GC, Morrill TC (1991) Spectrometric identification of organic compounds. Wiley, New York
Patel HA, Somani RS, Bajaj HC, Jasra RV (2007) Preparation and characterization of phosphonium montmorillonite with enhanced thermal stability. Appl Clay Sci 35:194–200
Kumirska J, Czerwicka M, Kaczyński Z, Bychowska A, Brzozowski K, Thöming J, Stepnowski P (2010) Application of spectroscopic methods for structural analysis of chitin and chitosan. Mar Drugs 8:1567–1636
Kabiri K, Mirzadeh H, Zohuriaan-Mehr MJ (2007) Highly rapid preparation of a bio-modified nanoclay with chitosan. Iran Polym J 16:147–151
Zhang JP, Xi LF, Zhang HL, Yao KD (2003) Correlation between reaction environment and intercalation effect in the synthesis of gelatin/montmorillonite hybrid nanocomposite. J Mater Sci Lett 22:1179–1181
Xu SW, Zhang JP, Tong L, Yao KD (2006) Interaction of functional groups of gelatin and montmorillonite in nanocomposite. J Appl Polym Sci 101:1556–1561
Ferfera-Harrar H, Dairi N (2013) Elaboration of cellulose acetate nanobiocomposites using acidified gelatin-montmorillonite as nanofiller morphology, properties, and biodegradation studies. Polym Compos 34:1515–1524
Darder M, Colilla M, Ruiz-Hitzky E (2003) Biopolymer-clay nanocomposites based on chitosan intercalated in montmorillonite. Chem Mater 15:3774–3780
Xu Y, Ren X, Hanna MA (2006) Chitosan/clay nanocomposite film preparation and characterization. J Appl Polym Sci 99:1684–1691
Martucci JF, Vázquez A, Ruseckaite RA (2007) Nanocomposites based on gelatin and montmorillonite morphological and thermal studies. J Therm Anal Calorim 89:117–122
Zhang K, Xu J, Wang KY, Cheng L, Wang J, Liu B (2009) Preparation and characterization of chitosan nanocomposites with vermiculite of different modification. Polym Degrad Stabil 94:2121–2127
Vazquez A, López M, Kortaberria G, Martín L, Mondragon I (2008) Modification of montmorillonite with cationic surfactants. Thermal and chemical analysis including CEC determination. Appl Clay Sci 41:24–36
Rodríguez FJ, Galotto MJ, Guarda A, Bruna JE (2012) Modification of cellulose acetate films using nanofillers based on organoclays. J Food Eng 110:262–268
Wang SF, Shen L, Tong YJ, Chen L, Phang IY, Lim PQ, Liu TX (2005) Biopolymer chitosan/montmorillonite nanocomposites: preparation and characterization. Polym Degrad Stabil 90:123–131
McLauchlin AR, Thomas NL (2009) Development of a novel organoclay for poly(lactic acid) nanocomposites. Polym Degrad Stabil 94:868–872
Park HM, Misra Drzal LT, Mohanty AK (2004) Green nanocomposites from cellulose acetate bioplastic and clay: effect of eco-friendly triethyl citrate plasticizer. Biomacromolecules 5:2281–2288
Romero RB, Ferrarezi MMF, Leite CAP, Alves RMV, Gonçalves MC (2013) Influence of the layered silicate type on the structure, morphology and properties of cellulose acetate nanocomposites. Cellulose 20:675–686
Tsai TY, Lin MJ, Chuang YC, Chou PC (2013) Effects of modified clay on the morphology and thermal stability of PMMA/clay nanocomposites. Mater Chem Phys 138:230–237
Kanmani P, Rhim JW (2014) Physical, mechanical and antimicrobial properties of gelatin based active nanocomposite films containing AgNPs and nanoclay. Food Hydrocolloid 35:644–652
Kiliaris P, Papaspyrides CD (2010) Polymer/layered silicate (clay) nanocomposites: an overview of flame retardancy. Prog Polym Sci 35:902–958
Bahramian AR, Ahmadi LS, Kokabi M (2014) Performance evaluation of polymer/clay nanocomposite thermal protection systems based on polyethylene glycol phase change material. Iran Polym J 23:163–169
Sun X, Lu C, Zhang W, Tian D, Zhang X (2013) Acetone-soluble cellulose acetate extracted from waste blended fabrics via ionic liquid catalyzed acetylation. Carbohydr Polym 98:405–411
Wertz JL, Bédué O, Mercier JP (2010) Cellulose science and technology. EPFL Press, Switzerland
Choudalakis G, Gotsis AD (2009) Permeability of polymer/clay nanocomposites. Eur Polym J 45:967–984
Gu J, Eberiel DT, McCarthy SP, Gross RA (1993) Degradation and mineralization of cellulose acetate in simulated thermophilic compost environments. J Environ Polym Degrad 1:281–291
Buchahnan CM, Gardner RM, Komarek RJ (1993) Aerobic biodegradation of cellulose acetate. J Appl Polym Sci 47:1709–1719
Olaru L, Olaru N, Popa VI (2004) On enzymatic degradation of cellulose acetate. Iran Polym J 13:235–240
Puls J, Wilson SA, Hölter D (2011) Degradation of cellulose acetate-based materials. J Polym Environ 19:152–165
Calil MR, Gaboardi F, Bardi MAG, Rezende ML, Rosa DS (2007) Enzymatic degradation of poly (ε-caprolactone) and cellulose acetate blends by lipase and α-amylase. Polym Test 26:257–261
Maiti P, Batt CA, Giannelis EP (2003) Renewable plastics: synthesis and properties of PHB nanocomposites. Polym Mater Sci Eng 88:58–59
Wu TM, Wu CY (2006) Biodegradable poly(lactic acid)/chitosan-modified montmorillonite nanocomposites: preparation and characterization. Polym Degrad Stabil 91:2198–2204
Fukushima K, Abbate C, Tabuani D, Gennari M, Camino G (2009) Biodegradation of poly (lactic acid) and its nanocomposites. Polym Degrad Stabil 94:1646–1655
Fukushima K, Abbate C, Tabuani D, Gennari M, Rizzarelli P, Camino G (2010) Biodegradation trend of poly (ε-caprolactone) and nanocomposites. Mater Sci Eng C 30:566–574
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Ferfera-Harrar, H., Dairi, N. Green nanocomposite films based on cellulose acetate and biopolymer-modified nanoclays: studies on morphology and properties. Iran Polym J 23, 917–931 (2014). https://doi.org/10.1007/s13726-014-0286-z
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DOI: https://doi.org/10.1007/s13726-014-0286-z