Abstract
PHB is a thermoplastic biopolymer produced by fermentation of renewable resources. Secondary crystallization during storage leading to an increased degree of crystallinity is a principal reason of PHB brittleness. In addition, pure PHB has no residues of catalysts, meaning low nucleation density and slow crystallization rates, leading to the formation of large spherulites with cracks and brittleness. To overcome the brittleness of PHB, polymer composites based on PHB, plasticizers, and nano-clays A and B were prepared by solvent casting. The addition of plasticizer decreases T g from 5 to −13 °C in all composites. Furthermore, the addition of nano-clays acts as a nucleating agent to PHB. The effect of nano-clays A and B on spherulites morphology, thermal behavior, and crystal structure of PHB composites were tested by several techniques. Differential scanning calorimetry analysis shows that the addition of nano-clay A does not change the crystallization temperature and the crystallization half-time (t 1/2) of the PHB matrix but that nano-clay B accelerates the crystallization process. Thermogravimetric analysis revealed an increase in thermal stability of composites containing nano-clay B. Polarized optical microscopy showed that nano-clays serve as nucleating agents in PHB matrix. Therefore, the spherulites become smaller and the nuclei density increases at the selected crystallization temperature, compared to pure PHB.
Similar content being viewed by others
References
Steinbuchel A (2003) Biopolymers: general aspects and special applications, vol 10. Wiley, Weinheim, pp 516–530
El-Hadi A, Schnabel R, Straube E, Müller G, Riemschneider M (2002) Effect of melts processing on crystallization behavior and rheology of poly (3-hydroxybutyrate) PHB and its blends. Macromol Mater Eng 287:363–372
El-Hadi A, Schnabel R, Straube E, Muller G, Henning S (2002) Correlation between degree of crystallinity, morphology, glass temperature, mechanical properties and biodegradation of poly (3-hydroxyalkanoate) PHAs and their blends. Polym Test 21:665–674
Hobbs JK, McMaster TJ, Miles MJ, Barham PJ (1996) Cracking in spherulites of poly(hydroxybutyrate). Polymer 37:32413246
Kulkarni SO, Jog JP, Nilegaonkar SS, Sarnaik SS, Kshirsagar PR (2011) Characterisation of copolymer, poly(hydroxybutyrate-co-hydroxyvalerate) (PHB-co-PHV) produced by Halomonas campisalis (MCM B-1027), its biodegrability and potential application. Biores Technol 102:6625–6628
Zagar E, Krzan A, Adamus G, Kowalczuk M (2006) Sequence distribution in microbial poly(3-hydroxybutyrate-co-3-hydroxyvalerate) co-polyesters determined by NMR and MS. Biomacromolecules 7:2210–2216
Qu XH, Wu Q, Liang J, Qu X, Wang SG, Chen GQ (2005) Enhanced vascular-related cellular affinity on surface modified copolyesters of 3-hydroxybutyrate and 3-hydroxyhexanoate (PHBHHx). Biomaterials 26:6991–7001
Asrar J, Valentin HE, Berger PA, Tran M, Padgette SR, Garbow JR (2002) Biosynthesis and properties of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) polymers. Biomacromolecules 3:1006–1012
Vogel R, Taendler B, Voigt D, Jehnichen D, Haeußler L, Peitzsch L, Bruenig H (2007) Melt spinning of bacterial aliphatic polyester using reactive extrusion for improvement of crystallization. Macromol Biosci 7:820–828
Hermida EB, Mega VI, Yashchuk O, Fernandez V, Eisenberg P, Miyazaki SS (2008) Gamma irradiation effects on mechanical and thermal properties and biodegradation of poly (3-hydroxybutyrate) based films. Macromol Symposia 263:102–113
Carswell-Pomerantz T, Hill DJT, O’Donnell JH, Pomery P (1995) J Radiat Phys Chem 45:737–744
Bibers K, Kalnis M (1999) Control of biopolymer poly-β-hydroxybutyrate characteristics by γ-irradiation. Mech Compos Mater 35:169–178
Oliveira LM, Araujo ES, Guedes SML (2006) Gamma irradiation effects on poly(hydroxybutyrate). Polym Degrad Stab 91:2157–2162
Choi JS, Park WH (2004) Effect of biodegradable plasticizers on thermal and mechanical properties of poly(3-hydroxybutyrate). Polym Test 23:455–460
Janigová I, Lacík I, Chodák I (2002) Thermal degradation of plasticized poly(3-hydroxybutyrate) investigated by DSC. Polym Degrad Stab 77:35–41
Baltier RC, Innocentini Mei LH, Bartoli J (2003) Study of the effect of plasticizers on thermal and mechanical properties of poly(3-hydroxybutyrate) PHB compounds. Macromol Symp 197:33–44
Yoshie N, Nakato K, Fujiwara M, Kasuya K, Abe H, Doi Y, Inoue Y (2000) Effect of low molecular weight additives on enzymatic degradation of poly(3-hydroxybutyrate). Polymer 41:3227–3233
Wang L, Zhu W, Wang X, Chen X, Chen GQ, Xu K (2008) Processability modifications of poly(3-hydroxybutyrate) by plasticizing, blending, and stabilizing. J Appl Polym Sci 107:166–173
Grillo Fernandes E, Pietrini M, Chiellini E (2004) Thermo-mechanical and morphological characterization of plasticized poly((R)-3-hydroxybutyric acid). Macromol Symposia 218:157–164
Rodrigues JAFR, Parra DF, Lug AB (2005) Crystallization on films of PHB/PEG blends, evaluation by DSC. J Therm Anal Calorim 79:379–381
Parra DF, Fusaro J, Gaboardi F, Rosa DS (2006) Influence of poly (ethylene glycol) on the thermal, mechanical, morphological, physicalechemical and biodegradation properties of poly (3-hydroxybutyrate). Polym Degrad Stab 91:1954–1959
Hong SG, Hsu HW, Ye MT (2013) Thermal properties and applications of low molecular weight polyhydroxybutyrate. J Therm Anal Calorim 111:1243–1250
Choi JS, Park WH (2004) Effect of biodegradable plasticizers on thermal and mechanical properties of poly(3-hydroxybutyrate). Polym Test 23:455–460
Rajan PAR, Sreekumar K, Joseph M (2012) Thermal and mechanical properties of chitosan reinforced polyhydroxybutyrate composites. J Appl Poly Sci 124:3357–3362
El-Hadi AM (2013) Influence of microcrystalline cellulose fiber (MCCF) on the morphology of poly(3-hydroxybutyrate) (PHB). Colloid Polym Sci 291:743–756
Kai W, He Y, Inoue Y (2005) Fast crystallization of poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with talc and boron nitride as nucleating agents. Polym Int 54:780–789
He Y, Inoue Y (2004) Effect of α-cyclodextrin on the crystallization of poly(3-hydroxybutyrate). J Poly Sci Part B Poly Phys 42:3461–3469
Jing X (2012) Effect of low thermally reduced graphene loadings on the crystallization kinetics and morphology of biodegradable poly(3-hydroxybutyrate). Ind Eng Chem Res 51:13686–13691
Miloaga D, Hosein H, Misra M, Drzal L (2007) Crystallization of poly(3-hydroxybutyrate) by exfoliated graphite nanoplatelets. J Appl Polym Sci 106:2548–2558
Yun S, Gadd G, Latella B, Lo V, Russell R, Holden P (2008) Mechanical properties of biodegradable polyhydroxyalkanoates/single wall carbon nanotube nanocomposite films. Polym Bull 61:267–275
Alata H, Hexig B, Inoue Y (2006) Effect of poly(vinyl alcohol) fine particles as a novel biodegradable nucleating agent on the crystallization of poly(3-hydroxybutyrate). J Poly Sci Part B Poly Phys 44:1813–1820
Braham PJ (1984) Nucleation behaviour of poly-3-hyd roxy-butyrate. J Mater Sci 19:3826–3834
Jacquel N, Tajima K, Nakamura N, Kawachi H, Pan P, Inoue Y (2010) Nucleation mechanism of polyhydroxybutyrate and poly(hydroxybutyrate-co-hydroxyhexanoate) crystallized by orotic acid as a nucleating agent. J Appl Polym Sci 115:709–715
Maiti P, Batt C, Giannelis E (2007) New biodegradable polyhydroxybutyrate and layered silicate nanocomposites. Biomacromolecules 8:3393–3400
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 108:2787–2801
Bordes P, Hablot E, Pollet E, Avérous L (2009) Polym Degrad Stab 94:789–796
Botana A, Mollo M, Eisenberg P, Sanchez RMT (2010) Effect of modified montmorillonite on biodegradable PHB nanocomposites. Appl Clay Sci 47:263–270
Xu C, Qiu Z (2011) Crystallization behavior and thermal property of biodegradable poly(3-hydroxybutyrate)/multi-walled carbon nanotubes nanocomposites. Polym Adv Technol 22:538–544
Xu C, Qiu Z (2009) Nonisothermal melt crystallization and subsequent melting behavior of biodegradable poly(hydroxybutyrate) and multiwalled carbon nanotubes nanocomposites. J Poly Sci Part B Poly Phys 47:2238–2246
Bertini F, Canetti M, Cacciamani A, Elegir G, Orlandi M, Zoia L (2012) Effect of ligno-derivatives on thermal properties and degradation behavior of poly(3-hydroxybutyrate)-based biocomposites. Polym Degrad Stab 97:1979–1987
Weihua K, He Y, Asakawa N, Inoue Y (2004) Effect of lignin particles as a nucleating agent on crystallization of poly(3-hydroxybutyrate). J Appl Polym Sci 94:2466–2474
Mousavioun P, George GA, Doherty WOS (2012) Environmental degradation of lignin/poly(hydroxybutyrate) blends. Polym Degrad Stab 97:1114–1122
de Koning GJM, Scheeren AHC, Lemstra PJ (1994) Crystallization phenomena in bacterial poly((R)-3-hydroxybutyrate): 3. Toughening via texture changes. Polymer 35:4598–4605
Black SN, Dobbs BP, Dempsey S, Davey R (1990) Crystal chemistry and nucleating agents; saccharin and poly-3-hydroxybutyrate. J Mater Sci Lett 9:51–56
Al-Salah HA (1998) Crystallization and morphology of poly(ethylene succinate) and poly(b-hydroxybutyrate) blends. Polym Bull 41:593–600
El-Hadi AM (2011) Effect of processing conditions on the development of morphological features of banded or nonbanded spherulites of poly(3-hydroxybutyrate) (PHB) and polylactic acid (PLLA) blends. Polym Eng Sci 51:2191–2201
Avella M, Martuscelli E, Greco P (1991) Crystallization behaviour of poly(ethylene oxide) from poly(3-hydroxybutyrate)/poly(ethylene oxide) blends: phase structuring, morphology and thermal behavior. Polymer 32:1647–1653
Roa JPB, de O’Patrício PSR, Oréfice L, Lago RM (2013) Improvement of the thermal properties of poly(3-hydroxybutyrate) (PHB) by low molecular weight polypropylene glycol (LMWPPG) addition. J Appl Polym Sci 128:3019–3025
Abdel-Hady EE, Abdel-Hamed MO, Hammam AM (2011) Miscibility and crystallization behavior of poly(3-hydroxybutyrate) and poly(ethylene glycol) blends studied by positron annihilation spectroscopy. J Phys Conf Ser (IOP Sci) 262:012004
Reusch RN (2013) The role of short-chain conjugated poly-(R)-3-hydroxybutyrate (phb) in protein folding. Int J Mol Sci 14:10727–10748
Ziabicki A (1976) Fundamental of fiber spinning. Wiley, New York, pp 112–114
Razumovskii LP, Iordonskii AL, Zaikov GE (1992) Water in polymer, year book. In: Pethric RA, Chur NY (eds) Harwood Acodemic puplishers, vol 9 pp 139–150
Razumovskii LP, Iordonskii AL, Zaikov GE, Zagreba ED, McNeil TC (1994) Sorption and diffusion of water and organic solvents in poly(β-hydroxybutyrate) films. Polym Degrad Stab 44:175–177
Geoffry P, Morchessoult RH (1994) Spreading of poly(β-hydroxylalkanoate)s at the air-water interface: a model system for the nascent lyotropic state of bacterial polyesters polymer 35 :435–437
Hobbs JK, Barham PJ (1997) The effect of water on the crystallization of thin films of poly(hydroxybutyrate). Polymer 38:3879–3883
Lauzier C, Reval JF, Marchessault RH (1992) Topotactic crystallization of isolated poly(β-hydroxybutyrate) granules from alcaligenes eutrophus. FEMS Microbiol Lett 103:299–310
Bloembergen S, Holden DA (1986) Studies of composition and crystalinity of bacteria poly(β-hydroxybutyrate-co-β-hydroxyvalerate). Macromolecules 19:2865–2871
Padermshoke A, Katsumoto Y, Sato H, Ekgasit S, Noda I, Ozaki Y (2005) Melting behavior of poly(3-hydroxybutyrate) investigated by two-dimensional infrared correlation spectroscopy. Spectrochim Acta Part A Mol Biomol Spectrosc 61:541–550
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Mohamed El-Hadi, A. Investigation of the effect of nano-clay type on the non-isothermal crystallization kinetics and morphology of poly(3(R)-hydroxybutyrate) PHB/clay nanocomposites. Polym. Bull. 71, 1449–1470 (2014). https://doi.org/10.1007/s00289-014-1135-0
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00289-014-1135-0