Abstract
Detailed knowledge of the organization of amorphous and crystalline phases in a semicrystalline polymer such as poly(l-lactic acid) (PLLA) is crucial for complete understanding and prediction of its physical properties. In semicrystalline polymers, amorphous segments located at different distances from the crystalline domains can exhibit different properties. In PLLA, there exist (1) two distinct mobile amorphous fractions (a bulk-like totally mobile amorphous fraction and a slightly constrained mobile amorphous fraction), which vitrify/devitrify in the region of the bulk glass transition temperature (T g); and (2) a rigid amorphous fraction, located at the crystal–amorphous interface, which vitrifies/devitrifies at temperatures higher than the bulk T g. Knowledge of these three amorphous phases was derived through the use of different experimental techniques. The results together suggested a link between the crystalline morphology and the percentage content and segmental dynamics of the three amorphous fractions of PLLA. These studies are collected and summarized in the present contribution, with special emphasis on the evolution of the different amorphous fractions during crystallization of PLLA at different temperatures. A connection between the presence of rigid amorphous fraction at the crystal–amorphous interface and the melting behavior of PLLA is discussed. In addition, some physical properties of completely amorphous PLLA and poly(lactic acid) copolymers containing different percentages of d-lactic acid co-units are presented and compared.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Wunderlich B (2003) Reversible crystallization and rigid-amorphous phase in semicrystalline macromolecules. Prog Polym Sci 28:383–450
Di Lorenzo ML, Righetti MC (2008) The three-phase structure of isotactic poly(1-butene). Polymer 49:1323–1331
Kolesov I, Androsch R (2012) The rigid amorphous fraction of cold-crystallized polyamide 6. Polymer 53:4770–4777
Martin S, Exposito MT, Vega JF, Martinez-Salazar J (2013) Microstructure and properties of branched polyethylene: application of a three-phase structural model. J Appl Polym Sci 128:1871–1878
Nguyen TL, Bédoui F, Mazeran P-E, Guigon M (2015) Mechanical investigation of confined amorphous phase in semicrystalline polymers: Case of PET and PLA. Polym Eng Sci 55:397–405
Lin J, Shenogin S, Nazarenko S (2002) Oxygen solubility and specific volume of rigid amorphous fraction in semicrystalline poly(ethylene terephthalate). Polymer 43:4733–4743
Olson BG, Lin J, Nazarenko S, Jamieson AM (2003) Positron annihilation lifetime spectroscopy of poly(ethylene terephthalate): contributions from rigid and mobile amorphous fractions. Macromolecules 36:7618–7623
Drieskens M, Peeters R, Mullen J, Franco D, Lemstra PJ, Hristova-Bogaerds DG (2009) Structure versus properties relationship of poly(lactic acid). I. Effect of crystallinity on barrier properties. J Polym Sci Polym Phys 7:2247–2258
Delpouve N, Stoclet G, Saiter A, Dargent E, Marais S (2012) Water barrier properties in biaxially drawn poly(lactic acid) films. J Phys Chem B 116:4615–4625
Guinault A, Sollogoub C, Ducruet V, Domenek S (2012) Impact of crystallinity of poly(lactide) on helium and oxygen barrier properties. Eur Polym J 48:779–788
Kitamaru R, Nakaoki T, Alamo RG, Mandelkern L (1996) A carbon-13 NMR study of the phase structure of semicrystalline polymers: hydrogenated polybutadiene. Macromolecules 29:6847–6852
Tapash A, DesLauriers PJ, White JL (2015) Simple NMR experiments reveal the influence of chain length and chain architecture on the crystalline/amorphous interface in polyethylenes. Macromolecules 48:3040–3048
Stribeck N, Alamo RG, Manelkern L, Zachmann HG (1995) Study of the phase structure of linear polyethylene by means of small-angle X-ray scattering and Raman spectroscopy. Macromolecules 28:5029–5036
Chen H, Cebe P (2007) Investigation of the rigid amorphous fraction in nylon-6. J Therm Anal Calorim 89:417–425
Alamo RG, Chan EKM, Mandelkern L, Voigt-Martin IG (1992) Influence of molecular weight on the melting and phase structure of random copolymers of ethylene. Macromolecules 25:6381–6394
Alamo RG, Viers BD, Mandelkern L (1993) Phase structure of random ethylene copolymers: a study of counit content and molecular weight as independent variables. Macromolecules 26:5740–5747
Schick C, Wurm A, Mohammed A (2003) Formation and disappearance of the rigid amorphous fraction in semicrystalline polymers revealed from frequency dependent heat capacity. Thermochim Acta 396:119–132
Androsch R, Wunderlich B (2005) The link between rigid amorphous fraction and crystal perfection in cold-crystallized poly(ethylene terephthalate). Polymer 46:12556–12566
Righetti MC, Tombari E, Angiuli M, Di Lorenzo ML (2007) Enthalpy-based determination of crystalline, mobile amorphous and rigid amorphous fractions in semicrystalline polymers: poly(ethylene terephthalate). Thermochim Acta 462:15–24
Chen H, Cebe P (2009) Vitrification and devitrification of rigid amorphous fraction of PET during quasi-isothermal cooling and heating. Macromolecules 42:288–292
Xu H, Ince S, Cebe P (2003) Development of the crystallinity and rigid amorphous fraction in cold-crystallized isotactic polystyrene. J Polym Sci Polym Phys 41:3026–3036
Xu H, Cebe P (2004) Heat capacity study of isotactic polystyrene: dual reversing crystal melting and relaxation of rigid amorphous fraction. Macromolecules 37:2797–2806
Righetti MC, Tombari E, Di Lorenzo ML (2008) Crystalline, mobile amorphous and rigid amorphous fractions in isotactic polystyrene. Eur Polym J 44:2659–2667
Righetti MC, Tombari E (2011) Crystalline, mobile amorphous and rigid amorphous fractions in poly(l-lactic acid) by TMDSC. Thermochim Acta 522:118–127
Di Lorenzo ML, Gazzano M, Righetti MC (2012) The role of the rigid amorphous fraction on cold crystallization of poly(3-hydroxybutyrate). Macromolecules 45:5684–5691
Righetti MC, Tombari E, Di Lorenzo ML (2013) The role of the crystallization temperature on the nanophase structure evolution of poly[(R)-3-hydroxybutyrate]. J Phys Chem B 117:12303–12311
Righetti MC, Laus M, Di Lorenzo ML (2014) Temperature dependence of the rigid amorphous fraction in poly(ethylene terephthalate). Eur Polym J 58:60–68
Righetti MC, Di Lorenzo ML (2016) Rigid amorphous fraction and multiple melting behavior in poly(butylene terephthalate) and isotactic polystyrene. J Therm Anal Calorim 126:521–530
Righetti MC, Prevosto D, Tombari E (2016) Time and temperature evolution of the rigid amorphous fraction and differently constrained amorphous fractions in PLLA. Macromol Chem Phys 217:2013–2026
Cheng SZD, Cao M-Y, Wunderlich B (1986) Glass transition and melting behavior of poly(oxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene). Macromolecules 19:1868–1876
Cheng SZD, Wu ZQ, Wunderlich B (1987) Glass transition and melting behavior of poly(thio-1,4-phenylene). Macromolecules 20:2802–2810
Cheng SZD, Wunderlich B (1988) Glass transition and melting behavior of poly(ethylene-2,6-naphthalenedicarboxylate). Macromolecules 21:789–797
Wunderlich B (1976) Macromolecular physics, vol 2. Academic, New York
Alizadeh A, Richardson L, Xu J, McCartney S, Marand H (1999) Influence of structural and topological constraints on the crystallization and melting behavior of polymers. 1. Ethylene/1-octene copolymers. Macromolecules 32:6221–6235
Righetti MC, Laus M, Di Lorenzo ML (2014) Rigid amorphous fraction and melting behaviour of poly(ethylene terephthalate). Colloid Polym Sci 292:1365–1374
Gupta AP, Kumar V (2007) New emerging trends in synthetic biodegradable polymers – Polylactide: a critique. Eur Polym J 43:4053–4074
Pan P, Inoue Y (2009) Polymorphism and isomorphism in biodegradable polyesters. Progr Polym Sci 34:605–640
Pan P, Kai W, Zhu B, Dong T, Inoue Y (2007) Polymorphous crystallization and multiple melting behavior of poly(l-lactide): molecular weight dependence. Macromolecules 40:6898–6905
Kawai T, Rahman N, Matsuba G, Nishida K, Kanaya T, Nakano M, Okamoto H, Kawada J, Usuki A, Honma N, Nakajima K, Matsuda M (2007) Crystallization and melting behavior of poly(l-lactic acid). Macromolecules 40:9463–9469
Zhang J, Tashiro K, Tsuji H, Domb AJ (2008) Disorder-to-order phase transition and multiple melting behavior of poly(l-lactide) investigated by simultaneous measurements of WAXS and DSC. Macromolecules 41:1352–1357
Cocca M, Di Lorenzo ML, Malinconico M, Frezza V (2011) Influence of crystal polymorphism on mechanical and barrier properties of poly(l-lactic acid). Eur Polym J 47:1073–1080
Androsch R, Schick C, Di Lorenzo ML (2014) Melting of conformationally disordered crystals α′-phase of poly(l-lactic acid). Macromol Chem Phys 215:1134–1139
Ikada Y, Jamshidi K, Tsuji H, Hyon S-H (1987) Stereocomplex formation between enantiomeric poly(lactides). Macromolecules 20:904–906
Tsuji H, Ikada Y (1996) Crystallization from the melt of poly(lactide)s with different optical purities and their blends. Macromol Chem Phys 197:3486–3499
Urayama H, Moon S-I, Kimara Y (2003) Microstructure and thermal properties of polylactides with different l- and d-unit sequences: importance of the helical nature of the l-sequenced segments. Macromol Mater Eng 288:137–143
Sarasua JR, Lopez Arraiza A, Balerdi P, Maiza I (2005) Crystallinity and mechanical properties of optically pure polylactides and their blends. Polym Eng Sci 45:745–753
Woo EM, Chang L (2011) Crystallization and morphology of stereocomplexes in nonequimolar mixtures of poly(l-lactic acid) with excess poly(d-lactic acid). Polymer 52:6080–6089
Pyda M, Bopp RC, Wunderlich B (2004) Heat capacity of poly(lactic acid). J Chem Thermodyn 36:731–742
Pyda M, Wunderlich B (2005) Reversing and nonreversing heat capacity of poly(lactic acid) in the glass transition region by TMDSC. Macromolecules 38:10472–10479
Saeidlou S, Huneault MA, Li H, Park CB (2012) Poly(lactic acid) crystallization. Prog Polym Sci 37:1657–1677
Jamishidi K, Hyon SH, Ikada Y (1988) Thermal characterization of polylactides. Polymer 29:2229–2234
Abe H, Kikkawa Y, Inoue Y, Doi Y (2001) Morphological and kinetic analyses of regime transition for poly[(S)-lactide] crystal growth. Biomacromolecules 2:1007–1014
Dorgan JR, Janzen J, Clayton MP, Hait SB, Knauss DM (2005) Melt rheology of variable l-content poly(lactic acid). J Rheol 49:607–619
Di Lorenzo ML, Rubino P, Romain L, Helou M (2014) Influence of chain structure on crystal polymorphism of poly(lactic acid). Part 1: effect of optical purity of monomer. Colloid Polym Sci 292:399–409
Di Lorenzo ML, Rubino P, Immirzi B, Luijkx R, Helou M, Androsch R (2015) Influence of chain structure on crystal polymorphism of poly(lactic acid). Part 2. Effect of molecular mass on the crystal growth rate and semicrystalline morphology. Colloid Polym Sci 293:2459–2467
Baratian S, Hall ES, Lin JS, Xu R, Runt J (2001) Crystallization and solid-state structure of random polylactide copolymers: poly(l-lactide-co-d-lactide)s. Macromolecules 34:4857–4864
Urayama H, Kanamori T, Kimura Y (2001) Microstructure and thermomechanical properties of glassy polylactides with different optical purity of the lactate units. Macromol Mater Eng 286:705–713
Hodge IM (1994) Enthalpy relaxation and recovery in amorphous materials. J Non-Cryst Solids 169:211–266
Hutchinson JM (1995) Physical aging of polymers. Prog Polym Sci 20:703–760
Pan P, Zhu B, Inoue Y (2007) Enthalpy relaxation and embrittlement of poly(l-lactide) during physical ageing. Macromolecules 40:9664–9671
Cowie JMG, Ferguson R (1989) Physical aging studies in poly(vinyl methyl ether). 1. Enthalpy relaxation as a function of aging temperature. Macromolecules 22:2307–2312
Pan P, Zhu B, Dong T, Yazawa K, Shimizu T, Tansho M, Inoue Y (2008) Conformational and microstructural characteristics of poly(l-lactide) during glass transition and physical aging. J Chem Phys 129:184902
Na B, Lv R, Zou S, Li Z, Tian N (2010) Spectroscopic evidence of melting of ordered structures in the aged glassy poly(l-lactic acid). Macromolecules 43:1702–1705
Zhang T, Hu J, Duan Y, Pi F, Zhang J (2011) Physical aging enhanced mesomorphic structure in melt-quenched poly(l-lactic acid). J Phys Chem B 115:13835–13841
Pan P, Liang Z, Zhu B, Dong T, Inoue Y (2008) Roles of physical aging on crystallization kinetics and induction period of poly(l-lactide). Macromolecules 41:8011–8019
Androsch R, Di Lorenzo ML (2013) Crystal nucleation in glassy poly(l-lactic acid). Macromolecules 46:6048–6056
Androsch R, Iqbal HMN, Schick C (2015) Non-isothermal crystal nucleation of poly(l-lactic acid). Polymer 81:151–158
Androsch R, Schick C (2016) Interplay between the relaxation of the glass of random l/d-lactide copolymers and homogeneous crystal nucleation: evidence for segregation of chain defects. J Phys Chem B 120:4522–4528
Androsch R, Di Lorenzo ML, Schick C (2016) Crystal nucleation in random l/d-lactide copolymers. Eur Polym J 75:474–485
Aou K, Hsu SL, Kleiner LW, Tang F-W (2007) Roles of configurational and configurational defects on the physical ageing of amorphous poly(lactic acid). J Phys Chem B 111:12322–12327
Kwon M, Lee SC, Jeoung YG (2010) Influence of physical aging on enthalpy relaxation behavior, gas permeability, and dynamic mechanical property of polylactide films with various d-isomer contents. Macromol Res 18:246–351
Rodney RD, Ellison CJ, Broadbelt LJ, Torkelson JM (2005) Structural relaxation of polymer glasses at surfaces, interfaces, and in between. Science 309:456–459
Zhuravlev E, Schmelzer JWP, Wunderlich B, Schick C (2011) Kinetics of nucleation and crystallization in poly(ε-caprolactone) (PCL). Polymer 52:1983–1997
Iannace S, Nicolais L (1997) Isothermal crystallization and chain mobility of poly(l-lactide). J Appl Polym Sci 64:911–919
Kanchanasopa M, Runt J (2004) Broadband dielectric investigation of amorphous and semicrystallline l-lactide/meso-lactide copolymers. Macromolecules 37:863–871
Wang Y, Funari SS, Mano JF (2006) Influence of semicrystalline morphology on the glass transition of poly(l-lactic acid). Macromol Chem Phys 207:1262–1271
Arnoult M, Dargent E, Mano JF (2007) Mobile amorphous fragility in semi-crystalline polymers: comparison of PET and PLLA. Polymer 48:1012–1019
Delpouve N, Saiter A, Mano JF, Dargent E (2008) Cooperative rearranging region size in semi-crystalline poly(l-lactic acid). Polymer 49:3130–3135
Zuza E, Ugartemendia JM, Lopez A, Meaurio E, Lejardi A, Sarasua J-R (2008) Glass transition behavior and dynamic fragility in polylactides containing mobile and rigid amorphous fractions. Polymer 49:4427–4432
Magon A, Pyda M (2009) Study of crystalline and amorphous phase of biodegradable poly(lactic acid) by advanced thermal analysis. Polymer 50:3967–3973
del Rio J, Etxeberria A, Lopez-Rodriguez N, Lizundia E, Sarasua JR (2010) A PALS contribution to the supramolecular structure of poly(l-lactide). Macromolecules 43:4698–4707
Badrinarayanan P, Dowdy KB, Kessler MR (2010) A comparison of crystallization behavior for melt and cold crystallized poly(l-lactide) using rapid scanning rate calorimetry. Polymer 5:4611–4618
Di Lorenzo ML, Cocca M, Malinconico M (2011) Crystal polymorphism of poly(l-lactic acid) and its influence on thermal properties. Thermochim Acta 522:110–117
Delpouve N, Saiter A, Dargent E (2011) Cooperatively length evolution during crystallization of poly(lactic acid). Eur Polym J 47:2414–2423
Lizundia E, Petisco S, Sarasua J-R (2013) Phase-structure and mechanical properties of isothermally melt- and cold-crystallized poly(l-lactide). J Mech Behav Biomed Mater 17:242–251
Saiter A, Delpouve N, Dargent E, Oberhauser W, Conzatti L, Cicogna F, Passaglia E (2016) Probing the chain segment mobility at the interface of semi-crystalline polylactide/clay nanocomposites. Eur Polym J 78:274–289
Wunderlich B (1995) The ATHAS database on heat capacities of polymers. Pure Appl Chem 67:1019–1026. Polymer thermodynamics in http://materials.springer.com/
Righetti MC, Gazzano M, Di Lorenzo ML, Androsch R (2015) Enthalpy of melting of α'- and α-crystals of poly(l-lactic acid). Eur Polym J 70:215–220
Androsch R (2008) Surface structure of folded-chain crystals of poly(R-3-hydroxybutyrate) of different chain length. Polymer 49:4673–4679
Di Lorenzo ML, Androsch R, Righetti ML (2015) The irreversible Form II to Form I transformation in random butene-1/ethylene copolymers. Eur Polym J 67:264–273
Di Lorenzo ML (2005) Crystallization behavior of poly(l-lactic acid). Eur Polym J 41:569–575
Righetti MC (1999) Reversible melting in poly(butylene terephthalate). Thermochim Acta 330:131–135
Aharoni SM (1997) Increased glass transition temperature in motionally constrained semicrystallline polymers. Polym Adv Technol 9:169–201
Righetti MC, Di Lorenzo ML (2011) Melting temperature evolution of non-reorganized crystals. Poly(3-hydroxybutyrate). Thermochim Acta 512:59–66
Di Lorenzo ML (2006) Calorimetric analysis of the multiple melting behavior of poly(l-lactic acid). J Appl Polym Sci 100:3145–3151
Yasuniwa M, Tsubakihara S, Sugimoto Y, Nakafuku C (2004) Thermal analysis of the double-melting behavior of poly(l-lactic acid). J Polym Sci Polym Phys 42:25–32
Yasuniwa M, Iura K, Dan Y (2007) Melting behavior of poly(l-lactic acid): effects of crystallization temperature and time. Polymer 48:5398–5407
Yasuniwa M, Sakamo K, Ono Y, Kawahara W (2008) Melting behavior of poly(l-lactic acid): X-ray and DSC analyses of the melting process. Polymer 49:1943–1951
Ren J, Adachi K (2003) Dielectric relaxation in blends of amorphous poly(dl-lactic acid) and semicrystalline poly(l-lactic acid). Macromolecules 36:5180–5186
Mano JF (2007) Structural evolution of the amorphous phase during crystallization of poly(l-lactic acid): a synchrotron wide-angle X-ray scattering study. J Non-Cryst Solids 353:2567–2572
Dionisio M, Viciosa MT, Wang Y, Mano JF (2005) Glass transition dynamics of poly(l-lactic acid) during isothermal crystallization monitored by real-time dielectric relaxation spectroscopy measurements. Macromol Rapid Commun 26:1423–1427
Bras AR, Viciosa MT, Wang Y, Dionisio M, Mano JF (2006) Crystallization of poly(l-lactic acid) probed with dielectric relaxation spectroscopy. Macromolecules 39:6513–6520
Saiter A, Delpouve N, Dargent E, Saiter JM (2007) Cooperative rearranging region size determination by temperature modulated DSC in semi-crystalline poly(l-lactide acid). Eur Polym J 43:4675–4682
Bras AR, Malik P, Dionisio M, Mano JF (2008) Influence of crystallinity in molecular motions of poly(l-lactic acid) investigated by dielectric relaxation spectroscopy. Macromolecules 41:6419–6430
Delpouve N, Arnoult M, Saiter A, Dargent E, Saiter J-M (2014) Evidence of two mobile amorphous phases in semicrystalline polylactide observed from calorimetric investigations. Polym Eng Sci 54:1144–1150
Wunderlich B (2005) Thermal analysis of polymeric materials. Springer, Heidelberg
Natesan B, Xu H, Ince S, Cebe P (2004) Molecular relaxation of isotactic polystyrene: real-time dielectric spectroscopy and X-ray scattering studies. J Polym Sci Polym Phys 42:777–789
Xu H, Cebe P (2005) Heat capacity study of solution grown crystals of isotactic polystyrene. Macromolecules 38:770–779
Hong P-D, Chuang W-T, Yeh W-J, Lin T-L (2002) Effect of rigid amorphous phase on glass transition behavior of poly(trimethylene terephthalate). Polymer 43:6879–6886
Coburn JC, Boyd RH (1986) Dielectric relaxation in poly(ethylene terephthalate). Macromolecules 19:2238–2245
Kanchanasopa M, Manias E, Runt J (2003) Solid-state microstructure of poly(l-lactide) and l-lactide/meso-lactide random copolymers by atomic force microscopy (AFM). Biomacromolecules 4:1203–1213
Donth E (1982) The size of cooperatively rearranging regions at the glass transition. J Non-Cryst Solids 53:325–330
Donth E, Hempel E, Schick C (2000) Does temperature fluctuate? Indirect proof by dynamic glass transition in confined geometries. J Phys Condens Matter 12:L281–L286
Adam G, Gibbs JH (1965) On the temperature dependence of cooperative relaxation properties in glass-forming liquids. J Chem Phys 43:139–146
Schick C (2010) Glass transition under confinement-what can be learned from calorimetry. Eur Phys J 189:3–36
Klug HP, Alexander LE (1974) X-ray diffraction procedures: for polycrystalline and amorphous materials, 2nd edn. Wiley, Hoboken
Wang Y, Gomez Ribelles JL, Salmeron Sanchez M, Mano JF (2005) Morphological contributions to glass transition in poly(l-lactic acid). Macromolecules 38:4712–4718
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2017 Springer International Publishing AG
About this chapter
Cite this chapter
Righetti, M.C. (2017). Amorphous Fractions of Poly(lactic acid). In: Di Lorenzo, M., Androsch, R. (eds) Synthesis, Structure and Properties of Poly(lactic acid). Advances in Polymer Science, vol 279. Springer, Cham. https://doi.org/10.1007/12_2016_14
Download citation
DOI: https://doi.org/10.1007/12_2016_14
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-319-64229-1
Online ISBN: 978-3-319-64230-7
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)