Definition
The most common higher order structure of crystalline polymers is called spherulite. A spherulite is a polycrystalline aggregate densely filled with thin lamellar crystals and formed by consecutive lamellar branching and reorientation of those crystals in non-crystallographic directions. Polymer spherulites have inner structures characterized by periodic banding or patchy patterns that are created by the reorientation with correlated twisting or in random directions, respectively. The specific reorientation is related to the unbalance of surface stresses caused by the chain folding on the upper and lower basal planes of the lamellar crystals. The branching mechanism is related to the fingering instability of the growth front caused by a gradient in chemical potential ahead of the growth front. The dynamical coupling of the branching and reorientation evolves the spherulitic growth in crystalline polymers.
Introduction
Crystalline polymeric materials form higher order...
References
Abo el Maaty MI, Bassett DC (2001) On fold surface ordering and re-ordering during the crystallization of polyethylene from the melt. Polymer 42:4957–4963
Bassett DC (2003) Polymer spherulites: a modern assessment. J Macromol Sci B42:227–256
Bassett DC, Hodge AM (1981) On the morphology of melt-crystallized polyethylene. Proc R Soc Lond A377:61–71
Bassett DC, Frank FC, Keller A (1959) Evidence for distinct sectors in polymer single crystals. Nat (Lond) 184:810–811
Bassett DC, Olley RH, Sutton SJ, Vaughan AS (1996) On chain conformations and spherulitic growth in monodisperse n-C294H590. Polymer 37:4993–4997
Bernauer F (1929) Gedrillte Kristalle. Borntraeger, Berlin
Duan YX, Jiang Y, Jiang SD, Li L, Yan SK, Schultz JM (2004) Depletion-induced nonbirefringent banding in thin isotactic polystyrene thin films. Macromolecules 37:9283–9286
Gałeski A, Koenczoel L, Piórkowska E, Baer E (1987) Acoustic emission during polymer crystallization. Nature 325:40–41
Gránásy L, Pusztai T, Börzsönyi T, Warren JA, Douglas JF (2004) A general mechanism of polycrystalline growth. Nat Mater 3:645–650
Hatwalne Y, Muthukumar M (2010) Chiral symmetry breaking in crystals of achiral polymers. Phys Rev Lett 105:107801
Kajioka H, Hikosaka M, Taguchi K, Toda A (2008) Branching and re-orientation of lamellar crystals in non-banded poly(butene-1) spherulites. Polymer 49:1685–1692
Kajioka H, Yoshimoto S, Taguchi K, Toda A (2010) Morphology and crystallization kinetics of it-polystyrene spherulites. Macromolecules 43:3837–3843
Kajioka H, Taguchi K, Toda A (2011) Cellular crystallization in thin melt film of it-poly(butene-1): an implication to spherulitic growth. Macromolecules 44:9239–9246
Keith HD (1964) On the relation between different morphological forms in high polymers. J Polym Sci Part A Polym Chem 2:4339–4360
Keith HD, Padden FJ Jr (1963) A phenomenological theory of spherulitic crystallization. J Appl Phys 34:2409–2421
Keith HD, Padden FJ Jr (1984) Twisting orientation and the role of transient states in polymer crystallization. Polymer 25:28–42
Keith HD, Padden FJ Jr, Russell TP (1989) Morphological changes in polyesters and polyamides induced by blending with small concentrations of polymer diluents. Macromolecules 22:666–675
Kyu T, Chiu H-W, Guenthner AJ, Okabe Y, Saito H, Inoue T (1999) Rhythmic growth of target and spiral spherulites of crystalline polymer blends. Phys Rev Lett 83:2749–2753
Li CY, Cheng SZD, Weng X, Ge JJ, Bai F, Zhang JZ, Calhoun BH, Harris FW, Chien L-C, Lotz B (2001) Left or right, it is a matter of one methylene unit. J Am Chem Soc 123:2462–2463
Lotz B, Cheng SZD (2005) A critical assessment of unbalanced surface stress as the mechanical origin of twisting and scrolling of polymer crystals. Polymer 46:577–610
Magill JH (2001) Review spherulites: a personal perspective. J Mater Sci 36:3143–3164
Okano K (1964) Note on the lamellar twist is polymer spherulites. Jpn J Appl Phys 3:351–353
Reneker DH, Geil PH (1960) Morphology of polymer single crystals. J Appl Phys 31:1916–1925
Saracovan J, Keith HD, Manley RSJ, Brown GR (1999) Banding in spherulites of polymers having uncompensated main-chain chirality. Macromolecules 32:8918–8922
Schultz JM (2001) Polymer crystallization, Chapter 10. Oxford University Press, Oxford
Schultz JM, Kinloch DR (1969) Transverse screw dislocations: a source of twist in crystalline polymer ribbons. Polymer 10:271–278
Tiller WA (1991) The science of crystallization: macroscopic phenomena and defect generation, Chapter 5 and 6. Cambridge University Press, New York
Toda A, Keller A (1993) Growth of polyethylene single crystals from the melt: morphology. Colloid Polym Sci 271:328–342
Toda A, Okamura M, Taguchi K, Hikosaka M, Kajioka H (2008) Branching and higher order structure in banded polyethylene spherulites. Macromolecules 41:2484–2493
Toda A, Taguchi K, Kajioka H (2012) Growth of banded spherulites of poly(epsilon-caprolactone) from the blends: an examination of the modeling of spherulitic growth. Polymer 53:1765–1771
Vaughan AS (1993) Etching and morphology of poly(vinylidene fluoride). J Mater Sci 28:1805–1813
Ye H-M, Wang J-S, Tang S, Xu J, Feng X-Q, Guo B-H, Xie X-M, Zhou J-J, Li L, Wu Q, Chen G-Q (2010) Surface stress effects on the bending direction and twisting chirality of lamellar crystals of chiral polymer. Macromolecules 43:5762–5770
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Toda, A. (2013). Spherulitic Growth in Crystalline Polymers. In: Palsule, S. (eds) Encyclopedia of Polymers and Composites. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-37179-0_24-1
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DOI: https://doi.org/10.1007/978-3-642-37179-0_24-1
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