Abstract
Here, we report on the three-dimensional structural analyses of huge spherulites of poly(oxyethylene) (PEG) using X-ray computerized tomography (CT) in blends of PEG and amorphous poly(d,l-lactic acid). Large spherulite formation is characteristic of PEG, and its direct observation using X-ray CT is reported here for the first time. Slit-shaped cracks that were straight or curved were clearly observed using X-ray CT. Furthermore, scanning electron microscopic observation revealed that the cracks were parallel to bundles of lamellar crystallites. From these observations, we conclude that a set of radial cracks observed by X-ray CT is a signature of a huge spherulite. Several aspects that are representative of an axialite structure are presented, and they are in good agreement with the intuitively proposed structural model for axialite long ago, although the size scale is much larger in our study.
Similar content being viewed by others
Log in or create a free account to read this content
Gain free access to this article, as well as selected content from this journal and more on nature.com
or
References
Coish R. A ., Taylor L. A . The effects of cooling rate on texture and pyroxene chemistry in DSDP Leg 34 basalt: A microprobe study. Earth Planet. Sci. Lett. 42, 389–398 (1979).
Davis B. K ., McPhie J . Spherulites, quench fractures and relict perlite in a Late Devonian rhyolite dyke, Queensland, Australia. J. Volcanol. Geothermal Res. 71, 1–11 (1996).
Fowler A. D ., Berger B ., Shore M ., Jones M. I ., Ropchan J . Supercooled rocks: development and significance of varioles, spherulites, dendrites and spinifex in Archaean volcanic rocks, Abitibi Greenstone belt, Canada. Precambrian Res. 115, 311–328 (2002).
Prasad P. B. V . Crystal growth of fatty acids from melt: CH3(CH2)14COOH and CH3(CH2)16COOH. Crystal Res. Technol. 19, 1549–1552 (1984).
Price F. P ., Fritzsche A. K . Kinetics of spherulite growth in cholesteryl esters. J. Phys. Chem. 77, 396–399 (1973).
Khoury F . The Spherulitic crystallization of isotactic polypropylene from solution: on the evolution of monoclinic spherulites from dendritic chain-folded crystal precusors. J. Res. Natl Bureau Standard - A. Phys. Chem. 70A, 29 (1966).
Wang Z ., Alfonso G. C ., Hu Z ., Zhang J ., He T . Rhythmic growth-induced ring-banded spherulites with radial periodic variation of thicknesses grown from poly(ɛ-caprolactone) solution with constant concentration. Macromolecules 41, 7584–7595 (2008).
Gránásy L ., Pusztai T ., Warren J. A ., Douglas J. F ., Börzsönyi T ., Ferreiro V . Growth of 'dizzy dendrites' in a random field of foreign particles. Nat. Mater. 2, 92–96 (2003).
Inoue M . Spherulitic crystallization and cracking during heat aging of polypropylene. J. Polymer Sci. 55, 443–450 (1961).
Sand K. K ., Rodriguez-Blanco J. D ., Makovicky E ., Benning L. G ., Stipp S. L. S . Crystallization of CaCO3 in water-alcohol mixtures: spherulitic growth, polymorph stabilization, and morphology change. Cryst. Growth Des. 12, 842–853 (2011).
Schultz J. M . Polymer Crystallization: The Development of Crystalline Order in Thermoplastic Polymers (American Chemical Society, Washington DC, USA, 2001).
Woodward A. E . Atlas of Polymer Morphology (Hanser Publishers, Munich, Vienna, New York, 1989).
Bassett D. C ., Vaughan A. S . On the lamellar morphology of melt-crystallized isotactic polystyrene. Polymer 26, 717–725 (1985).
Khoury F ., Passaglia E . in Treatise on Solid State Chemistry (ed. Hannay N. B.) Ch. 6, 335–496 (Springer, New York, USA, 1976).
Sperling L. H . Introduction to Physical Polymer Science (John Wiley & Sons, New York, USA, 1986).
Nishikawa Y ., Baba S ., Takahashi M . Optimization of X-Ray computerized tomography for polymer materials. Int. J. Polymeric Mater. Polymeric Biomater. 62, 295–300 (2012).
Nishikawa Y ., Hatanaka Y ., Iizuka S ., Takahashi M . Survey of contrasts of polymers under a high-contrast X-ray computerized tomography. Polymer 53, 4287–4292 (2012).
Tien N.-D ., Hoa T.-P ., Mochizuki M ., Saijo K ., Hasegawa H ., Sasaki S ., Sakurai S . Higher-order crystalline structures of poly(oxyethylene) in poly(d,l-lactide)/poly(oxyethylene) blends. Polymer 54, 4653–4659 (2013).
Tien N.-D ., Sasaki S ., Masunaga H ., Shimizu N ., Igarashi N ., Sakurai S . Small-angle X-ray scattering studies on melting and recrystallization behaviors of poly(oxyethylene) crystallites in poly(d,l-lactide)/poly(oxyethylene) blends. Polymer 55, 2562–2569 (2014).
Herman G. T . Fundamentals of Computerized Tomography: Image Reconstruction from Projections. Advances in Pattern Recognition, 2nd edn (Springer, London, UK, 2009).
Brandrup J ., Immergut E. H . Polymer Handbook, 3rd edn Wiley-Interscience, Hoboken, NJ, USA, 1989).
Tanaka H ., Nishi T . New Types of Phase Separation Behavior during the Crystallization Process in Polymer Blends with Phase Diagram. Phys. Rev. Lett. 55, 1102–1105 (1985).
Fraschini C ., Plesu R ., Sarasua J.-R ., Prud'homme R. E . Cracking in polylactide spherulites. J. Polymer Sci. Part B 43, 3308–3315 (2005).
Bassett D. C ., Olley R. H . On the lamellar morphology of isotactic polypropylene spherulites. Polymer 25, 935–943 (1984).
Keller A ., Waring J. R. S . The spherulitic structure of crystalline polymers. Part III. Geometrical factors in spherulitic growth and the fine-structure. J. Polymer Sci. 17, 447–472 (1955).
Acknowledgements
This study was partially supported by the Grant-in-Aid for Scientific Research on Innovative Areas, ‘New Polymeric Materials Based on Element-Blocks’ (No. 25102524), from the Ministry of Education, Culture, Sports, Science, and Technology of Japan.
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Tien, ND., Nishikawa, Y., Hashimoto, M. et al. Three-dimensional analyses of spherulite morphology in poly(oxyethylene) and its blends with amorphous poly(d,l-lactic acid) using X-ray computerized tomography. Polym J 47, 37–44 (2015). https://doi.org/10.1038/pj.2014.83
Received:
Revised:
Accepted:
Published:
Issue date:
DOI: https://doi.org/10.1038/pj.2014.83