Abstract
The crystalline structures of isotactic polypropylene (iPP) thin films were investigated using grazing incident wide-angle X-ray diffraction (GIWAXD), atomic force microscopy (AFM), and transmission electron microscopy (TEM). The out-of-plane (110) reflection split with 99° inclination in the GIWAXD pattern. The film surface was covered with flat-on mother lamellae with orthogonal daughter lamellae. The cross-sectional TEM image and the fast Fourier transform-processed image showed vertically aligned daughter lamellae and cross-hatched lateral mother lamellae. Flat-on lamellae may be preferentially produced at the substrate interface, after which the mother lamellae may yield daughter lamellae from the ac plane to give vertically aligned lamellae. The daughter lamellae yield in-plane lamellae with flat-on alignment from the ac plane, resulting in the global growth of a cross-hatched lamellar structure.
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References
- 1.
Lotz B, Wittmann JC. The molecular origin of lamellar branching in the α (monoclinic) form of isotactic polypropylene. J Polym Sci Part B Polym Phys. 1986;24:1541–58.
- 2.
Brückner S, Meille SV, Petraccone V, Pirozzi B. Polymorphism in isotactic polypropylene. Progress Polym Sci. 1991;16:361–404.
- 3.
Meille SV, Brückner S, Porzio W. γ-Isotactic polypropylene. A structure with nonparallel chain axes. Macromolecules. 1990;23:4114–21.
- 4.
Mileva D, Androsch R, Zhuravlev E, Schick C. Temperature of melting of the mesophase of isotactic polypropylene. Macromolecules. 2009;42:7275–8.
- 5.
Stocker W, Schumacher M, Graff S, Thierry A, Wittmann J-C, Lotz B. Epitaxial crystallization and AFM investigation of a frustrated polymer structure: isotactic poly(propylene), β phase. Macromolecules. 1998;31:807–14.
- 6.
Padden FJ, Keith HD. Mechanism for lamellar branching in isotactic polypropylene. J Appl Phys. 1973;44:1217–23.
- 7.
Yamada K, Matsumoto S, Tagashira K, Hikosaka M. Isotacticity dependence of spherulitic morphology of isotactic polypropylene. Polymer. 1998;39:5327–33.
- 8.
Lotz B, Wittmann JC, Lovinger AJ. Structure and morphology of poly(propylenes): a molecular analysis. Polymer. 1996;37:4979–92.
- 9.
Natta G, Corradini P. Structure and properties of isotactic polypropylene. Il Nuovo Cim (1955–1965). 1960;15:40–51.
- 10.
Mencik Z. Crystal structure of isotactic polypropylene. J Macromol Sci Part B Phys. 1972;6:101–15.
- 11.
Frank CW, Rao V, Despotopoulou MM, Pease RFW, Hinsberg WD, Miller RD, et al. Structure in thin and ultrathin spin-cast polymer films. Science. 1996;273:912–5.
- 12.
Nishino T, Matsumoto T, Nakamae K. Surface structure of isotactic polypropylene by X‐ray diffraction. Polym Eng Sci. 2000;40:336–43.
- 13.
Cho K, Kim D, Yoon S. Effect of substrate surface energy on transcrystalline growth and its effect on interfacial adhesion of semicrystalline polymers. Macromolecules. 2003;36:7652–60.
- 14.
Yakabe H, Sasaki S, Sakata O, Takahara A, Kajiyama T. Paracrystalline lattice distortion in the near-surface region of melt-crystallized polyethylene films evaluated by synchrotron-sourced grazing-incidence X-ray diffraction. Macromolecules. 2003;36:5905–7.
- 15.
Sakai A, Tanaka K, Fujii Y, Nagamura T, Kajiyama T. Structure and thermal molecular motion at surface of semi-crystalline isotactic polypropylene films. Polymer. 2005;46:429–37.
- 16.
Liu Y-X, Chen E-Q. Polymer crystallization of ultrathin films on solid substrates. Coord Chem Rev. 2010;254:1011–37.
- 17.
Grozev N, Botiz I, Reiter G. Morphological instabilities of polymer crystals. Eur Phys J E Soft Matter. 2008;27:63–71.
- 18.
Kikkawa Y, Abe H, Fujita M, Iwata T, Inoue Y, Doi Y. Crystal growth in poly(L‐lactide) thin film revealed by in situ atomic force microscopy. Macromol Chem Phys. 2003;204:1822–31.
- 19.
Mareau VH, Prud’homme RE. In-situ hot stage atomic force microscopy study of poly(ε-caprolactone) crystal growth in ultrathin Films. Macromolecules. 2005;38:398–408.
- 20.
Takenaka Y, Miyaji H, Hoshino A, Tracz A, Jeszka JK, Kucinska I. Interface structure of epitaxial polyethylene crystal grown on HOPG and MoS2 substrates. Macromolecules. 2004;37:9667–9.
- 21.
Liang Y, Zheng M, Park KH, Lee HS. Thickness-dependent crystal orientation in poly(trimethylene 2,6-naphthalate) films studied with GIWAXD and RA-FTIR methods. Polymer. 2008;49:1961–7.
- 22.
Wang Y, Rafailovich M, Sokolov J, Gersappe D, Araki T, Zou Y, et al. Substrate effect on the melting temperature of thin polyethylene films. Phys Rev Lett. 2006;96:028303.
- 23.
Asada M, Jiang N, Sendogdular L, Gin P, Wang Y, Endoh MK, et al. Heterogeneous lamellar structures near the polymer/substrate interface. Macromolecules. 2012;45:7098–106.
- 24.
Sasaki S, Masunaga H, Tajiri H, Inoue K, Okuda H, Noma H, et al. In situ investigation of annealing effect on lamellar stacking structure of polyethylene thin films by synchrotron grazing-incidence small-angle and wide-angle X-ray scattering. J Appl Crystallogr. 2007;40(s1):s642–4.
- 25.
Wang Y, Ge S, Rafailovich M, Sokolov J, Zou Y, Ade H, et al. Crystallization in the thin and ultrathin films of poly(ethylene−vinyl acetate) and linear low-density polyethylene. Macromolecules. 2004;37:3319–27.
- 26.
Hu Z, Huang H, Zhang F, Du B, He T. Thickness-dependent molecular chain and lamellar crystal orientation in ultrathin poly(di-n-hexylsilane) films. Langmuir. 2004;20:3271–7.
- 27.
Rueda DR, Hernández JJ, García-Gutiérrez MC, Ezquerra TA, Soccio M, Lotti N, et al. Flat-on lamellae in spin-coated, stable films of poly(propylene azelate). Langmuir. 2010;26:17540–5.
- 28.
Maillard D, Prud’homme RE. Crystallization of ultrathin films of polylactides: from chain chirality to lamella curvature and twisting. Macromolecules. 2008;41:1705–12.
- 29.
Wang Y, Chan C-M, Ng K-M, Li L. What controls the lamellar orientation at the surface of polymer films during crystallization? Macromolecules. 2008;41:2548–53.
- 30.
Sun X, Guo L, Sato H, Ozaki Y, Yan S, Takahashi I. A study on the crystallization behavior of poly(β-hydroxybutyrate) thin films on Si wafers. Polymer. 2011;52:3865–70.
- 31.
Yang J-P, Liao Q, Zhou J-J, Jiang X, Wang X-H, Zhang Y, et al. What determines the lamellar orientation on substrates? Macromolecules. 2011;44:3511–6.
- 32.
Zhou J-J, Liu J-G, Yan S-K, Dong J-Y, Li L, Chan C-M, et al. Atomic force microscopy study of the lamellar growth of isotactic polypropylene. Polymer. 2005;46:4077–87.
- 33.
Wang X, Hou W, Zhou J, Li L, Li Y, Chan C-M. Melting behavior of lamellae of isotactic polypropylene studied using hot-stage atomic force microscopy. Colloid Polym Sci. 2007;285:449–55.
- 34.
Padden FJ, Keith HD. Crystallization in thin films of isotactic polypropylene. J Appl Phys. 1966;37:4013–20.
- 35.
Zhang B, Chen J, Liu B, Wang B, Shen C, Reiter R, et al. Morphological changes of isotactic polypropylene crystals grown in thin films. Macromolecules. 2017;50:6210–7.
- 36.
Koga T, Morita M, Ishida H, Yakabe H, Sasaki S, Sakata O, et al. Dependence of the molecular aggregation state of octadecylsiloxane monolayers on preparation methods. Langmuir. 2005;21:905–10.
- 37.
Owens DK, Wendt R. Estimation of the surface free energy of polymers. J Appl Polym Sci. 1969;13:1741–7.
- 38.
Masunaga H, Ogawa H, Takano T, Sasaki S, Goto S, Tanaka T, et al. Multipurpose soft-material SAXS/WAXS/GISAXS beamline at SPring-8. Polym J. 2011;43:471–7.
- 39.
Ogawa H, Masunaga H, Sasaki S, Goto S, Tanaka T, Seike T, et al. Experimental station for multiscale surface structural analyses of soft-material films at SPring-8 via a GISWAX/GIXD/XR-integrated system. Polym J. 2013;45:109–16.
- 40.
Hatsui T, Graafsma H. X-ray imaging detectors for synchrotron and XFEL sources. IUCrJ. 2015;2:371–83.
- 41.
Giannuzzi LA, Stevie FA. A review of focused ion beam milling techniques for TEM specimen preparation. Micron. 1999;30:197–204.
- 42.
Norton DR, Keller A. The spherulitic and lamellar morphology of melt-crystallized isotactic polypropylene. Polymer. 1985;26:704–16.
- 43.
Yamada K, Kajioka H, Nozaki K, Toda A. Morphology and growth of single crystals of isotactic polypropylene from the melt. J Macromol Sci Part B Phys. 2010;50:236–47.
- 44.
Clark EJ, Hoffman JD. Regime III crystallization in polypropylene. Macromolecules. 1984;17:878–85.
- 45.
Roe R-J. Surface tension of polymer liquids. J Phys Chem. 1968;72:2013–7.
- 46.
Theodorou DN. Variable-density model of polymer melt surfaces: structure and surface tension. Macromolecules. 1989;22:4578–89.
- 47.
Beers KL, Douglas JF, Amis EJ, Karim A. Combinatorial measurements of crystallization growth rate and morphology in thin films of isotactic polystyrene. Langmuir. 2003;19:3935–40.
- 48.
Binsbergen FL, de Lange BGM. Morphology of polypropylene crystallized from the melt. Polymer. 1968;9:23–40.
Acknowledgements
This work was partially supported by the Photon and Quantum Basic Research Coordinated Development Program of MEXT. The GIWAXD measurements were carried out at the first hutch of SPring-8 BL03XU constructed by the Consortium of Advanced Softmaterial Beamline (FSBL) (Proposal Nos. 2013A7218, 2013B7266, 2015A7216, 2015B7267, 2016A7217, and 2017B7267).
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Uchida, K., Mita, K., Higaki, Y. et al. Lamellar orientation in isotactic polypropylene thin films: a complement study via grazing incidence X-ray diffraction and surface/cross-sectional imaging. Polym J 51, 183–188 (2019). https://doi.org/10.1038/s41428-018-0138-3
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