Abstract
For bulk crystallization, the growth rate is governed by the nucleation process and depends mainly on the crystallization temperature and composition of the blends. If the crystallization process is confined in ultrathin films, then the diffusion-controlled growth process is remarkably retarded due to the thickness confinement. This study reports the retardation of the growth rate of the basal and overgrown lamellar crystals of neat Poly(ε-caprolactone) (PCL) and poly(vinyl methyl ether) (PVME) crystalline/amorphous miscible binary blends with various thicknesses. The morphological variations and the corresponding crystal growth rate were analyzed using real-time microscopy, and the crystal structures were evaluated by transmission electron microscopy. The growth rate was strongly dependent on the crystallization temperature, film thickness, and composition ratios in the blend. Moreover, the longitudinal and lateral growth rates of basal and overgrown lamellar crystals were discussed. This study revealed that the film thickness significantly retards the growth rate of basal and overgrown lamellar crystals and reduces the number of overgrowths on the basal lamellar crystals.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Xu J, Reiter G, Alamo RG. Concepts of nucleation in polymer crystallization. Crystals. 2021;11:304.
Mamun A, Umemoto S, Okui N, Ishihara N. Self-seeding effect on primary nucleation of isotactic polystyrene. Macromolecules. 2007;40:6296–303.
Michell RM, Müller AJ. Confined crystallization of polymeric materials. Prog Polym Sci. 2016;55:183–213.
Reiter G, Sommer J-U. Crystallization of adsorbed polymer monolayers. Phys Rev Lett. 1998;80:3771–4.
Ferreiro V, Douglas JF, Warren JA, Karim A. Nonequilibrium pattern formation in the crystallization of polymer blend films. Phys Rev E. 2002;65:042802.
Mareau VH, Prud’homme RE. In-situ hot stage atomic force microscopy study of poly(e-caprolactone) crystal growth in ultrathin films. Macromolecules. 2005;38:398–408.
Nettesheim S, Zeisel D, Handschuh M, Zenobi R. Self-assembly and desorption behavior of poly(ethylene glycol) monolayers on silica. Langmuir. 1998;14:3101–6.
Wang M, Braun H-G, Meyer E. Branched crystalline patterns formed around poly(ethylene oxide) dots in humidity. Macromol Rapid Commun. 2002;23:853–8.
Wang K, Cai L, Jesse S, Wang S. Poly(ε-caprolactone)-banded spherulites and interaction with MC3T3-E1 cells. Langmuir. 2012;28:4382–95.
Pearce R, Vancso GJ. Imaging of melting and crystallization of poly(ethylene oxide) in real-time by hot-stage atomic force microscopy. Macromolecules. 1997;30:5843–8.
Basire C, Ivanov DA. Evolution of the lamellar structure during crystallization of a semicrystalline-amorphous polymer blend: time-resolved hot-stage SPM study. Phys Rev Lett. 2000;85:5587–90.
Ni’mah H, Woo EM. Dendritic morphology composed of stacked single crystals in poly(ethylene succinate) melt-crystallized with poly(p-vinyl phenol). Cryst Growth Des. 2014;14:576–84.
Hahm S, Kim D, Khang D. One-dimensional confinement in crystallization of P(VDF-TrFE) thin films with transfer-printed metal electrode. Polymer. 2014;55:175–81.
Kovacs AJ, Straupe C. Isothermal growth, thickening and melting of poly(ethylene oxide) single crystals in the bulk. Part 4.—Dependence of pathological crystal habits on temperature and thermal history. Faraday Discuss Chem Soc. 1979;68:225–38.
Lovinger AJ, Keith HD. Electron diffraction investigation of a high-temperature form of poly(vinylidene fluoride). Macromolecules. 1979;12:919–24.
Martínez-Tong DE, Vanroy B, Wübbenhorst M, Nogales A, Napolitano S. Crystallization of poly(l-lactide) confined in ultrathin films: competition between finite size effects and irreversible chain adsorption. Macromolecules. 2014;47:2354–60.
Sommer J-U, Reiter G. Polymer crystallization in quasi-two dimensions. II. Kinetic models and computer simulations. J Chem Phys. 2000;112:4384–93.
Malwela T, Ray SS. Study of morphology and crystal growth behaviour of nanoclay-containing biodegradable polymer blend thin films using atomic force microscopy. Polymer. 2012;53:2705–16.
Qiao C, Zhao J, Jiang S, Ji X, An L, Jiang B. Crystalline morphology evolution in PCL thin films. J Polym Sci Part B: Polym Phys. 2005;43:1303–9.
Reiter G, Sommer J-U. Polymer crystallization in quasi-two dimensions. I. Experimental results. J Chem Phys. 2000;112:4376–83.
Samanta P, T V, Singh S, Srivastava R, Nandan B, Liu C-L, et al. Crystallization behaviour of poly(ethylene oxide) under confinement in the electrospun nanofibers of polystyrene/poly(ethylene oxide) blends. Soft Matter. 2016;12:5110–20.
Nojima S, Fukagawa Y, Ikeda H. Interactive crystallization of a strongly segregated double crystalline block copolymer with close crystallizable temperatures. Macromolecules. 2009;42:9515–22.
Harada K, Sugimoto T, Kato F, Watanabe K, Matsumoto Y. Thickness dependent homogeneous crystallization of ultrathin amorphous solid water films. Phys Chem Chem Phys. 2020;22:1963–73.
Mamun A, Bazuin CG, Prud’homme RE. Morphologies of various polycaprolactone/polymer blends in ultrathin films. Macromolecules. 2015;48:1412–7.
Fujie T, Kawamoto Y, Haniuda H, Saito A, Kabata K, Honda Y, et al. Selective molecular permeability induced by glass transition dynamics of semicrystalline polymer ultrathin films. Macromolecules. 2013;46:395–402.
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.
Mamun A, Mareau VH, Chen J, Prud’homme RE. Morphologies of miscible PCL/PVC blends confined in ultrathin films. Polymer. 2014;55:2179–87.
Toda A, Keller A. Growth of polyethylene single crystals from the melt: morphology. Colloid Polym Sci. 1993;271:328–42.
Keller A. Investigations on banded spherulites. J Polym Sci. 1959;39:151–73.
Keith HD, Padden FJ. The optical behavior of spherulites in crystalline polymers. Part I. Calculation of theoretical extinction patterns in spherulites with twisting crystalline orientation. J Polym Sci. 1959;39:101–22.
Keith HD, Padden FJ. Twisting orientation and the role of transient states in polymer crystallization. Polymer. 1984;25:28–42.
Keith HD, Padden FJ, Russell TP. Morphological changes in polyesters and polyamides induced by blending with small concentrations of polymer diluents. Macromolecules. 1989;22:666–75.
Nunez E, Vansco GJ, Gedde UW. Morphology, crystallization and melting of single crystals and thin films of star–branched polyesters with poly(epsilon-caprolactone) arms as revealed by atomic force microscopy. J Macromol Sci Part B Physics. 2008;47:589–607.
Zhou X, Thompson GE. Electron and photon based spatially resolved techniques, Reference module in materials science and materials engineering. Manchester, UK: Elsevier; 2017.
Taguchi K, Miyaji H, Izumi K, Hoshino A, Miyamoto Y, Kokawa R. Growth shape of isotactic polystyrene crystals in thin films. Polymer. 2001;42:7443–7.
Mamun A. Effect of acrylonitrile content of SAN on the bending morphology and its quantitative variation inside crystals of PCL/SAN blends confined in thin films. J Polym Sci. 2020;58:3283–93.
Mamun A. Advance application of Raman spectroscopy for quantitative analysis of noncrystalline components in thin films of poly(ε-caprolactone)/poly(butadiene) blends. Polym Eng Sci. 2020;60:2702–9.
Mamun A, Mahmood R. Comonomer effect on the thermal, morphological and mechanical properties of poly(ethylene-co-octene)/poly(ethylene-co-vinyl acetate) blends. Polym Sci, Ser A. 2020;62:660–9.
Kressler J, Svoboda P, Inoue T. Influence of copolymer composition on the crystallization in PCL/SAN blends. Polymer. 1993;34:3225–33.
Fox TG, Loshaek S. Influence of molecular weight and degree of crosslinking on the specific volume and glass temperature of polymers. J Polym Sci. 1955;15:371–90.
Koleske JV, Lundberg RD. Lactone polymers. I. Glass transition temperature of poly-ε-caprolactone by means on compatible polymer mixtures. J Polym Sci Part A-2: Polym Phys. 1969;7:795–807.
Hoffman JD, Miller RL. Kinetic of crystallization from the melt and chain folding in polyethylene fractions revisited: theory and experiment. Polymer. 1997;38:3151–212.
Hoffman JD, Davis GT, Lauritzen JI Jr. Treaties on solid state chemistry. New York: Plenum Press; 1976.
Schönherr H, Frank CW. Ultrathin films of poly(ethylene oxides) on oxidized silicon. 1. Spectroscopic characterization of film structure and crystallization kinetics. Macromolecules. 2003;36:1188–98.
Zuo B, Qian C, Yan D, Liu Y, Liu W, Fan H, et al. Probing glass transitions in thin and ultrathin polystyrene films by stick–slip behavior during dynamic wetting of liquid droplets on their surfaces. Macromolecules. 2013;46:1875–82.
Wang Y, Chan C-M, Jiang Y, Li L, Ng K-M. AFM studies of the molecular weight dependence of lamellar growth kinetics of polymers near the glass transition temperature. Macromolecules. 2007;40:4002–8.
Zhang F, Baralia GG, Nysten B, Jonas AM. Melting and van der Waals stabilization of PE single crystals grown from ultrathin films. Macromolecules. 2011;44:7752–7.
Bartczak Z, Argon AS, Cohen RE, Kowalewski T. The morphology and orientation of polyethylene in films of sub-micron thickness crystallized in contact with calcite and rubber substrates. Polymer. 1999;40:2367–80.
Acknowledgements
The author is grateful to the Deanship of Scientific Research at the University of Hafr Al Batin, Saudi Arabia, for providing the experimental facilities. The author thanks Professor Robert Prudhomme, Department of Chemistry, UdeM, for his assistant during manuscript preparation.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The author declares no competing interests.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Rights and permissions
About this article
Cite this article
Mamun, A. Retardation of the growth rate of the basal and overgrown lamellar crystals of PCL/PVME miscible binary blends with thickness confinement. Polym J 54, 653–665 (2022). https://doi.org/10.1038/s41428-021-00610-y
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41428-021-00610-y