Reexamining the Crystallization of Poly(ε-caprolactone) and Isotactic Polypropylene under Hard Confinement: Nucleation and Orientation
Abstract
The crystallization of poly(ε-caprolactone) (PCL) and isotactic polypropylene (iPP) infiltrated in nanoporous anodic alumina oxide (AAO) templates was reexamined to demonstrate the importance of obtaining polymer-free, clean AAO surfaces on the nucleation, size dependence of crystallization temperature ( T c ), and texture. The AAO pore diameters cover a broad range from 400 to 20 nm. When the AAO templates were completely free of any residual polymer on their surfaces, differential scanning calorimetry (DSC) experiments exhibited a single crystallization peak for all the samples with different AAO pore sizes. A drastic decrease in T c with density of domains indicated a transition from heterogeneous to homogeneous/surface nucleation. A regular decrease of T c with pore size was observed in the low T c regime, as a result of the volume dependence of nucleation events. The chain alignment of the two polymers infiltrated in AAO was studied by two-dimensional wide-angle X-ray scattering (WAXS). By comparing the experimental and simulated WAXS patterns, the orientation modes of the polymers were identified and compared with previous studies.
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With proper cleaning measures, all infiltrated PCL and iPP samples exhibited a single exothermic peak during cooling.
“With proper cleaning measures, all the infiltrated PCL and iPP samples exhibited a single exothermic peak during cooling ( Fig. 24 ).”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [282]
Cites
Masuda, H., & Fukuda, K. (1995) · Science · doi:10.1126/science.268.5216.1466 · Cited by 5,197 · see citing works
Nanomaterials: A Membrane-Based Synthetic Approach
Martin, C. R. (1994) · Science · doi:10.1126/science.266.5193.1961 · Cited by 4,066 · see citing works
Kinetische Behandlung der Keimbildung in übersättigten Dämpfen
Becker, R., & Döring, W. (1935) · Annalen der Physik · doi:10.1002/andp.19354160806 · Cited by 3,155 · see citing works
Keimbildung in übersättigten Gebilden
Volmer, M., & Weber, Α. (1926) · Zeitschrift für Physikalische Chemie · doi:10.1515/zpch-1926-11927 · Cited by 1,936 · see citing works
A General Theory of Heterophase Fluctuations and Pretransition Phenomena
Frenkel, J. (1939) · The Journal of Chemical Physics · doi:10.1063/1.1750484 · Cited by 360 · see citing works
Confined crystallization of polymeric materials
Michell, R. M., & Müller, A. J. (2016) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2015.10.007 · Cited by 351 · see citing works
Self-citationStructural Studies of Polyesters. III. Crystal Structure of Poly-ε-caprolactone
Chatani, Y., Okita, Y., Tadokoro, H., & Yamashita, Y. (1970) · Polymer Journal · doi:10.1295/polymj.1.555 · Cited by 305 · see citing works
Kinetics of Homogeneous Nucleation in the Freezing of Large Water Clusters
Huang, J., & Bartell, L. S. (1995) · The Journal of Physical Chemistry · doi:10.1021/j100012a010 · Cited by 247 · see citing works
Handbook of Polymer Applications in Medicine and Medical Devices
(2014) · Elsevier eBooks · doi:10.1016/c2012-0-07906-9 · Cited by 245 · see citing works
The density of supercooled water. II. Bulk samples cooled to the homogeneous nucleation limit
Hare, D. E., & SORENSEN, C. M. (1987) · The Journal of Chemical Physics · doi:10.1063/1.453710 · Cited by 244 · see citing works
Homogeneous nucleation and fractionated crystallization in block copolymers
Müller, A. J., Balsamo, V., Arnal, M. L., Jakob, T., Schmalz, H., & Abetz, V. (2002) · Macromolecules · doi:10.1021/ma012026w · Cited by 226 · see citing works
Self-citationSteinhart, M., Göring, P., Dernaika, H., Prabhukaran, M., Gösele, U., Hempel, E., & Thurn‐Albrecht, T. (2006) · Physical Review Letters · doi:10.1103/physrevlett.97.027801 · Cited by 214 · see citing works
Duran, H., Steinhart, M., Butt, H.-J., & Floudas, G. (2011) · Nano Letters · doi:10.1021/nl200153c · Cited by 197 · see citing works
Mareau, V. H., & Prud'homme, R. E. (2005) · Macromolecules · doi:10.1021/ma0482359 · Cited by 193 · see citing works
Massa, M. V., & Dalnoki-Veress, K. (2004) · Physical Review Letters · doi:10.1103/physrevlett.92.255509 · Cited by 192 · see citing works
Confinement effects on polymer crystallization: From droplets to alumina nanopores
Michell, R. M., Blaszczyk-Lezak, I., Mijangos, C., & Müller, A. J. (2013) · Polymer · doi:10.1016/j.polymer.2013.05.029 · Cited by 184 · see citing works
Self-citationNucleation of polymer droplets
Koutsky, J. A., Walton, A. G., & Baer, E. (1967) · Journal of Applied Physics · doi:10.1063/1.1709769 · Cited by 180 · see citing works
Influence of processing conditions on polymer crystallization measured by fast scanning DSC
Schawe, J. E. K. (2013) · Journal of Thermal Analysis and Calorimetry · doi:10.1007/s10973-013-3563-8 · Cited by 176 · see citing works
Microdomain-Tailored Crystallization Kinetics of Block Copolymers
Chen, H., Hsiao, S.-C., Lin, T., Yamauchi, K., Hasegawa, H., & Hashimoto, T. (2001) · Macromolecules · doi:10.1021/ma001485e · Cited by 172 · see citing works
Self-citationWoo, E., Huh, J., Jeong, Y. G., & Shin, K. (2007) · Physical Review Letters · doi:10.1103/physrevlett.98.136103 · Cited by 152 · see citing works
Polanyl, M. (1921) · The European Physical Journal A · doi:10.1007/bf01332786 · Cited by 150 · see citing works
Microstructure and unit‐cell orientation in α‐polypropylene
Lovinger, A. J. (1983) · Journal of Polymer Science Polymer Physics Edition · doi:10.1002/pol.1983.180210107 · Cited by 147 · see citing works
Michell, R. M., Lorenzo, A. T., Müller, A. J., Lin, M.-C., Chen, H.-L., Blaszczyk-Lezak, I., Martín, J., & Mijangos, C. (2012) · Macromolecules · doi:10.1021/ma202327f · Cited by 128 · see citing works
Self-citationPérez, R., Córdova, M. E., Vergara-López, J., Hoskins, J. N., Zhang, B., Grayson, S. M., & Müller, A. J. (2013) · Reactive and Functional Polymers · doi:10.1016/j.reactfunctpolym.2013.10.013 · Cited by 125 · see citing works
Self-citationCrystallization kinetics and solidified structure in iPP under high cooling rates
Coccorullo, I., Pantani, R., & Titomanlio, G. (2002) · Polymer · doi:10.1016/s0032-3861(02)00762-0 · Cited by 124 · see citing works
Suzuki, Y., Duran, H., Akram, W., Steinhart, M., Floudas, G., & Butt, H.-J. (2013) · Soft Matter · doi:10.1039/c3sm50907a · Cited by 118 · see citing works
Suzuki, Y., Duran, H., Steinhart, M., Butt, H.-J., & Floudas, G. (2013) · Soft Matter · doi:10.1039/c2sm27618f · Cited by 115 · see citing works
Ponting, M. T., Lin, Y., Keum, J. K., Hiltner, A., & Baer, E. (2010) · Macromolecules · doi:10.1021/ma101625h · Cited by 97 · see citing works
Nakagawa, S., Kadena, K., Ishizone, T., Nojima, S., Shimizu, T., Yamaguchi, K., & Nakahama, S. (2012) · Macromolecules · doi:10.1021/ma202566f · Cited by 87 · see citing works
Homogeneous Bulk, Surface, and Edge Nucleation in Crystalline Nanodroplets
Carvalho, J. L., & Dalnoki-Veress, K. (2010) · Physical Review Letters · doi:10.1103/physrevlett.105.237801 · Cited by 83 · see citing works
Pérez, R., Vergara-López, J., Hoskins, J. N., Zhang, B., Grayson, S. M., Casas, M. T., Puiggalı́, J., & Müller, A. J. (2014) · Macromolecules · doi:10.1021/ma5005869 · Cited by 78 · see citing works
Self-citationCharacter of crystallization nuclei in isotactic polypropylene
Rybnikár̆, F. (1982) · Journal of Applied Polymer Science · doi:10.1002/app.1982.070270507 · Cited by 73 · see citing works
Confined crystallization of polymers within anodic aluminum oxide templates
Michell, R. M., Blaszczyk‐Lezak, I., Mijangos, C., & Müller, A. J. (2014) · Journal of Polymer Science Part B Polymer Physics · doi:10.1002/polb.23553 · Cited by 72 · see citing works
Self-citationManipulating Crystal Orientation of Poly(ethylene oxide) by Nanopores
Guan, Y., Liu, G., Gao, P., Li, L., Ding, G., & Wang, D. (2013) · ACS Macro Letters · doi:10.1021/mz300592v · Cited by 71 · see citing works
Self-citationSpherulitic Nucleation and Growth Rates in an iPP under Continuous Shear Flow
Coccorullo, I., Pantani, R., & Titomanlio, G. (2008) · Macromolecules · doi:10.1021/ma801524t · Cited by 69 · see citing works
Suzuki, Y., Duran, H., Steinhart, M., Butt, H., & Floudas, G. A. (2014) · Macromolecules · doi:10.1021/ma4026477 · Cited by 68 · see citing works
Kim, C. Y., Kim, Y. C., & Kim, S. (1993) · Polymer Engineering and Science · doi:10.1002/pen.760332202 · Cited by 60 · see citing works
Guan, Y., Liu, G., Ding, G., Yang, T., Müller, A. J., & Wang, D. (2015) · Macromolecules · doi:10.1021/acs.macromol.5b00108 · Cited by 59 · see citing works
Self-citationNucleation and crystallization of blends of poly(propylene) and ethylene/α-olefin copolymers
Manaure, A. C., & Müller, A. J. (2000) · Macromolecular Chemistry and Physics · doi:10.1002/1521-3935(20000601)201:9 · Cited by 56 · see citing works
Self-citationFormation and transformation of smectic polypropylene nanodroplets
Jin, Y., Hiltner, A., Baer, E., Masirek, R., Piórkowska, E., & Gałęski, A. (2006) · Journal of Polymer Science Part B Polymer Physics · doi:10.1002/polb.20839 · Cited by 55 · see citing works
Polymorphic Behavior of Syndiotactic Polystyrene Crystallized in Cylindrical Nanopores
Wu, H., Wang, W., Huang, Y., Wang, C., & Su, Z. (2008) · Macromolecules · doi:10.1021/ma801498b · Cited by 52 · see citing works
Kailas, L., Vasilev, C., Audinot, J., Migeon, H. ‐., & Hobbs, J. K. (2007) · Macromolecules · doi:10.1021/ma070861t · Cited by 50 · see citing works
Transformation of isotactic polypropylene droplets from the mesophase into the α-phase
Langhe, D. S., Hiltner, A., & Baer, E. (2011) · Journal of Polymer Science Part B: Polymer Physics · doi:10.1002/polb.22357 · Cited by 39 · see citing works
Suzuki, Y., Steinhart, M., Kappl, M., Butt, H.-J., & Floudas, G. (2016) · Polymer · doi:10.1016/j.polymer.2016.07.021 · Cited by 33 · see citing works
New insight in the level structure of 153Er
Foin, C., Farget, F., Gizon, A., et al. (2000) · The European Physical Journal A · doi:10.1007/pl00013591 · Cited by 28 · see citing works
Lin, M.-C., Chen, H.-L., Lin, W.-F., Huang, P.-S., & Tsai, J.-C. (2012) · The Journal of Physical Chemistry B · doi:10.1021/jp306410j · Cited by 27 · see citing works
Self-citationUsing rheometry to determine nucleation density in a colored system containing a nucleating agent
Ma, Z., Steenbakkers, R. J. A., Giboz, J., et al. (2010) · Rheologica Acta · doi:10.1007/s00397-010-0506-1 · Cited by 22 · see citing works
Liu, C., & Chen, H. (2017) · Macromolecules · doi:10.1021/acs.macromol.6b02347 · Cited by 22 · see citing works
Self-citationCrystallization and orientation of isotactic poly(propylene) in cylindrical nanopores
Reid, D. K., Ehlinger, B. A., Shao, L., & Lutkenhaus, J. L. (2014) · Journal of Polymer Science Part B: Polymer Physics · doi:10.1002/polb.23577 · Cited by 17 · see citing works
Sanz, B., Blaszczyk-Lezak, I., Mijangos, C., Palacios, J. K., & Müller, A. J. (2016) · Langmuir · doi:10.1021/acs.langmuir.6b01258 · Cited by 13 · see citing works
Self-citationSantis, F. D., Vietri, A. R., & Pantani, R. (2006) · Macromolecular Symposia · doi:10.1002/masy.200650202 · Cited by 8 · see citing works
Thermal Driving Fast Fabrication of Porous Anodic Alumina
Ding, J., Zhu, Y., Yuan, N., et al. (2011) · Journal of The Electrochemical Society · doi:10.1149/2.019112jes · Cited by 6 · see citing works
Theory of Crystals and Interfaces in Polyethylene and Isotactic Polypropylene
Feng, J., Zhou, H., Wang, X., et al. (2016) · The Journal of Physical Chemistry C · doi:10.1021/acs.jpcc.6b00376 · Cited by 5 · see citing works
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Fractionated crystallization in semicrystalline polymers
Sangroniz, L., Wang, B., Su, Y., Liu, G., Cavallo, D., Wang, D., & Müller, A. J. (2021) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2021.101376 · Cited by 102 · see citing works
Self-citationWang, B., Utzeri, R., Castellano, M., Stagnaro, P., Müller, A. J., & Cavallo, D. (2020) · Macromolecules · doi:10.1021/acs.macromol.0c01167 · Cited by 82 · see citing works
Self-citationSegmental Dynamics Govern the Cold Crystallization of Poly(lactic acid) in Nanoporous Alumina
Shi, G., Guan, Y., Liu, G., Müller, A. J., & Wang, D. (2019) · Macromolecules · doi:10.1021/acs.macromol.9b00542 · Cited by 48 · see citing works
Safari, M., Maiz, J., Shi, G., Juanes, D., Liu, G., Wang, D., Mijangos, C., Alegría, Á., & Müller, A. J. (2019) · Langmuir · doi:10.1021/acs.langmuir.9b02215 · Cited by 27 · see citing works
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Self-citationCrystal orientation of PEO confined within the nanorod templated by AAO nanochannels
Liu, C.-L., & Chen, H.-L. (2018) · Soft Matter · doi:10.1039/c8sm00795k · Cited by 22 · see citing works
Su, C., Chen, Y., Shi, G., Li, T., Liu, G., Müller, A. J., & Wang, D. (2019) · Langmuir · doi:10.1021/acs.langmuir.9b01968 · Cited by 16 · see citing works
Self-citation
- Authors
- Shi, G., Liu, G., Su, C., Chen, H., Chen, Y., Su, Y., Müller, A. J., & Wang, D.
- Affiliations
- Chinese Academy of Sciences (CN)
- Ikerbasque (ES)
- Corresponding author
- Liu, Guoming
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2017-11-15
- Volume
- 50
- Issue
- 22
- Pages
- 9015-9023
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2770446151
- Cited by
- 50
- References
- 54
- Citations by year
- 2026: 5 · 2025: 4 · 2024: 3 · 2023: 4 · 2022: 6 · 2021: 7 · 2020: 6 · 2019: 6 · 2018: 9
- FWCI
- 3.29
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- Funders
- Ministerio de Econom?a y Competitividad (MAT2014-53437-C2-P)
- Youth Innovation Promotion Association of the Chinese Academy of Sciences (2015026)
- National Natural Science Foundation of China (21274156, 51203170)
- Topics
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Materials Science › Materials Chemistry › Block Copolymer Self-Assembly
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Keywords
- polycaprolactone, isotactic polypropylene, crystallization, surface nucleation, homogeneous nucleation, crystallization temperature, pore size dependence, chain orientation, polymer infiltration
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