Thermorheologically complex self-seeded melts of propylene–ethylene copolymers
Abstract
A novel approach to study self-nucleation in semicrystalline polymers is presented. Self-nucleation, i.e., the peculiar increase of recrystallization kinetics associated with a range of melting temperatures above or below the melting point, is investigated in parallel with differential scanning calorimetry (DSC) and rheological measurements, for a series of metallocene propene/ethylene random copolymers of varying comonomer content. DSC experiments revealed the exact temperature region where self-nucleation effects are detected in the various samples, while with dynamic viscoelastic results the obedience to the time–temperature superposition principle (TTS) is tested, for both self-nucleated and homogeneous melts. Self-nucleated melts do not obey to the TTS principle, contrary to fully isotropic copolymer melts. Such rheological thermocomplexity constitutes the first physical experimental evidence of the presence of melt heterogeneities, which act as self-nuclei when the melt is cooled and recrystallizes. The degree of thermorheological complexity of the different copolymers is quantified and correlated with the original crystalline content of the copolymer.
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It has been postulated that self-nuclei in Domain IIa can be regions in the melt where partial orientation of the chains remains, due to the survival of inter-segmental interactions that were present in the crystalline state.
“It has been postulated that they can be regions in the melt where partial orientation of the chains remain, thanks to the survival of inter-segmental interactions that were present in the crystalline state [ 321 , 322 , 333-337 ].”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [334]
Cites
Viscoelastic Properties of Polymers
Jones, W. (1981) · Journal of Non-Newtonian Fluid Mechanics · doi:10.1016/0377-0257(81)80036-5 · Cited by 11,142 · see citing works
Physical properties of polymers handbook
Mark, J. (2007) · Springer eBooks · doi:10.1007/978-0-387-69002-5 · Cited by 1,670 · see citing works
Dynamics of polymeric liquids: Fluid mechanics
Bird, R. B., Armstrong, R. C., & Hassager, O. (1987) · Cited by 1,290 · see citing works
Polyethylene multiwalled carbon nanotube composites
McNally, T., Pötschke, P., Halley, P. J., Murphy, M., Martin, D. J., Bell, S. E. J., Brennan, G. P., Bein, D., Lemoine, P., & Quinn, J. P. (2005) · Polymer · doi:10.1016/j.polymer.2005.06.094 · Cited by 805 · see citing works
Fillon, B., Wittmann, J. C., Lotz, B., & Thierry, A. (1993) · Journal of Polymer Science Part B Polymer Physics · doi:10.1002/polb.1993.090311013 · Cited by 653 · see citing works
Blundell, D. J., Keller, A., & Kovacs, A. J. (1966) · Journal of Polymer Science Part B Polymer Letters · doi:10.1002/pol.1966.110040709 · Cited by 444 · see citing works
Prashantha, K., Soulestin, J., Lacrampe, M., Krawczak, P., Dupin, G., & Claes, M. (2008) · Composites Science and Technology · doi:10.1016/j.compscitech.2008.10.005 · Cited by 376 · see citing works
Van Gurp-Palmen Plot II - classification of long chain branched polymers by their topology
Trinkle, S., Walter, P., & Friedrich, C. (2002) · Rheologica Acta · doi:10.1007/s003970200010 · Cited by 364 · see citing works
Eckstein, A., Suhm, J., Friedrich, C., Maier, R.-D., Saßmannshausen, J., Bochmann, M., & Mülhaupt, R. (1998) · Macromolecules · doi:10.1021/ma971270d · Cited by 294 · see citing works
Cloning polymer single crystals through self-seeding
Xu, J., Ma, Y., Hu, W., Rehahn, M., & Reiter, G. (2009) · Nature Materials · doi:10.1038/nmat2405 · Cited by 286 · see citing works
Effect of annealing time on the self-nucleation behavior of semicrystalline polymers
Lorenzo, A. T., Arnal, M. L., Sánchez, J. J., & Müller, A. J. (2006) · Journal of Polymer Science Part B: Polymer Physics · doi:10.1002/polb.20832 · Cited by 245 · see citing works
Self-citationStrong Memory Effect of Crystallization above the Equilibrium Melting Point of Random Copolymers
Reid, B. O., Vadlamudi, M., Mamun, A., Janani, H., Gao, H., Hu, W., & Alamo, R. G. (2013) · Macromolecules · doi:10.1021/ma400839d · Cited by 196 · see citing works
Self-citation1995 Bingham Medal Address: Oh, thermorheological simplicity, wherefore art thou?
Plazek, D. J. (1996) · Journal of Rheology · doi:10.1122/1.550776 · Cited by 183 · see citing works
Frozen topology: entanglements control nucleation and crystallization in polymers
Luo, C., & Sommer, J.-U. (2014) · Physical Review Letters · doi:10.1103/physrevlett.112.195702 · Cited by 183 · see citing works
Michell, R. M., Mugica, A., Zubitur, M., & Müller, A. J. (2015) · Advances in Polymer Science · doi:10.1007/12_2015_327 · Cited by 159 · see citing works
Self-citationTemperature dependence of polyolefin melt rheology
Mavridis, H., & Shroff, R. N. (1992) · Polymer Engineering and Science · doi:10.1002/pen.760322307 · Cited by 159 · see citing works
Arandia, I., Múgica, A., Zubitur, M., Arbe, A., Liu, G., Wang, D., Mincheva, R., Dúbois, P., & Müller, A. J. (2014) · Macromolecules · doi:10.1021/ma5023567 · Cited by 139 · see citing works
Self-citationA thermodynamic multiphase scheme treating polymer crystallization and melting
Strobl, G. R. (2005) · The European Physical Journal E · doi:10.1140/epje/e2005-00032-y · Cited by 121 · see citing works
Morphological Partitioning of Ethylene Defects in Random Propylene−Ethylene Copolymers
Alamo, R. G., VanderHart, D. L., Nyden, M. R., et al. (2000) · Macromolecules · doi:10.1021/ma000267i · Cited by 120 · see citing works
Self-citationMonte Carlo Simulations of Strong Memory Effect of Crystallization in Random Copolymers
Gao, H., Vadlamudi, M., Alamo, R. G., & Hu, W. (2013) · Macromolecules · doi:10.1021/ma400842h · Cited by 103 · see citing works
Self-citationGonzález, O., Peña, J. J., Muñoz, M. E., et al. (2002) · Energy & Fuels · doi:10.1021/ef020049l · Cited by 98 · see citing works
Thermorheological Behavior of Various Long-Chain Branched Polyethylenes
Stadler, F. J., Kaschta, J., & Münstedt, H. (2008) · Macromolecules · doi:10.1021/ma702367a · Cited by 91 · see citing works
Communication: Theory of melt-memory in polymer crystallization
Muthukumar, M. (2016) · The Journal of Chemical Physics · doi:10.1063/1.4959583 · Cited by 91 · see citing works
Jeon, K., Palza, H., Quijada, R., et al. (2008) · Polymer · doi:10.1016/j.polymer.2008.10.032 · Cited by 90 · see citing works
Fernández–d’Arlas, B., Balko, J., Baumann, R.-P., Pöselt, E., Dabbous, R., Eling, B., Thurn‐Albrecht, T., & Müller, A. J. (2016) · Macromolecules · doi:10.1021/acs.macromol.6b01527 · Cited by 76 · see citing works
Self-citationLifetime of Flow-Induced Precursors in Isotactic Polypropylene
Hamad, F. G., Colby, R. H., & Milner, S. T. (2015) · Macromolecules · doi:10.1021/acs.macromol.5b01408 · Cited by 74 · see citing works
Alamo, R. G., Ghosal, A., Chatterjee, J., & Thompson, K. L. (2005) · Polymer · doi:10.1016/j.polymer.2005.02.128 · Cited by 73 · see citing works
Self-citationSelf-Seeding Effect on Primary Nucleation of Isotactic Polystyrene
Mamun, A., Umemoto, S., Okui, N., & Ishihara, N. (2007) · Macromolecules · doi:10.1021/ma070963j · Cited by 72 · see citing works
Mamun, A., Chen, X., & Alamo, R. G. (2014) · Macromolecules · doi:10.1021/ma501937c · Cited by 72 · see citing works
Self-citationMaus, A., Hempel, E., Thurn‐Albrecht, T., & Saalwächter, K. (2007) · The European Physical Journal E · doi:10.1140/epje/i2007-10183-6 · Cited by 65 · see citing works
Jeon, K., Chiari, Y., & Alamo, R. G. (2007) · Macromolecules · doi:10.1021/ma070757b · Cited by 55 · see citing works
Self-citationChen, X., Mamun, A., & Alamo, R. G. (2015) · Macromolecular Chemistry and Physics · doi:10.1002/macp.201500068 · Cited by 54 · see citing works
Self-citationSome aspects of linear and nonlinear viscoelastic behaviour of polymer melts in shear
Booij, H. C., & Palmen, J. H. M. (1982) · Rheologica Acta · doi:10.1007/bf01534297 · Cited by 49 · see citing works
A rheological analysis of interactions in phenoxy/organoclay nanocomposites
Fernandez, I., Santamarı́a, A., Muñoz, M. E., et al. (2007) · European Polymer Journal · doi:10.1016/j.eurpolymj.2007.05.025 · Cited by 34 · see citing works
Sealey, J. E., Frazier, C. E., Samaranayake, G., & Glasser, W. G. (2000) · Journal of Polymer Science Part B Polymer Physics · doi:10.1002/(sici)1099-0488(20000201)38:3 · Cited by 32 · see citing works
Nyden, M. R., VanderHart, D. L., & Alamo, R. G. (2001) · Computational and Theoretical Polymer Science · doi:10.1016/s1089-3156(00)00016-7 · Cited by 31 · see citing works
Self-citationCrystallization of Statistical Copolymers
Hu, W., Mathot, V., Alamo, R. G., Gao, H., & Chen, X. (2016) · Advances in polymer science · doi:10.1007/12_2016_349 · Cited by 29 · see citing works
Self-citationMorphological and kinetic partitioning of comonomer in random propylene 1-butene copolymers
Ruiz‐Orta, C., & Alamo, R. G. (2011) · Polymer · doi:10.1016/j.polymer.2011.12.032 · Cited by 23 · see citing works
Self-citationRen, M., Chen, X., Sang, Y., & Alamo, R. G. (2015) · Macromolecular Symposia · doi:10.1002/masy.201500053 · Cited by 16 · see citing works
Self-citationLINEAR VISCOELASTIC PROPERTIES OF A MISCIBLE POLYMER BLEND SYSTEM
Booij, H. C., & Palmen, J. H. M. (1992) · Elsevier eBooks · doi:10.1016/b978-0-444-89007-8.50132-5 · Cited by 16 · see citing works
A Study of the Use of Oscillatory Flow to Characterize Isotactic and Syndiotactic Poly(propylene)s
Rojo, E., Peña, B., Muñoz, M. E., et al. (2006) · Macromolecular Chemistry and Physics · doi:10.1002/macp.200600281 · Cited by 14 · see citing works
Calafel, I., Muñoz, M. E., Santamarı́a, A., Boix, M., Conde, J. I., & Pascual, B. (2015) · European Polymer Journal · doi:10.1016/j.eurpolymj.2015.10.013 · Cited by 14 · see citing works
Ugartemendia, J. M., Muñoz, M. E., Santamaría, A., & Sarasua, J.-R. (2015) · Journal of the mechanical behavior of biomedical materials/Journal of mechanical behavior of biomedical materials · doi:10.1016/j.jmbbm.2015.04.007 · Cited by 11 · see citing works
Thermorheological Properties of Hydrogenated Pseudorandom Styrene−Butadiene Copolymers
Yoshida, J., & Friedrich, C. (2005) · Macromolecules · doi:10.1021/ma050889+ · Cited by 10 · see citing works
synthesis and polymerization of vinylcyclopropanes
Moszner, N., Zeuner, F., Völkel, T., & Rheinberger, V. (1999) · Macromolecular Chemistry and Physics · doi:10.1002/(sici)1521-3935(19991001)200:10
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- Authors
- Sangroniz, L., Cavallo, D., Santamaria, A., Müller, A. J., & Alamo, R. G.
- Affiliations
- University of the Basque Country (ES)
- University of Genoa (IT)
- POLYMAT and Polymer Science and Technology Department, Faculty of Chemistry, University of the Basque Country UPV/EHU, Paseo Manuel de Lardizabal 3, 20018, Donostia-San Sebastián, Spain
- Ikerbasque (ES)
- Florida A&M University - Florida State University College of Engineering (US)
- Corresponding author
- Cavallo, Dario
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2017-01-06
- Volume
- 50
- Issue
- 2
- Pages
- 642-651
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2569082314
- Cited by
- 82
- References
- 45
- Citations by year
- 2026: 9 · 2025: 11 · 2024: 13 · 2023: 6 · 2022: 15 · 2021: 9 · 2020: 6 · 2019: 3 · 2018: 5 · 2017: 5
- FWCI
- 2.97
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- CINECA IRIS Institutial Research Information System (University of Genoa) (submittedVersion)
- Funders
- Ministerio de Economía y Competitividad (MAT2014-53437-C2-P)
- Eusko Jaurlaritza (IT586-13)
- Euskal Herriko Unibertsitatea
- Division of Materials Research (DMR 1607786)
- Topics
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Chemical Engineering › Fluid Flow and Transfer Processes › Rheology and Fluid Dynamics Studies
- Physical Sciences › Materials Science › Materials Chemistry › Material Dynamics and Properties
- Keywords
- self-nucleation, semicrystalline polymers, ethylene-propylene copolymer, metallocene catalysts, random copolymers, recrystallization kinetics, thermorheological complexity, time-temperature superposition, crystallinity, polymer melts
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