Kinetics of Crystal Nucleation in Polyethylene
Abstract
Observations of the freezing behavior of droplets of a linear polyethylene (Marlex-50) suspended in an inert medium have been made. It is possible to cool such suspensions of molten droplets to 85°—87°C before the majority of the droplets freeze, provided precautions are taken to minimize nucleation by the vessel walls. This indicates unambiguously that spherulites formed near 120°C (the usual crystallization range) are nucleated by heterogeneities in the melt. Analysis of experiments performed at various cooling rates indicate an end surface interfacial energy of rod-shaped nuclei of 168 ergs/cm2. This is similar to the estimates made of the fold-surface energy in crystals formed from dilute solution. The cooling-rate experiments also indicated that the transport processes in the production of the polymeric nucleus are similar to those involved in the production of nuclei of n-alkane crystals.
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In those droplet experiments, larger droplets solidified at higher temperature because they are more likely to contain nucleating heterogeneities, and droplets smaller than 3 micrometers solidified at the critical temperature of 85°C, tentatively attributed to homogeneous nucleation.
“Typically, larger droplets solidified at higher temperature since they are more likely to contain nucleating heterogeneities, and droplets smaller than 3 micrometer solidified at the critical temperature of 85 °C, which was tentatively attributed to the homogeneous nucleation regime.”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [1]
In the Cormia, Price and Turnbull droplet experiments, only 5% of polyethylene droplets solidified above 100°C, about 40% crystallized between 100 and 90°C, and more than 50% solidified at around 85-87°C.
“During continu-ous cooling, only 5 % of the droplets solidified above 100 °C, with a minor fraction crystallizing at 122-123 °C, which is the typical temperature range where nucleation of spherulites in the bulk material become appreciable.About 40 % of the droplets crystallize between 100 and 90 °C, while more than 50 % of them solidified at around 85-87 °C.”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [1]
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References 13 · Cited by 335
- Authors
- Cormia, R. L., Price, F. P., & Turnbull, D.
- Affiliations
- General Electric (United States) (US)
- ORCID
- Turnbull, D.
- Venue
- The Journal of Chemical Physics
- Publisher
- AIP Publishing
- Published
- 1962-09-15
- Volume
- 37
- Issue
- 6
- Pages
- 1333-1340
- ISSN
- 0021-9606 (ISSN-L)
- 1089-7690
- OpenAlex
- W2081324328
- Cited by
- 335
- References
- 13
- Citations by year
- 2026: 5 · 2025: 3 · 2024: 3 · 2023: 4 · 2022: 5 · 2021: 8 · 2020: 7 · 2019: 8 · 2018: 7 · 2017: 6 · 2016: 5 · 2015: 9 · 2014: 9 · 2013: 11 · 2012: 7
- FWCI
- 14.20
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- The Journal of Chemical Physics (publishedVersion)
- Funders
- National Science Foundation
- Topics
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Earth and Planetary Sciences › Atmospheric Science › nanoparticles nucleation surface interactions
- Physical Sciences › Materials Science › Materials Chemistry › Crystallization and Solubility Studies
- Keywords
- crystal nucleation, polyethylene, spherulites, heterogeneous nucleation, interfacial energy, cooling rate, droplet freezing, nucleation kinetics, polymer crystallization
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