Characterization of the interaction of poly(ethylene oxide) with nanosize fumed silica: Surface effects on crystallization
Abstract
Abstract Poly(ethylene oxide) (PEO) of 4600 molar mass (PEO‐4600) was crystallized from methanol in the presence of hydrophilic fumed silicas (A380, A200, and OX50) with nominal surface areas of 380, 200, and 50 m2/g and a hydrophobic fumed silica (R812s) modified with methyl groups. The composites were characterized by thermogravimetric analysis and differential scanning calorimetry. The inhibition of crystallization and the tendency for chain reorganization after melting were in the order of A380 > A200 > OX50 > R812s, respectively, that is, both were least for the hydrophobic silica and increased with increasing specific surface area for the hydrophilic silica. The interaction of PEO with the silica increased in the melt state as compared with the solution‐cast samples, resulting in enhanced suppression of crystallization. The following took place at a high silica content: (1) crystallization occurred at crystallization temperatures [Tc < Tc (bulk)], suggesting that the silica inhibited crystallization; (2) crystallites with melt temperatures [Tm < Tm (bulk)] were observed, indictive of smaller and/or less perfect crystals; and (3) melt entropies [ΔSm (surface) < ΔSm (bulk)] suggested that the interaction of surface silanols, SisOH, with PEO decreased both the melt entropy and crystallite size/perfection. Crystallinity was observed in solution‐cast composites when there were greater than ∼0.03 PEO molecules/nm2 for native and ∼0.01 PEO molecules/nm2 for methylated fumed silica, similar to reported plateau equilibrium adsorption values from methanol. These results were consistent with a model in which PEO interacted more strongly with native fumed silica as compared with hydrophobically modified silica because of hydrogen bonding of the ether oxygens of PEO with the acidic silanols, preventing chain mobility and crystallization. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1978–1993, 2003
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Fractionated crystallization behavior has been observed in PEO/silica and PE/silica at very high loadings of silica.
“Interestingly, fractionated crystallization behavior has been observed in PEO/silica (SiO 2 ) [308][309][310] and PE/SiO 2 [311] at very high loadings of SiO 2 .”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [310]
The degree of suppression of PEO crystallization increases with increasing φSiO2 and decreasing SiO2 size.
“It is also found that the degree of suppression of PEO crystallization increases with increasing ϕ SiO2 and decreasing SiO 2 size.”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [310]
Ding et al. reported a very weak low-temperature crystallization peak (-30 °C) at a low percentage of PEO, resulting from PEO chains interacting with the silica surface.
“Ding et al. also reported a very weak low-temperature crystallization peak (-30 °C) which appeared at a low percentage of PEO, resulting from the PEO chains interacting with the silica surface [310] .”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [310]
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- Authors
- Ding, J., Maitra, P., & Wunder, S. L.
- Affiliations
- Temple University (US)
- Corresponding author
- Wunder, Stephanie L.
- Venue
- Journal of Polymer Science Part B: Polymer Physics
- Publisher
- Wiley
- Published
- 2003-07-17
- Volume
- 41
- Issue
- 17
- Pages
- 1978-1993
- ISSN
- 0887-6266 (ISSN-L)
- 1099-0488
- OpenAlex
- W2010281475
- Cited by
- 28
- References
- 51
- Citations by year
- 2026: 1 · 2023: 1 · 2021: 2 · 2020: 1 · 2019: 5 · 2018: 2 · 2017: 2 · 2016: 1 · 2015: 1 · 2014: 1 · 2013: 2 · 2012: 1
- FWCI
- 0.98
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of Polymer Science Part B Polymer Physics (publishedVersion)
- Topics
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer Nanocomposites and Properties
- Physical Sciences › Materials Science › Materials Chemistry › Crystallization and Solubility Studies
- Keywords
- poly(ethylene oxide), fumed silica, polymer-silica interaction, crystallization suppression, surface silanols, methylated silica, specific surface area, crystallite size, hydrogen bonding, adsorption, polymer nanocomposites
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