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Cited by 128Polymer crystallization and propertiesBlock Copolymer Self-AssemblyAnodic Oxide Films and Nanostructures

The Crystallization of Confined Polymers and Block Copolymers Infiltrated Within Alumina Nanotube Templates

Michell, Rose Mary, Lorenzo, Arnaldo T., Müller, Alejandro J., Lin, Ming-Champ, Chen, Hsin-Lung, Blaszczyk-Lezak, Iwona, Martín, Jaime, Mijangos, Carmen·2012·Macromolecules
DOI 10.1021/ma202327f
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Abstract

Porous anodic aluminum oxide (AAO) templates with 20, 35, and 60 nm cylindrical pores were prepared and subsequently infiltrated with poly(ethylene oxide), PEO, polyethylene, PE, and polyethylene- block -polystyrene diblock copolymers, PE- b -PS, of various compositions. The crystallization of the nanocylinders within the AAO templates was studied by differential scanning calorimetry (DSC) and wide angle X-ray diffraction (WAXD). A clear change from heterogeneous to homogeneous bulk nucleation was detected in the PEO before and after infiltration within a 20 nm template, respectively. The homogeneously nucleated nanocylinders needed extreme supercooling in order to crystallize, and their low crystallization temperature was successfully correlated with the volume of the crystallizing phase. 2D-WAXD measurements demonstrated that the PEO chains within the crystals formed inside the nanocylinders, preferentially orient perpendicular to the cylinder axis. This chain orientation is probably due to the easier crystal growth propagation along the cylinder length (200 μm for the templates employed to infiltrate PEO). In the case of the infiltrated PE, although its crystallization temperature was also lowered by confinement within a large number of nanocylinders, its value is still at least 75 °C above T g; therefore, its nucleation is probably originated at the surface of the nanocylinders and cannot be considered homogeneous bulk nucleation. Strongly segregated semicrystalline PE- b -PS diblock copolymers were infiltrated into AAO templates for the first time, thereby creating a nanostructured hybrid material where the PE phase experienced double confinement for some compositions (i.e, the phase-segregated confinement within a vitreous PS matrix and the physical confinement within the nanopores). Fractionated crystallization was observed for the PE block microdomains within both neat copolymers and infiltrated ones. However, in the case of the infiltrated block copolymers, the dominant crystallization was always that produced at maximum supercooling, as expected for the extreme confinement environment. In the cases of PE blocks that self-assemble to form 42 nm diameter cylinders and 24 nm spheres within the neat block copolymers, the PE phase crystallization was impossible to detect once they were infiltrated into the 35 nm templates, as opposed to the 60 nm case where the lowest crystallization and melting temperatures were recorded. The crystallization and melting temperatures decreased as the volume of the crystallizing phase decreased (i.e., with a decrease in template pore volume, for neat PE, or PE phase volume within neat of infiltrated copolymers). The nucleation of the confined PE block microdomains is probably originated at their surface.

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  • The majority of studies show that PEO exhibits a single exothermic peak during cooling when confined within AAO.

    “The majority of studies have shown that the PEO exhibits a single exothermic peak during cooling when confined within AAO [ 218 , 277-280 ].”

    From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [218]

  • Similar low crystallization temperatures were also found in PEO confined within block copolymers or AAO templates.

    “Similar low crystallization temperatures were also found in PEO confined within block copolymers or AAO templates (see previous sections) [ 128 , 218 , 277-280 ].”

    From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [218]

  • For polymer crystallization within AAO templates, a possible nucleation effect of the AAO wall has been frequently proposed to explain the relatively high T c compared to T g.

    “As for polymer crystallization within AAO templates, a possible nucleation effect of the AAO wall has been frequently proposed to explain the relatively high T c as compared to the T g , such as in PE [218] , PBS [344] , PVDF [274] , etc.”

    From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [218]

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Authors
Michell, R. M., Lorenzo, A. T., Müller, A. J., Lin, M.-C., Chen, H.-L., Blaszczyk-Lezak, I., Martín, J., & Mijangos, C.
Affiliations
  • Universidad Simón Bolívar (VE)
  • National Tsing Hua University (TW)
  • Instituto de Ciencia y Tecnología de Polímeros, CSIC, Juan de la Cierva, 3, 28006 Madrid, Spain
  • Instituto de Ciencia y Tecnología de Polímeros (ES)
Corresponding author
Müller, Alejandro J.
ORCID
Venue
Macromolecules
Publisher
American Chemical Society (ACS)
Published
2012-01-31
Volume
45
Issue
3
Pages
1517-1528
ISSN
  • 0024-9297 (ISSN-L)
  • 1520-5835
DOI
10.1021/ma202327f
OpenAlex
W2059509278
Cited by
128
References
95
Citations by year
2025: 5 · 2024: 5 · 2023: 3 · 2022: 6 · 2021: 9 · 2020: 3 · 2019: 5 · 2018: 11 · 2017: 22 · 2016: 15 · 2015: 15 · 2014: 12 · 2013: 14 · 2012: 3
FWCI
11.07
Type
journal article
Language
en
Open access
closed
Locations
Macromolecules (publishedVersion)
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 › Materials Chemistry › Anodic Oxide Films and Nanostructures
Keywords
confined polymers, block copolymers, porous alumina templates, polymer crystallization, poly(ethylene oxide), polyethylene, heterogeneous nucleation, supercooling, chain orientation, phase segregation, fractional crystallization, nanopore confinement

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