The glass transition (Tg) behavior and enthalpy recovery of polystyrene nanorods within an anodic aluminum oxide (AAO) template (supported nanorods) and after removal from AAO (unsupported nanorods) is studied using Flash differential scanning calorimetry. Tg is found to be depressed relative to the bulk by 20 ± 2 K for 20 nm-diameter unsupported polystyrene (PS) nanorods at the slowest cooling rate and by 9 ± 1 K for 55 nm-diameter rods. On the other hand, bulk-like behavior is observed in the case of unsupported 350 nm-diameter nanorods and for all supported rods in AAO. The size-dependent Tg behavior of the PS unsupported nanorods compares well with results for ultrathin films when scaled using the volume/surface ratio. Enthalpy recovery was also studied for the 20 and 350 nm unsupported nanorods with evolution toward equilibrium found to be linear with logarithmic time. The rate of enthalpy recovery for the 350 nm rods was similar to that for the bulk, whereas the rate of recovery was enhanced for the 20 nm rods for down-jump sizes larger than 17 K. A relaxation map summarizes the behavior of the nanorods relative to the bulk and relative to that for the 20 nm-thick ultrathin film. Interestingly, the fragility of the 20 nm-diameter nanorod and the 20 nm ultrathin film are identical within the error of measurements, and when plotted vs departure from Tg (i.e., T − Tg), the relaxation maps of the two samples are identical in spite of the fact that the Tg is depressed 8 K more in the nanorod sample.
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Photomechanical molecular crystals and nanowire assemblies based on the [2+2] photodimerization of a phenylbutadiene derivative
( E )-4-Fluoro-cinnamaldehyde malononitrile (( E )- 4FCM ) is a new phenylbutadiene derivative that undergoes a [2+2] photocycloaddition in the crystal form. Optical absorption and proton nuclear magnetic resonance ( 1 H-NMR) measurements demonstrate that the solid-state ( E )- 4FCM photodimerization is a negative photochromic reaction that proceeds to 97% completion. The large geometry change and full conversion allow bulk crystals of ( E )- 4FCM to show strong photosalient effects when exposed to 405 nm ultraviolet light. When ( E )- 4FCM nanowires are grown in an anodic alumina oxide (AAO) template, they maintain a high degree of crystallinity and orientation, as determined by X-ray diffraction measurements. When illuminated, ( E )- 4FCM nanowire bundles exhibit a rapid expansion, during which they spread by as much as 300% in the lateral direction. This lateral expansion is at least partially due to a photoinduced crystal expansion along the diameter of the nanowires. When ( E )- 4FCM nanowires are confined inside the AAO template, the photoinduced expansion can be harnessed to deform the template, causing it to bend under UV light irradiation. The bending motion due to 2.0 mg of 4FCM in a template can cause the template to bend by up to 1.0 mm and lift up to 200 g. These results represent a significant improvement in work output relative to previous composite actuator membranes based on diarylethene photochromes.
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- Award ID(s):
- 1810514
- PAR ID:
- 10177110
- Date Published:
- Journal Name:
- Journal of Materials Chemistry C
- Volume:
- 8
- Issue:
- 15
- ISSN:
- 2050-7526
- Page Range / eLocation ID:
- 5036 to 5044
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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