Chain entanglements play a crucial role in polymer crystallization, yet their effects on crystallization remain not fully understood. Freeze-drying is one way to potentially preserve disentangled states of long polymer chains. In fact, it is known that freeze-drying (FD) significantly accelerates the crystallization kinetics of semicrystalline polymers. However, the chain-level structure of the FD polymer chains without a long-range order (glass) has been a debatable matter. In this study, we investigate the effect of freeze-drying on single chain-level structures of 13CH3 enriched poly(L-lactic Acid) and 13CH enriched poly(D-lactic acid) racemate by using 1H-1H spin diffusion via 13C detection solid-state NMR spectroscopy. Spatial distributions of PLLA and PDLA glassy chains in the range of a few Å – 30 nm are evaluated via 1H-1H spin diffusion. This analysis provides core-shell morphology of single chains where the outer shell layers include both PDLA and PLLA mixture and the inner core possess a single component.
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Visualizing the Orientation of Single Polymers Induced by Spin-Coating
The orientation of chains within polymeric materials influences their electrical, mechanical, and thermal properties. While many techniques can infer the orientation distribution of a bulk ensemble, it is challenging to determine this information at the single-chain level, particularly in an environment of otherwise identical polymers. Here, we use single-molecule localization microscopy (SMLM) to visualize the directions of chains within spin-coated polymer films. We find a strong relationship between shear force and the degree and direction of orientation, and additionally, we reveal the effects of chain length and solvent evaporation rate. This work utilizes single-chain resolution to observe the important, though often overlooked, property of chain orientation in the common fabrication process of spin-coating.
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- Award ID(s):
- 1945249
- PAR ID:
- 10339560
- Date Published:
- Journal Name:
- Nano Letters
- ISSN:
- 1530-6984
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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