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In the earlier theoretical research, impact of entanglement on folding during crystallization was minimized. The combination of 13C isotope labeling and NMR spectroscopy allows us to quantitatively determine stem to stem distance as well as chain folding distance, hence, we are able to probe chain-level structure. Our recent work indicated that polymer chains are possible to fold prior to crystallization. In this poster, we would like to investigate the folding structure of a semi-crystalline polymer in melt-grown crystals (mgc) by using solid-state NMR spectroscopy and SAXS measurement. First, various 13C enriched poly(L-lactic acid) (PLLA) samples with different molecular weights (Mw = 2.5k – 300k g/mol) across critical entanglement length (Mc = 16k g/mol) were prepared in order to observe the molecular weight dependence of folding structure of PLLA. We revealed that entanglements influence the folding number during crystallization. Second, we attempt to observe the entanglement effect through diluting entanglement density, i.e., blending the PLLA above and below the Mc with different ratio and molecular weight. Based on the experimental results, we would like to highlight the impact of entanglements on folding of semicrystalline polymer in the melt-grown crystal.
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Oligoaniline-assisted self-assembly of polyaniline crystals
The conductivity and charge transport mobility of conjugated polymers (CPs) are largely correlated with their degree of crystallinity, rendering the crystallization of CPs an important endeavour. However, such tasks can be challenging, especially in the absence of sidechain functionalization. In this study, we demonstrate that the incorporation of a small amount of oligomers, specifically tetraaniline, can induce crystallization of the parent polymer, polyaniline, through a single-step self-assembly process. The resulting crystals are compositionally homogeneous because the oligomers and their parent polymer share the same repeating unit and are both electroactive. Mechanistic studies reveal that the tetraaniline forms a crystalline seed that subsequently guides the assembly of polyaniline due to their structural similarities. Applying this oligomer-assisted crystallization approach to polyaniline with defined molecular weights resulted in single crystalline nanowires for 5000 Da polyaniline, and nanowires with strong preferential chain orientation for those with molecular weights between 10 000 and 100 000 Da. Absorption studies reveal that the polymer chains are in an expanded conformation, which likely contributed to the high degree of packing order. Two-probe, single nanowire measurements show that the crystals have conductivity as high as 19.5 S cm −1 . This method is simple, general, and can potentially be applied to other CPs.
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- Award ID(s):
- 1945664
- PAR ID:
- 10415472
- Date Published:
- Journal Name:
- Materials Horizons
- Volume:
- 10
- Issue:
- 4
- ISSN:
- 2051-6347
- Page Range / eLocation ID:
- 1282 to 1291
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D2MH01344D
