Abstract
Chain-level structure of semicrystalline polymers in melt- and solution-grown crystals has been debated over the past half century. Recently, 13C–13C double quantum (DQ) Nuclear Magnetic Resonance (NMR) spectroscopy has been successfully applied to investigate chain-folding (CF) structure and packing structure of 13C enriched polymers after solution and melt crystallization. We review recent NMR studies for (i) packing structure, (ii) chain trajectory, (iii) conformation of the folded chains, (iv) nucleation mechanisms, (v) deformation mechanism, and (vi) molecular dynamics of semicrystalline polymers.
Highlights
Crystallization of long polymer chains leads to drastic structural change from random coils in the melt and solution states into folded chains in thin crystalline lamellae [1,2,3,4,5]
Thereby, ssNMR techniques have successfully revealed the three dimensional structure of peptides, as well as lacking in kinetics effects on chain-level structure is critical in understanding polymer crystallization
In (e) and (f), the simulated red and blue double quantum (DQ) curves based on the closest interstem 13 C–13 C internuclear distance; of 4.0 Å; and an exponential T2 of 8.3 ms and = 4.2 Å and T2 = 10.5 ms, respectively
Summary
Crystallization of long polymer chains leads to drastic structural change from random coils in the melt and solution states into folded chains in thin crystalline lamellae [1,2,3,4,5]. Thereby, ssNMR techniques have successfully revealed the three dimensional structure of peptides, as well as lacking in kinetics effects on chain-level structure is critical in understanding polymer crystallization. Solid-state (ss) NMR spectroscopy is a sophisticated and powerful means to investigate the and amplitude of re-orientations the glassy [27], crystalline [31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47],anisotropic and meltinformation [48,49] states, and local structure and dynamics ofin organic and inorganic systems [27]. We review recent progress for the chain-level structure chains experimental DQ results were compared with the simulated ones based on 13C atomic positions and molecular dynamics of folding various semicrystalline ssNMR. Average values of chain-folding number , chain-folding fraction , and shape and size ofof folded
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