RESUMO
The general aspects of polymer crystallization under external flow, i.e., flow-induced crystallization (FIC) from fundamental theoretical background to multi-scale characterization and modeling results are presented. FIC is crucial for modern polymer processing, such as blowing, casting, and injection modeling, as two-third of daily-used polymers is crystalline, and nearly all of them need to be processed before final applications. For academics, the FIC is intrinsically far from equilibrium, where the polymer crystallization behavior is different from that in quiescent conditions. The continuous investigation of crystallization contributes to a better understanding on the general non-equilibrium ordering in condensed physics. In the current review, the general theories related to polymer nucleation under flow (FIN) were summarized first as a preliminary knowledge. Various theories and models, i.e., coil-stretch transition and entropy reduction model, are briefly presented together with the modified versions. Subsequently, the multi-step ordering process of FIC is discussed in detail, including chain extension, conformational ordering, density fluctuation, and final perfection of the polymer crystalline. These achievements for a thorough understanding of the fundamental basis of FIC benefit from the development of various hyphenated rheometer, i.e., rheo-optical spectroscopy, rheo-IR, and rheo-x-ray scattering. The selected experimental results are introduced to present efforts on elucidating the multi-step and hierarchical structure transition during FIC. Then, the multi-scale modeling methods are summarized, including micro/meso scale simulation and macroscopic continuum modeling. At last, we briefly describe our personal opinions related to the future directions of this field, aiming to ultimately establish the unified theory of FIC and promote building of the more applicable models in the polymer processing.
RESUMO
The chain dynamics and crystalline network structure of poly[R-3-hydroxybutyrate-co-4-hydroxybutyrate] (P(3HB-co-4HB)) were systematically investigated by the combination of various solid-state NMR techniques. High-resolution 13C cross-polarization (CP) and direct-polarization (DP) MAS with selective recycle delay times were first used to check the presence or absence of the 4HB unit in the crystalline domain. The results show that the 4HB unit is excluded from the crystalline domain. Afterward, 1H MAS Nuclear Overhauser Effect Spectroscopy (NOESY) with different mixing times was used, which shows that no micro-phase separation exists in the amorphous domain. 1H magic-sandwich-echo (MSE)-FID at elevated temperature shows the absence of motions on a timescale of 100 µs and below in the crystalline domain, as evidenced by the invariant second moment M2 of the proton line shape. Finally, the crystalline based network density was characterized directly by magic and polarization echo (MAPE)-double quantum (DQ) NMR, which shows a significant decreasing tendency after 80 °C. Such a decreasing crystalline network density, together with the reduced relaxation time, results in the significant decrement of the maximum stretch ratio and modulus in the high-temperature region.
RESUMO
We investigate the chain conformation of ring polymers confined to a cylindrical nanochannel using both theoretical analysis and three-dimensional Langevin dynamics simulations. We predict that the longitudinal size of a ring polymer scales with the chain length and the diameter of the channel in the same manner as that for linear chains based on scaling analysis and Flory-type theory. Moreover, Flory-type theory also gives the ratio of the longitudinal sizes for a ring polymer and a linear chain with identical chain length. These theoretical predictions are confirmed by numerical simulations. Finally, our simulation results show that this ratio first decreases and then saturates with increasing the chain stiffness, which explains the discrepancy in experiments. Our results have biological significance.
