Comparing crystallization rates between linear and cyclic poly(epsilon-caprolactones) via fast-scan chip-calorimeter measurements

Wang, Jing; Li, Zhaolei; Pérez, Ricardo; Müller, Alejandro J.; Zhang, Boyu; Grayson, Scott M.; Hu, Wenbing

doi:10.1016/j.polymer.2015.02.039

Cited by 45 publications

(41 citation statements)

References 49 publications

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“…Figure 11 shows that the high molecular weight cyclic PCL crystallizes faster than its linear counterpart at a crystallization temperature (T c ) of 45 C. The same trend was found for other crystallization temperatures (30 C, 35 C and 45 C) (for more details see [43]). Recently, Wang et al [50] compared the overall crystallization rates of linear and cyclic oligomeric PCLs with M n ¼ 2 kg/mol via fast-scanning chip calorimetry measurements (for further details of the specific techniques employed, see [50]). Figure 12 shows an inverse bell-shaped curve for the overall crystallization time, which can be explained by the classical theory of nucleation and growth.…”

Section: Isothermal Overall Crystallization Kineticsmentioning

confidence: 99%

“…12. On the other hand, the quantitative differences between the standard DSC data and fast-scanning chip calorimetry are a result of the different equipment involved in the measurements and also in the ways in which the isothermal crystallization experiments were performed [50]. Figure 13 shows the apparent nucleation half-time derived from the data shown in Fig.…”

Section: Isothermal Overall Crystallization Kineticsmentioning

confidence: 99%

“…Figure 13 shows the apparent nucleation half-time derived from the data shown in Fig. 12 (see [50] for details on how to derive nucleation half-times from fastscanning chip calorimetry experiments). The curve of the nucleation half-time as a function of T c exhibits two minima: one related to apparent homogeneous nucleation (low-temperature peak) and the other related to heterogeneous nucleation (high-temperature peak).…”

Section: Isothermal Overall Crystallization Kineticsmentioning

confidence: 99%

“…The crystallization half-times obtained previously [48] by conventional DSC were added for comparison purposes. Reprinted with permission from [50] …”

Section: Isothermal Overall Crystallization Kineticsmentioning

confidence: 99%

“…This result was attributed to the free chain ends in L-PCL, which enhance chain mobility and favor diffusion at lower temperatures [50].…”

Section: à25mentioning

confidence: 99%

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Crystallization of Cyclic Polymers

Pérez-Camargo

Múgica

Zubitur

et al. 2015

Polymer Crystallization I

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The effect of chain topology (ring versus linear polymer chains) on polymer crystallization is reviewed. Recent advances in ring closure and ring expansion synthetic techniques have made available a range of well-characterized samples with higher levels of purity than available decades ago. Cyclic molecules are fascinating because the structural difference between them and linear chains is relatively small, yet their behavior can be completely different from that of their linear analogs of identical chain length. The effect of having no chain ends can dramatically change the polymer coil conformation and diffusion rate, as well as the chain entanglement density in the melt. These changes are reflected in different nucleation and crystallization kinetics for cyclic and linear polymeric chains. However, the results published so far seem to be dependent on the type of polymer employed. Therefore, a careful look at the literature and evidence reported for each group of materials has been assembled and compared. The possible reasons for some of the contradictions in the evidence are also discussed.

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Section: Isothermal Overall Crystallization Kineticsmentioning

confidence: 99%

Section: Isothermal Overall Crystallization Kineticsmentioning

confidence: 99%

Section: Isothermal Overall Crystallization Kineticsmentioning

confidence: 99%

“…The crystallization half-times obtained previously [48] by conventional DSC were added for comparison purposes. Reprinted with permission from [50] …”

Section: Isothermal Overall Crystallization Kineticsmentioning

confidence: 99%

“…This result was attributed to the free chain ends in L-PCL, which enhance chain mobility and favor diffusion at lower temperatures [50].…”

Section: à25mentioning

confidence: 99%

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Crystallization of Cyclic Polymers

Pérez-Camargo

Múgica

Zubitur

et al. 2015

Polymer Crystallization I

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Comparison of Linear and Ring Polymers Partitioning into Pores Using Random Walks and Self‐Avoiding Walks Models

Litle,

Wang

2023

Macro Theory & Simulations

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We present Monte Carlo simulations that examine the partitioning of dilute solutions of ring or linear chains into a slit pore using two chain models, the random‐walk (RW) model and the self‐avoiding walk (SAW) model. We compared the partitioning coefficients K of the ring against the linear chains at the surface interaction that are both under the critical adsorption point (CAP), the exclusion regime, and above the CAP, the adsorptive regime. In both chain models, K for the ring remain larger than K for the linear chains at both regimes. The ring chain crosses over the point K = 1 at a weaker surface interaction than the linear chain. When extrapolated to infinite chain length, the cross‐over point for the ring and linear chain becomes the same (within statistical errors) for the RW model but remains different for the SAW model. The density profiles of the ring chain within the pore reveal the development of humps near the wall as the surface interaction crosses over the CAP. The excluded volume interaction in the SAW model additionally impacts the partitioning of chains in a solution consisting of a binary mixture of ring and linear chains and makes the K values in a binary mixture differ from the monodispersed solution.This article is protected by copyright. All rights reserved

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