Alternating crystalline lamellar structures from thermodynamically miscible poly(ε-caprolactone) H/D blends

Lengwan Li, Matthias M.L. Arras, Tianyu Li, Wei Li, Dongsook Chang, Jong K. Keum, Peter V. Bonnesen, Shuo Qian, Xiangfang Peng, Byeongdu Lee, Kunlun Hong

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

Thermodynamic interaction and non-isothermal crystallization behavior in a series of protiated (H-) and deuterated (D-) poly(ε-caprolactone) (PCL) blends have been systematically investigated. The blends were thermodynamically miscible in the melt. The Flory−Huggins interaction parameter (χ) between H- and D-PCL segments was estimated. The hydroxyl groups in the PCL chain-ends were found to contribute significantly to the negative χ values. Combined characterization of small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS) revealed that upon slow cooling, unique alternating H-rich and D-rich PCL lamellar structures are formed regardless of the blend ratio, which is attributed to the Tc difference between H- and D-PCLs. While upon rapid cooling, mixed crystals of H- and D-PCLs are predominantly formed. These results provide insightful information on the melt thermodynamics as well as detailed chain arrangements in lamellar crystals for semi-crystalline H/D polyester blends.

Original languageEnglish
Pages (from-to)320-328
Number of pages9
JournalPolymer
Volume175
DOIs
StatePublished - Jun 26 2019

Funding

The authors gratefully appreciate the support of the National Natural Science Foundation of China (NO. 51573063). L. Li thanks the Chinese Scholarship Council for its financial support. The polymers were synthesized at the Center for Nanophase Materials Sciences (CNMS) at the Oak Ridge National Laboratory, which is a DOE Office of Science User Facility. Neutron scattering studies were performed at the CG-3 Bio-SANS instrument at the High-Flux Isotope Reactor (HFIR), ORNL, which is sponsored by the Office of Biological and Environmental Research, and the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. This research used resources of the Advanced Photon Source, a U.S. Department of Energy Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. We thank Dr. Changwoo Do and Dr. Wei-Ren Chen (SNS, ORNL) for helping with the calculated SANS curves (SI). The authors gratefully appreciate the support of the National Natural Science Foundation of China (NO. 51573063 ). L. Li thanks the Chinese Scholarship Council for its financial support. The polymers were synthesized at the Center for Nanophase Materials Sciences (CNMS) at the Oak Ridge National Laboratory , which is a DOE Office of Science User Facility. Neutron scattering studies were performed at the CG-3 Bio-SANS instrument at the High-Flux Isotope Reactor (HFIR) , ORNL, which is sponsored by the Office of Biological and Environmental Research , and the Scientific User Facilities Division , Office of Basic Energy Sciences , U.S. Department of Energy . This research used resources of the Advanced Photon Source, a U.S. Department of Energy Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357 . We thank Dr. Changwoo Do and Dr. Wei-Ren Chen (SNS, ORNL) for helping with the calculated SANS curves (SI).

Keywords

  • Co-crystallization
  • Deuterated poly(ε-caprolactone)
  • Small-angle neutron scattering

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