Determining conformational order and crystallinity in polycaprolactone via Raman spectroscopy

Published

April 7, 2017

Author(s)

Anthony P. Kotula, Chad R. Snyder, Kalman D. Migler

Abstract

The Raman spectra of polycaprolactones have been measured over a temperature range of 20 °C to 160 °C to distinguish ordered chain conformers in the melt state and determine the quantitative crystalline bands. Principal component analysis of the spectra in the melt state allows for separation of conformationally ordered peaks from amorphous disordered ones, whereas analysis of spectra measured during crystal melting identify peaks primarily associated with crystallinity. Component spectra of amorphous chains and crystalline components are generated from linear combinations of the principal components associated with vibrations of the ester and methylene groups. A comparison of the component spectra and density functional theory calculations of the Raman spectra indicate that sharp peaks in the ester stretch, C-C stretch, CH₂ twist, and CH₂ bend vibrational modes can be attributed to single chain modes, not necessarily the crystalline order. Component spectra in the carbonyl stretch region, sensitive to dipole-dipole interactions, are used to quantify crystallinity over a range of molar masses and during melting.

Citation

Polymer

Volume

117

Pub Type

Journals

Download Paper

https://doi.org/10.1016/j.polymer.2017.04.006

Keywords

Polycaprolactone, Raman spectroscopy

Citation

Kotula, A. , Snyder, C. and Migler, K. (2017), Determining conformational order and crystallinity in polycaprolactone via Raman spectroscopy, Polymer, [online], https://doi.org/10.1016/j.polymer.2017.04.006 (Accessed October 8, 2025)