Estimating Percent Crystallinity of Polyethylene as a Function of Temperature by Raman Spectroscopy Multivariate Curve Resolution by Alternating Least Squares

Ashok Zachariah Samuel, Bo Han Lai, Shih Ting Lan, Masahiro Ando, Chien Lung Wang, Hiro O. Hamaguchi

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

We have recently demonstrated a methodology to estimate the percent crystallinity (PC) of polymers directly with Raman spectroscopy and multivariate curve resolution (MCR) by alternating least-squares (ALS). In the MCR-ALS methodology, the Raman spectrum of a semicrystalline polymer is separated into two constituent components (crystalline and molten/amorphous) and their corresponding concentrations. The methodology necessitates that the Raman spectrum at any temperature be a linear combination of two MCR spectral components (one molten and one crystalline). This is true in the case of simple systems such as crystalline pendant alkyl domains in polymers (Samuel et al. Anal. Chem. 2016, 88, 4644). However, in the case of main chain polymer crystals (e.g., polyethylene), the situation can be complicated owing to several molecular changes in the lattice in addition to conformational reorganizations during melting. Under this circumstance, a simple two-state model may not be adequate and we describe the modifications required to treat such systems, keeping the basic principles of the proposed methodology unchanged. A comparative study with wide-angle X-ray scattering (WAXS) and Raman spectroscopy is also performed to substantiate our findings. In addition to estimating percent crystallinity (PC), our methodology is capable of revealing additional information, such as interchain interactions in crystal lattice, that in principle will help distinguishing polymorphic transformations, subtle changes in lamellar lattice dimensions, and other phase changes in polymers.

Original languageEnglish
Pages (from-to)3043-3050
Number of pages8
JournalAnalytical Chemistry
Volume89
Issue number5
DOIs
Publication statusPublished - 2017 Mar 7

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Polyethylene
Raman spectroscopy
Polymers
Crystalline materials
Molten materials
Raman scattering
Temperature
Spectral resolution
X ray scattering
Crystal lattices
Melting
Crystals

ASJC Scopus subject areas

  • Analytical Chemistry

Cite this

Estimating Percent Crystallinity of Polyethylene as a Function of Temperature by Raman Spectroscopy Multivariate Curve Resolution by Alternating Least Squares. / Samuel, Ashok Zachariah; Lai, Bo Han; Lan, Shih Ting; Ando, Masahiro; Wang, Chien Lung; Hamaguchi, Hiro O.

In: Analytical Chemistry, Vol. 89, No. 5, 07.03.2017, p. 3043-3050.

Research output: Contribution to journalArticle

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