Terahertz time-domain spectroscopy as a novel tool for crystallographic analysis in cellulose: the potentiality of being a new standard for evaluating crystallinity

Given that terahertz (THz) radiation responds to intermolecular forces such as hydrogen bonds, THz time-domain spectroscopy (THz-TDS) has expanded possibilities in cellulose research. In this study, THz-TDS was used to investigate the crystallinity of three types of cellulose-based materials. Microcrystalline cellulose (MCC) and wood were ball milled at different times, and pseudo-wood was a mixture of MCC and lignin of different mass fractions. All the samples showed peaks at 3.04 THz in the THz mass absorption coefficient spectra. Further, the spectra from 2.79 THz to 3.32 THz were cut out and detrended by subtraction from a baseline. The integrated intensity of the detrended spectra showed a correlation with the mass fraction of lignin of the pseudo-wood samples, and ball milling time of the MCC and wood samples. The correlation was similar with the crystallinity index calculated from X-ray powder diffraction. Moreover, the original wood sample without ball milling had an integrated intensity that was about 30% that of the original MCC sample, matching with the cellulose concentration of the wood (about 30% to 40%). We normalized the integrated intensity of 2.79 THz to 3.32 THz into 1 to 0 by a min-max algorithm and proposed a new index for evaluating crystallinity.

Automated summary

This study used THz-TDS to investigate the crystallinity of different cellulose-based materials and found that the integrated intensity of detrended spectra correlated positively with the mass fraction of lignin in the samples and ball milling time. By normalizing the integrated intensity, a new index for evaluating crystallinity was proposed.