Discrimination of Cellulose I, II, III_I and III_II Polymorphs in Cellulosic Fibers by NIR Hyperspectral Imaging...

Native cellulose I can be converted into crystalline polymorphs II and III_I, while cellulose II can be further converted into III_II through chemical treatments that induce significant structural, physical, and chemical changes. Accurate identification and differentiation of these polymorphs is essential for predicting fiber reactivity and processing behavior, but current methods are time-consuming. This study demonstrates the potential of near-infrared hyperspectral imaging (HSI-NIR) combined with linear discriminant analysis as a rapid, non-destructive tool for polymorph discrimination. Cellulose I, II, III_I, and III_II were produced from bleached kraft pulps of eucalyptus and pine and from cotton linters using NaOH (20% w/v) and ethylenediamine treatments. HSI-NIR successfully differentiated polymorphs based on spectral signatures in the 1480-1600 nm range, regardless of botanical source. Complementary characterization by XRD confirmed polymorph conversions, showing crystallinity reductions of 10-15% for cellulose I→II and I→III_I conversions, with crystallite size decreasing from 7.2 nm (cotton CI) to 3.2-3.4 nm in all CIII_II samples. XPS analysis revealed increased C-O surface accessibility in cellulose II and III, with complete disappearance of COOH groups in cellulose III samples. These results establish HSI as a promising screening tool for cellulose polymorph identification (>95% classification accuracy) and provide comprehensive baseline data on structural and chemical transformations that govern fiber reactivity in chemical and enzymatic processes.