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Cellulose I crystallinity determination using FT–Raman spectroscopy: univariate and multivariate methods

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Abstract

Two new methods based on FT–Raman spectroscopy, one simple, based on band intensity ratio, and the other using a partial least squares (PLS) regression model, are proposed to determine cellulose I crystallinity. In the simple method, crystallinity in cellulose I samples was determined based on univariate regression that was first developed using the Raman band intensity ratio of the 380 and 1,096 cm−1 bands. For calibration purposes, 80.5% crystalline and 120-min milled (0% crystalline) Whatman CC31 and six cellulose mixtures produced with crystallinities in the range 10.9–64% were used. When intensity ratios were plotted against crystallinities of the calibration set samples, the plot showed a linear correlation (coefficient of determination R 2 = 0.992). Average standard error calculated from replicate Raman acquisitions indicated that the cellulose Raman crystallinity model was reliable. Crystallinities of the cellulose mixtures samples were also calculated from X-ray diffractograms using the amorphous contribution subtraction (Segal) method and it was found that the Raman model was better. Additionally, using both Raman and X-ray techniques, sample crystallinities were determined from partially crystalline cellulose samples that were generated by grinding Whatman CC31 in a vibratory mill. The two techniques showed significant differences. In the second approach, successful Raman PLS regression models for crystallinity, covering the 0–80.5% range, were generated from the ten calibration set Raman spectra. Both univariate-Raman and WAXS determined crystallinities were used as references. The calibration models had strong relationships between determined and predicted crystallinity values (R 2 = 0.998 and 0.984, for univariate-Raman and WAXS referenced models, respectively). Compared to WAXS, univariate-Raman referenced model was found to be better (root mean square error of calibration (RMSEC) and root mean square error of prediction (RMSEP) values of 6.1 and 7.9% vs. 1.8 and 3.3%, respectively). It was concluded that either of the two Raman methods could be used for cellulose I crystallinity determination in cellulose samples.

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Acknowledgments

The authors thank the reviewers for their review, comments, and insights which resulted in the improvement of the manuscript.

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Authors and Affiliations

  1. USDA Forest Service, Forest Products Laboratory, One Gifford Pinchot Drive, Madison, WI, 53705-2398, USA

    Umesh P. Agarwal, Richard S. Reiner & Sally A. Ralph

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  1. Umesh P. Agarwal
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  2. Richard S. Reiner
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  3. Sally A. Ralph
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Correspondence to Umesh P. Agarwal.

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Agarwal, U.P., Reiner, R.S. & Ralph, S.A. Cellulose I crystallinity determination using FT–Raman spectroscopy: univariate and multivariate methods. Cellulose 17, 721–733 (2010). https://doi.org/10.1007/s10570-010-9420-z

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  • DOI: https://doi.org/10.1007/s10570-010-9420-z

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