Comparison of sample crystallinity determination methods by X-ray diffraction for challenging cellulose I materials

Cellulose crystallinity assessment is important for optimizing the yield of cellulose products, such as bioethanol. X-ray diffraction is often used for this purpose for its perceived robustness and availability. In this work, the five most common analysis methods (the Segal peak height method and those based on peak fitting and/or amorphous standards) are critically reviewed and compared to two-dimensional Rietveld refinement. A larger (\(n=16\)) and more varied collection of samples than previous studies have presented is used. In particular, samples (\(n=6\)) with low crystallinity and small crystallite sizes are included. A good linear correlation (\(r^{2} \ge 0.90\)) between the five most common methods suggests that they agree on large-scale crystallinity differences between samples. For small crystallinity differences, however, correlation was not seen for samples that were from distinct sample sets. The least-squares fitting using an amorphous standard shows the smallest crystallite size dependence and this method combined with perpendicular transmission geometry also yielded values closest to independently obtained cellulose crystallinity values. On the other hand, these values are too low according to the Rietveld refinement. All analysis methods have weaknesses that should be considered when assessing differences in sample crystallinity.