4.7 Article

Characterization of the supramolecular structures of cellulose nanocrystals of different origins

Journal

CELLULOSE
Volume 28, Issue 3, Pages 1369-1385

Publisher

SPRINGER
DOI: 10.1007/s10570-020-03590-z

Keywords

Cellulose; Tunicin; Bacterial; Cladophora; Wood; Pulp; Cotton; Crystallinity; Raman spectroscopy

Funding

  1. NSF through the University of Wisconsin-Madison Materials Research Science and Engineering Center [DMR-1121288]

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The properties of cellulose nanocrystals (CNCs) depend on their supramolecular structures, which can influence characteristics such as crystallinity and water accessibility. Differences in CNCs largely arise from variances in starting materials, indicating the importance of understanding how CNCs are produced.
Properties of cellulose nanocrystals (CNCs) depend upon their supramolecular structures, which are important to understand in order to optimize their applications. In this investigation, the structures of CNCs produced upon 48-64% H2SO4 hydrolysis of hydrothermally-treated poplar, bleached kraft pulp, cotton microcrystalline cellulose, bacterial cellulose, tunicin, and cladophora cellulose were comparatively analyzed. TEM provided information on the morphological aspects. Raman, MAS-NMR, and XRD provided information on one aspect of the supramolecular organization, namely, crystallinity (CrI). Other characteristics of supramolecular structure were analyzed by various Raman methods, namely, accessibility to water, exocyclic CH2OH conformation ratio, and chain conformation disorder (CCONDIS)-the last method was developed in the present study. In general, CNCs retained the crystallinity of the starting material irrespective of the measurement method of CrI. Additionally, it was found that crystallite size and supramolecular organization influenced CrI as well. These analyses further indicated that poplar- and pulp-CNCs had significantly higher water accessibility as compared with CNCs from cladophora, bacterial, tunicin, and cotton MCC CNCs, implying higher molecular disorder, which was also reflected in measurements of CH2OH conformation ratio and CCONDIS. The findings indicate that significant differences among the CNCs seem to arise largely from differences between the starting materials. Additionally, considering that CNCs can have very different morphologies and structural properties depending upon how they are produced, the analyses carried out here can characterize such CNCs and estimate their applications. [GRAPHICS] .

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