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Using a fully recyclable dicarboxylic acid for producing dispersible and thermally stable cellulose nanomaterials from different cellulosic sources

Author:
Jia, Chao, Chen, Liheng, Shao, Ziqiang, Agarwal, Umesh P., Hu, Liangbing, Zhu, J. Y.
Source:
Cellulose 2017 v.24 no.6 pp. 2483-2498
ISSN:
0969-0239
Subject:
Eucalyptus, Fourier transform infrared spectroscopy, Picea, Raman spectroscopy, X-ray diffraction, acid hydrolysis, cellulose, cellulose microfibrils, cotton, crystal structure, dissolving pulp, esterification, nanocrystals, oxalic acid, sulfuric acid, thermal stability
Abstract:
We fabricated cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) from different cellulose materials (bleached eucalyptus pulp (BEP), spruce dissolving pulp (SDP) and cotton based qualitative filter paper (QFP) using concentrated oxalic acid hydrolysis and subsequent mechanical fibrillation (for CNFs). The process was green as acid can be easily recovered, and the prepared cellulose nanomaterials were carboxylated and thermally stable. In detail, the CNC yield from the different materials was similar. After hydrolysis, the DP of the cellulose materials decreased substantially, whereas the mechanical fibrillation of the cellulosic solid residues (CSRs) did not dramatically reduce the DP of cellulose. CNCs with different aspect ratios were produced from different starting materials by oxalic acid hydrolysis. The CNCs and CNFs obtained from BEP and QFP possessed more uniform dimensions than those from SDP. On the other hand, CNFs derived from SDP presented the best suspension stability. FTIR analyses verified esterification of cellulose by oxalic acid hydrolysis. The results from both XRD and Raman spectroscopy indicated that whereas XRD crystallinity of CNCs from BEP and QFP did not change significantly, there was some change in Raman crystallinity of these samples. Raman spectra of SDP CNCs indicated that the acid hydrolysis preferably removed cellulose I portion of the samples and therefore the CNCs became cellulose II enriched. TGA revealed that the CNCs obtained from QFP exhibited higher thermal stability compared to those from BEP and SDP, and all the CNCs possessed better thermal stability than that of CNCs from sulfuric acid hydrolysis. The excellent properties of prepared cellulose nanomaterials will be conducive to their application in different fields.
Agid:
5728411