SCIENCE CHINA Technological Sciences, Volume 62, Issue 6: 971-981(2019) https://doi.org/10.1007/s11431-018-9441-1

Structural characterization of carboxyl cellulose nanofibers extracted from underutilized sources

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  • ReceivedOct 10, 2018
  • AcceptedJan 10, 2019
  • PublishedMay 5, 2019


Two different chemical methods, TEMPO-oxidation and nitro-oxidation, were used to extract carboxyl cellulose nanofibers (CNFs) from non-wood biomass sources (i.e., jute, soft and hard spinifex grasses). The combined TEMPO-oxidation and homogenization approach was very efficient to produce CNFs from the cellulose component of biomass; however, the nitro-oxidation method was also found to be effective to extract CNFs directly from raw biomass even without mechanical treatment. The effect of these two methods on the resulting cross-section dimensions of CNFs was investigated by solution small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM) and atomic force microscopy (AFM). The UV-Vis spectroscopic data from 0.1 wt% TEMPO-oxidized nanofiber (TOCNF) and nitro-oxidized nanofiber (NOCNF) suspensions showed that TOCNF had the highest transparency (> 95%) because of better dispersion, resulted from the highest carboxylate content (1.2 mmol/g). The consistent scattering and microscopic results indicated that TOCNFs from jute and spinifex grasses possessed rectangular cross-sections, while NOCNFs exhibited near square cross-sections. This study revealed that different oxidation methods can result in different degrees of biomass exfoliation and different CNF morphology.

Funded by

the Polymer Program from Division of Materials Science of the National Science Foundation(Grant,No.,DMR-1808690)


This work was supported by the Polymer Program from Division of Materials Science of the National Science Foundation of USA (Grant No. DMR-1808690). The authors thank Professor Darren Martin group at University of Queensland for providing the raw materials and helpful discussions. The authors also thank Dr. YANG Lin and Dr. CHODANKAR Shirish at the LiX beamline, which operates under a DOE BER contract DE-SC0012704 and is supported by an NIH-NIGMS (Grant No. P41GM111244). This research used electron microscopy resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility. The facilities at Brookhaven National Laboratory operate under Contract No. DE-SC0012704. We also thank Dr. CHANG Chung-Chueh at AERTC for his assistance of the AFM measurement.


Supporting Information

The supporting information is available online at tech.scichina.com and link.springer.com. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.


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  • Figure 1

    (Color online) The UV-Vis spectra of TOCNF and NOCNF suspensions (0.1 wt%) from jute, soft spinifex (SS), and hard spinifex (HS). Photos of the biomass and the nanocellulose suspensions are listed on the bottom right corner. (a) From left to right, the raw biomass samples of jute, soft spinifex and hard spinifex; (b) from left to right, the pulp of jute, soft spinifex and hard spinifex; (c) from left to right, the 0.1 wt% TOCNF suspensions of jute, soft spinifex and hard spinifex; (d) from left to right, the 0.1 wt% NOCNF suspensions of jute, soft spinifex and hard spinifex.

  • Figure 2

    (Color online) AFM images of TOCNF and NOCNF suspensions of jute, soft spinifex and hard spinifex with concentration of 0.0015wt%. The region for each image was 1 μm×1 μm. The height distribution profiles of three selected sections of each sample (labeled by yellow rectangles) are shown underneath the image (the legends A, B and C represent the yellow rectangles from left to right). Upper row: (a) jute TOCNF suspension, (b) soft spinifex TOCNF, (c) hard spinifex TOCNF; bottom row: (d) jute NOCNF suspension, (e) soft spinifex NOCNF and (f) hard spinifex NOCNF.

  • Figure 3

    (Color online) Left column: AFM images of TOCNF suspensions of (a) jute, (b) soft spinifex and (c) hard spinifex. Right column: AFM images of NOCNF suspensions of (d) jute, (e) soft spinifex and (f) hard spinifex. The images were acquired with 0.0015 wt% suspensions and the chosen image size was 5 μm× 5 μm.

  • Figure 4

    TEM images for TOCNF and NOCNF samples. Left column: TOCNF prepared from (a) jute, (b) soft spinifex, and (c) hard spinifex. Right column: NOCNF prepared from (d) jute, (e) soft spinifex and (f) hard spinifex.

  • Figure 5

    (Color online) (a) The fitting results using the polydisperse ribbon model and the solution SAXS experimental profile for TOCNF and NOCNF suspensions of jute, soft spinifex (SS) and hard spinifex (HS) at the concentration of 0.2 wt%; and (b) the scattering curves and fits in the low-q region. For better clarity, the curves were manually shifted in the vertical direction for both figures. The bottom left diagram exhibits the shape and the parameters of ribbon model, and the fitting results (height, a; width, a+b) are listed on the top right corner.

  • Table 1   Height and width information measured by microscopy (AFM and TEM) and solution SAXS. The average and deviation for solution SAXS were extracted from the fitting results. The statistical average and deviation for microscopic data were calculated based on the image analysis


    Height (nm)

    Width (nm)


    Solution SAXS


    Solution SAXS

    Jute TOCNF

    1.5 ± 0.1

    1.4 ± 0.7

    4.0 ± 0.8

    4.7 ± 1.5

    Soft spinifex TOCNF

    1.5 ± 0.1

    1.5 ± 0.8

    4.2 ± 0.9

    6.2 ± 2.4

    Hard spinifex TOCNF

    1.8 ± 0.1

    1.6 ± 0.8

    4.4 ± 1.0

    6.6 ± 2.5

    Jute NOCNF

    3.0 ± 0.3

    3.2 ± 2.2

    5.6 ± 1.5

    7.1 ± 3.7

    Soft spinifex NOCNF

    3.9 ± 0.2

    3.9 ± 2.6

    5.2 ± 1.3

    6.5 ± 3.5

    Hard spinifex NOCNF

    4.6 ± 0.2

    4.7 ± 2.3

    5.6 ± 1.6

    7.0 ± 2.4

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