Cellulose nanocrystals (CNCs) have high aspect ratios, polydisperse size distributions, and a strong propensity for aggregation, all of which make them a challenging material for detailed size and morphology characterization. A CNC reference material produced by sulfuric acid hydrolysis of softwood pulp was characterized using a combination of dynamic light scattering (DLS), atomic force microscopy (AFM), transmission electron microscopy, and X-ray diffraction. As a starting point, a dispersion protocol using ultrasonication was developed to provide CNC suspensions with reproducible size distributions as assessed by DLS. Tests of various methods for AFM sample preparation demonstrated that spin coating on a positively charged substrate maximizes the number of individual particles for size analysis, while minimizing the presence of agglomerates. The effects of sample-to-sample variability, analyst bias, and sonication on size distributions were assessed by AFM. The latter experiment indicated that dispersion of agglomerates by sonication did not significantly change the size distribution of individual CNCs in suspension. Comparison with TEM data demonstrated that the two microscopy methods provide similar results for CNC length (mean ~ 80 nm); however, the particle width as measured by TEM is approximately twice that of the CNC height (mean 3.5 nm) measured by AFM. The individual crystallite size measured by X-ray diffraction is intermediate between the two values, although closer to the AFM height, possibly indicating that laterally agglomerated CNCs contribute to the TEM width. Overall, this study provides detailed information that can be used to assess the factors that must be considered in measuring CNC size distributions, information that will be useful for benchmarking the performance of different industrially sourced materials.
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Support for aspects of this work from NRCan’s Forest Innovation program is gratefully acknowledged. We thank Drs. Stephanie Beck and Jean Bouchard from FPInnovations, Montreal, for many useful discussions on CNC dispersion and characterization and CelluForce, Inc., Windsor, QC, for providing CNCs to produce the reference material. The content of this publication does not necessarily reflect the views or policies of the Department of Health and Human Services, nor does mention of trade names, commercial products, or organizations imply endorsement by the U.S. Government.
This study was partially funded by NRCan’s Forest Innovation Program (NRC contributors) and by National Institutes of Health (National Cancer Institute contributors, Contract No. HHSN261200800001E).
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The authors declare that they have no conflict of interest.
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Jakubek, Z.J., Chen, M., Couillard, M. et al. Characterization challenges for a cellulose nanocrystal reference material: dispersion and particle size distributions. J Nanopart Res 20, 98 (2018). https://doi.org/10.1007/s11051-018-4194-6
- Cellulose nanocrystals
- Particle size distribution
- Atomic force microscopy
- Transmission electron microscopy
- Dynamic light scattering