Characterization challenges for a cellulose nanocrystal reference material: dispersion and particle size distributions

  • Zygmunt J. Jakubek
  • Maohui Chen
  • Martin Couillard
  • Tianyang Leng
  • Leslie Liu
  • Shan Zou
  • Ulrich Baxa
  • Jeffrey D. Clogston
  • Wadood Y. Hamad
  • Linda J. Johnston
Research Paper
  • 130 Downloads

Abstract

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.

Keywords

Cellulose nanocrystals Dispersion Particle size distribution Atomic force microscopy Transmission electron microscopy Dynamic light scattering Biopolymer 

Notes

Acknowledgements

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.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

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References

  1. Babick F, Mielke J, Wohlleben W, Weigel S, Hodoroaba V-D (2016) How reliably can a material be classified as a nanomaterial? Available particle sizing techniques at work. J Nanopart Res 18:158CrossRefGoogle Scholar
  2. Beck S, Bouchard J, Berry R (2011) Controlling the reflection wavelength of iridescent solid films of nanocrystalline cellulose. Biomacromolecules 12:167–172CrossRefGoogle Scholar
  3. Beck S, Bouchard J, Berry R (2012) Dispersibility in water of dried nanocrystalline cellulose. Biomacromolecules 13:1486–1494CrossRefGoogle Scholar
  4. Bonevich JE, Haller WK (2010) Measuring the size of nanoparticles using transmission electron microscopy. NIST-NCL Joint Assay Protocol, PCC-7, Washington, DCGoogle Scholar
  5. Brinkmann A, Chen M, Couillard M, Jakubek ZJ, Leng T, Johnston LJ (2016) Correlating cellulose nanocrystal particle size and surface area. Langmuir 32:6105–6114CrossRefGoogle Scholar
  6. Cherhal F, Cousin F, Capron I (2015) Influence of charge density and ionic strength on the aggregation process of cellulose nanocrystals in aqueous suspension, as revealed by small-angle neutron scattering. Langmuir 31:5596–5602CrossRefGoogle Scholar
  7. Davis CS, Moon RJ, Ireland S, Foster EJ, Johnston LJ, Shatkin JA, Nelson K, Forster AM, Postek MT, Vladar AE, Gilman JW (2015) NIST-TAPPI workshop on measurement needs for cellulose nanomaterials. NIST Special Publication #1192. doi:  https://doi.org/10.6028/NIST.SP.1192
  8. De Temmerman P-J, Lammertyn J, De Ketelare B, Kestens V, Roebben G, Verleysen E, Mast J (2014) Measurement uncertainties of size, shape, and surface measurements using transmission electron microscopy of near-monodisperse, near-spherical nanoparticles. J Nanopart Res 16:2177CrossRefGoogle Scholar
  9. Delvallee A, Feltin N, Ducourtieux S, Trabelsi M, Hochepied JF (2016) Toward an uncertainty budget for measuring nanoparticles by AFM. Metrologia 53:41–50CrossRefGoogle Scholar
  10. Dufresne A (2013) Nanocellulose: a new ageless bionanomaterial. Mater Today 16:220–227CrossRefGoogle Scholar
  11. Eichhorn S (2011) Cellulose nanowhiskers: promising materials for advanced applications. Soft Matter 7:303–315CrossRefGoogle Scholar
  12. Elazzouzi-Hafraoui S, Nishiyama Y, Putaux J-L, Heux L, Dubreuilf F, Rochas C (2008) The shape and size distribution of crystalline nanoparticles prepared by acid hydrolysis of native cellulose. Biomacromolecules 9:57–65CrossRefGoogle Scholar
  13. Grulke EA, Yamamoto K, Kumagi K, Hausler I, Osterle W, Ortel E, Hodoroaba V-D, Brown SC, Chan C, Zheng J, Yamamoto K, Yashiki K, Song NW, Kim YH, Stefaniak AB, Schwegler-Berry D, Coleman VA, Jamting AK, Hermann J, Arakawa T, Burchett WW, Lambert JW, Stromberg AJ (2017) Size and shape distributions of primary crystallites in titania aggregates. Adv Powder Technol 28:1647–1659CrossRefGoogle Scholar
  14. Guan X, Cueto R, Russo P, Qi Y, Wu Q (2012) Asymmetric flow field-flow fractionation with multiangle light scattering detection for characterization of cellulose nanocrystals. Biomacromolecules 13:2671–2679CrossRefGoogle Scholar
  15. Hamad WY, Hu TQ (2010) Structure-property-yield inter-relationships in nanocrystalline cellulose extraction. Can J Chem Eng 88:392–402Google Scholar
  16. Hoo CM, Doan T, Starostin N, West PE (2010) Optimal sample preparation for nanoparticle metrology (statistical size measurements) using atomic force microscopy. J Nanopart Res 12:939–949CrossRefGoogle Scholar
  17. Hu Y, Abidi N (2016) Distinct nematic self-assembling behavior caused by different size-unified cellulose nanocrystals via a multistage separation. Langmuir 32:9863–9872CrossRefGoogle Scholar
  18. ISO (19716:2016) Characterization of cellulose nanocrystalsGoogle Scholar
  19. Jiang F, Esker AR, Roman M (2010) Acid-catalyzed and solvolytic desulfation of H2SO4-hydrolyzed cellulose nanocrystals. Langmuir 26:17919–17925CrossRefGoogle Scholar
  20. Kaushik M, Chen WC, van de Ven TGM, Moore A (2014) An improved methodology for imaging cellulose nanocrystals by transmission electron microscopy. Nord Pulp Pap Res J 29:77–84CrossRefGoogle Scholar
  21. Klemm D, Kramer F, Moritz S, Lindstrom T, Ankerfors M, Gray D, Dorris A (2011) Nanocelluloses: a new family of nature-based materials. Angew Chem Int Ed Engl 50:5438–5466CrossRefGoogle Scholar
  22. Kovacs T, Naishi V, O’Connor B, Blaise C, Gagnez F, Hall L, Trudeau V, Martel P (2010) An ecotoxicological characterization of nanocrystalline cellulose (NCC). Nanotoxicology 4:255–270CrossRefGoogle Scholar
  23. Meli F, Klein T, Buhr E, Frase CG, Gleber G, Krumrey M, Duta A, Duta S, Korpelainen V, Bellotti R, Picotto GB, Boyd RD, Cuenat A (2012) Traceable size determination of nanoparticles, a comparison among European Metrology Institutes. Meas Sci Technol 23:125005CrossRefGoogle Scholar
  24. Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40:3941–3994CrossRefGoogle Scholar
  25. Mukerjee A, Hackley VA (2017) Separation and characterization of cellulose nanocrystals by multi-detector asymmetric flow field-flow fractionation. Analyst 143:731–740CrossRefGoogle Scholar
  26. Postek MT, Vladar A, Dagata J, Farkas N, Ming B, Wagner R, Raman A, Moon RJ, Sabo R, Wegner TH, Beecher J (2011) Development of the metrology and imaging of cellulose nanocrystals. Meas Sci Technol 22:024005CrossRefGoogle Scholar
  27. Reid MS, Villalobos M, Cranston ED (2017) Benchmarking cellulose nanocrystals: from the laboratory to industrial production. Langmuir 33:1583–1598CrossRefGoogle Scholar
  28. Rice SB, Chan C, Brown SC, Eschbach P, Han L, Esnor DS, Stefaniak AB, Bonevich J, Vladar AE, Hight Walker AR, Zheng J, Starnes C, Stromberg A, Ye J, Grulke EA (2013) Particle size distributions by transmission electron microscopy: an interlaboratory comparison case study. Metrologia 50:663–678CrossRefGoogle Scholar
  29. Shafiei-Sabet S, Hamad WY, Hatzikiriakos SG (2012) Rheology of nanocrystalline cellulose aqueous suspensions. Langmuir 28:17124–17133CrossRefGoogle Scholar
  30. Shatkin JA, Kim B (2015) Cellulose nanomaterials: life cycle risk assessment and environmental health and safety roadmap. Environ Sci Nano 2:477–499CrossRefGoogle Scholar
  31. Shatkin JA, Wegner TH, Bilek EM, Cowie J (2014) Market projections of cellulose nanomaterial-enabled products—part 1: applications. TAPPI J 13:9–16Google Scholar
  32. Taurozzi JS, Hackley VA, Wiesner MR (2011) Ultrasonic dispersion of nanoparticles for environmental, health and safety assessment—issues and recommendations. Nanotoxicology 5:711–729CrossRefGoogle Scholar
  33. Trache D, Hussin MH, Haafiz MKM, Thakur VK (2017) Recent progress in cellulose nanocrystals: sources and production. Nanoscale 9:1763–1786CrossRefGoogle Scholar
  34. Uhlig M, Fall A, Wellert S, Lehmann M, Prévost S, Wågberg L, von Klitzing R, Nyström G (2016) Two-dimensional aggregation and semidilute ordering in cellulose nanocrystals. Langmuir 32:442–450CrossRefGoogle Scholar

Copyright information

© Crown 2018

Authors and Affiliations

  • Zygmunt J. Jakubek
    • 1
  • Maohui Chen
    • 1
  • Martin Couillard
    • 2
  • Tianyang Leng
    • 1
  • Leslie Liu
    • 1
  • Shan Zou
    • 1
  • Ulrich Baxa
    • 3
  • Jeffrey D. Clogston
    • 4
  • Wadood Y. Hamad
    • 5
  • Linda J. Johnston
    • 1
  1. 1.Measurement Science and StandardsNational Research Council CanadaOttawaCanada
  2. 2.Energy, Mining and EnvironmentNational Research Council CanadaOttawaCanada
  3. 3.Electron Microscopy LaboratoryFrederick National Laboratory for Cancer ResearchFrederickUSA
  4. 4.Nanotechnology Characterization LaboratoryFrederick National Laboratory for Cancer ResearchFrederickUSA
  5. 5.FPInnovationsVancouverCanada

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