Soft cellulose II nanospheres: Sol-gel behaviour, swelling and material synthesis

Marco Beaumont (Corresponding Author), Sabine Rosenfeldt, Blaise L. Tardy, Claudia Gusenbauer, Alexey Khakalo, Nonappa, Martina Opietnik, Antje Potthast, Orlando J. Rojas, Thomas Rosenau (Corresponding Author)

    Research output: Contribution to journalArticleScientificpeer-review

    Abstract

    High axial aspect crystalline nanomaterials have emerged as polymeric building blocks for the construction of supermaterials. In contrast to this form, amorphous nanospheres have remained largely untapped. This is especially peculiar in the context of material assembly, due to the wide range of opportunities they offer by virtue of their soft particle characteristics, high volume ratio at low solid content and their highly swollen and accessible structure. In the context of cellulose, these colloids represent a new field in the family of nanocelluloses. We report an organic solvent-free, heterogeneous and simple synthesis of spherical carboxylated nanoparticles bearing a distinctive, amorphous outer shell structure. The particle shape is evaluated by atomic force microscopy, cryo-transmission electron microscopy, dynamic light scattering and small-angle X-ray scattering. The soft shell structure of the particles and their responsiveness to ionic strength and pH are quantified by the combination of quartz-crystal microgravimetry and atomic force microscopy. Aqueous dispersions of the nanocolloids feature distinctive sol/gel behaviour: At solid content <2 wt% they behave as a low viscous liquid (sol state), whereas at higher concentrations the shells dominate the interparticle interactions, causing an exponential increase in viscosity, typical of a gel state (hydrogel). Gelation is reversible and can be triggered alternatively by protonation of the carboxylate groups under acidic conditions. Supercritical drying of the hydrogels yields a highly porous, isotropic aerogel composed of aggregated nanoparticles. In contrast, ambient drying results in an anisotropic, fully transparent film. These colloids will allow the study of the interaction between soft cellulose and rigid matter, and have high potential as toughening additives in composites. Furthermore, the amorphous nature of this new class of cellulose nanocolloids makes them attractive as support materials for catalysts and enzymes.

    Original languageEnglish
    Pages (from-to)17773-17781
    Number of pages9
    JournalNanoscale
    Volume11
    Issue number38
    DOIs
    Publication statusPublished - 14 Oct 2019
    MoE publication typeA1 Journal article-refereed

    Fingerprint

    Nanospheres
    Cellulose
    Sol-gels
    Swelling
    Colloids
    Hydrogels
    Atomic force microscopy
    Drying
    Bearings (structural)
    Nanoparticles
    Quartz
    Aerogels
    Hydrogel
    Protonation
    Toughening
    Polymethyl Methacrylate
    Dynamic light scattering
    Gelation
    Sols
    Ionic strength

    Cite this

    Beaumont, M., Rosenfeldt, S., Tardy, B. L., Gusenbauer, C., Khakalo, A., Nonappa, ... Rosenau, T. (2019). Soft cellulose II nanospheres: Sol-gel behaviour, swelling and material synthesis. Nanoscale, 11(38), 17773-17781. https://doi.org/10.1039/c9nr05309c
    Beaumont, Marco ; Rosenfeldt, Sabine ; Tardy, Blaise L. ; Gusenbauer, Claudia ; Khakalo, Alexey ; Nonappa ; Opietnik, Martina ; Potthast, Antje ; Rojas, Orlando J. ; Rosenau, Thomas. / Soft cellulose II nanospheres : Sol-gel behaviour, swelling and material synthesis. In: Nanoscale. 2019 ; Vol. 11, No. 38. pp. 17773-17781.
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    abstract = "High axial aspect crystalline nanomaterials have emerged as polymeric building blocks for the construction of supermaterials. In contrast to this form, amorphous nanospheres have remained largely untapped. This is especially peculiar in the context of material assembly, due to the wide range of opportunities they offer by virtue of their soft particle characteristics, high volume ratio at low solid content and their highly swollen and accessible structure. In the context of cellulose, these colloids represent a new field in the family of nanocelluloses. We report an organic solvent-free, heterogeneous and simple synthesis of spherical carboxylated nanoparticles bearing a distinctive, amorphous outer shell structure. The particle shape is evaluated by atomic force microscopy, cryo-transmission electron microscopy, dynamic light scattering and small-angle X-ray scattering. The soft shell structure of the particles and their responsiveness to ionic strength and pH are quantified by the combination of quartz-crystal microgravimetry and atomic force microscopy. Aqueous dispersions of the nanocolloids feature distinctive sol/gel behaviour: At solid content <2 wt{\%} they behave as a low viscous liquid (sol state), whereas at higher concentrations the shells dominate the interparticle interactions, causing an exponential increase in viscosity, typical of a gel state (hydrogel). Gelation is reversible and can be triggered alternatively by protonation of the carboxylate groups under acidic conditions. Supercritical drying of the hydrogels yields a highly porous, isotropic aerogel composed of aggregated nanoparticles. In contrast, ambient drying results in an anisotropic, fully transparent film. These colloids will allow the study of the interaction between soft cellulose and rigid matter, and have high potential as toughening additives in composites. Furthermore, the amorphous nature of this new class of cellulose nanocolloids makes them attractive as support materials for catalysts and enzymes.",
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    Beaumont, M, Rosenfeldt, S, Tardy, BL, Gusenbauer, C, Khakalo, A, Nonappa, Opietnik, M, Potthast, A, Rojas, OJ & Rosenau, T 2019, 'Soft cellulose II nanospheres: Sol-gel behaviour, swelling and material synthesis', Nanoscale, vol. 11, no. 38, pp. 17773-17781. https://doi.org/10.1039/c9nr05309c

    Soft cellulose II nanospheres : Sol-gel behaviour, swelling and material synthesis. / Beaumont, Marco (Corresponding Author); Rosenfeldt, Sabine; Tardy, Blaise L.; Gusenbauer, Claudia; Khakalo, Alexey; Nonappa; Opietnik, Martina; Potthast, Antje; Rojas, Orlando J.; Rosenau, Thomas (Corresponding Author).

    In: Nanoscale, Vol. 11, No. 38, 14.10.2019, p. 17773-17781.

    Research output: Contribution to journalArticleScientificpeer-review

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    AU - Beaumont, Marco

    AU - Rosenfeldt, Sabine

    AU - Tardy, Blaise L.

    AU - Gusenbauer, Claudia

    AU - Khakalo, Alexey

    AU - Nonappa,

    AU - Opietnik, Martina

    AU - Potthast, Antje

    AU - Rojas, Orlando J.

    AU - Rosenau, Thomas

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    Beaumont M, Rosenfeldt S, Tardy BL, Gusenbauer C, Khakalo A, Nonappa et al. Soft cellulose II nanospheres: Sol-gel behaviour, swelling and material synthesis. Nanoscale. 2019 Oct 14;11(38):17773-17781. https://doi.org/10.1039/c9nr05309c