TY - JOUR
T1 - Soft cellulose II nanospheres
T2 - Sol-gel behaviour, swelling and material synthesis
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
N1 - Funding Information:
We would like to acknowledge the financial support in the framework of Austrian Biorefinery Center Tulln. The authors also thank H2020-ERC-2017-Advanced Grant “BioELCell” (788489) and COST Action FP1205 for funding support. HYBER Centre of Excellence (2014–2019) and the Aalto University Nanomicroscopy Center (Aalto-NMC) are acknowledged for the use of its facilities. We are grateful to Lenzing AG for supplying cellulose II gel samples.
Publisher Copyright:
© 2019 The Royal Society of Chemistry.
Copyright:
Copyright 2019 Elsevier B.V., All rights reserved.
PY - 2019/10/14
Y1 - 2019/10/14
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85072942958&partnerID=8YFLogxK
U2 - 10.1039/c9nr05309c
DO - 10.1039/c9nr05309c
M3 - Article
C2 - 31553034
AN - SCOPUS:85072942958
VL - 11
SP - 17773
EP - 17781
JO - Nanoscale
JF - Nanoscale
SN - 2040-3364
IS - 38
ER -