Polysaccharides are attractive sustainable resources for the fabrication of advanced materials, but the assembly of these building blocks into complex-shaped structures combining the high strength and low weight required in many applications remains challenging. We have investigated and optimized the rheological and mechanical properties of polysaccharide-based composite foams based on mixtures of methylcellulose (MC), cellulose nanofibrils (CNF), montmorillonite (MMT), and glyoxal and tannic acid. Such foams were found to be stabilized by the coadsorption of MC, CNF, and MMT at the air-water interface, while the complexation of the polysaccharides with tannic acid improved the foam stability. Tannic acid could also be used to tune and optimize the microstructure and the viscoelastic properties of the wet foam for direct ink writing of robust cellular architectures. Glyoxal had no noticeable effect on the properties of the wet foams but significantly enhanced the water resilience and stiffness of the lightweight material obtained after drying at ambient pressure and elevated temperatures with minimum shrinkage. The foams possessed a high porosity and displayed a specific Youngs modulus and yield strength that outperformed other biobased foams and commercially available expanded polystyrene. The strong and water-resilient 3D printed foams can be surface modified using, for example, aminosilanes, which opens up applications for air purification and thermal insulation.

Assembly of bio-based nano-sized particles into complex architectures and morphologies is an area of fundamental interest and technical importance. We have investigated the assembly of sulfonated cellulose nanocrystals (CNC) dispersed in a shrinking levitating aqueous drop using time-resolved small angle X-ray scattering (SAXS). Analysis of the scaling of the particle separation distance (d) with particle concentration (c) was used to follow the transition of CNC dispersions from an isotropic state at 1-2 vol% to a compressed nematic state at particle concentrations above 30 vol%. Comparison with SAXS measurements on CNC dispersions at near equilibrium conditions shows that evaporation-induced assembly of CNC in large levitating drops is comparable to bulk systems. Colloidal states with d vs. c scalings intermediate between isotropic dispersions and unidirectional compression of the nematic structure could be related to the biphasic region and gelation of CNC. Nanoscale structural information of CNC assembly up to very high particle concentrations can help to fabricate nanocellulose-based materials by evaporative methods.

Foams are applied in many areas including thermal insulation of buildings, flotation devices, packaging, filters for water purification, CO₂ sorbents and for biomedical devices. Today, the market is dominated by foams produced from synthetic, non-renewable polymers, which raises serious concerns for the sustainable and ecological development of our society. This thesis will demonstrate how lightweight foams based on nanocellulose can be processed and how the properties in both the wet and dry state can be optimized.

Lightweight and highly porous foams were successfully prepared using a commercially available surface-active polyoxamer, Pluronic P123^TM, cellulose nanofibers (CNFs), and soluble CaCO₃ nanoparticles. The stability of wet and dry composite foams was significantly improved by delayed aggregation of the CNF matrix by gluconic acid-triggered dissolution of the CaCO₃ nanoparticles, which generated a strong and dense CNF network in the foam walls. Drying the Ca²⁺-reinforced foam at 60 °C resulted in moderate shrinkage but the overall microstructure and pore/foam bubble size distribution were preserved after drying. The elastic modulus of Ca²⁺-reinforced composite foams with a density of 9 – 15 kg/m³ was significantly higher than fossil-based polyurethane foams.

Lightweight hybrid foams have been prepared from aqueous dispersions of a surface-active aminosilane (AS) and CNF for a pH range of 10.4 – 10.8. Evaporative drying at a mild temperature (60 °C) resulted in dry foams with low densities (25 – 50 kg/m³) and high porosities (96 – 99%). The evaporation of water catalyzed the condensation of the AS to form low-molecular linear polymers, which contributed to the increase in the stiffness and strength of the CNF-containing foam lamella.

Strong wet foams suitable for 3D printing were produced using methylcellulose (MC), CNFs and montmorillonite clay (MMT) as a filler and tannic acid and glyoxal as cross-linkers. The air-water interface of the foams was stabilized by the co-adsorption of MC, CNF and MMT. Complexation of the polysaccharides with tannic acid improved the foam stability and the viscoelastic properties of the wet foam for direct ink writing of robust cellular architectures. Glyoxal improved the water resistance and stiffened the lightweight material that had been dried at ambient pressure and elevated temperatures with minimum shrinkage. The highly porous foams displayed a specific Young’s modulus and yield strength that outperformed other bio-based foams and commercially available expanded polystyrene.

Unidirectional freezing, freeze-casting, of nanocellulose dispersions produced cellular foams with high alignment of the rod-like nanoparticles in the freezing direction. Quantification of the alignment with X-ray diffraction showed high orientation of CNF and short and stiff cellulose nanocrystals (CNC).

Organosilica foams are commonly formed by a multistep process involving hydrolysis and condensationof organosilanes followed by solvent exchange and e.g. supercritical CO2 drying. Here, we propose astraightforward route to synthesize lightweight hybrid foams from aqueous dispersions of a surfaceactiveaminosilane (AS) and TEMPO-oxidized cellulose nanofibrils (TCNFs). Air bubbles were introducedin the TCNF/AS dispersion by mechanical blending, and the foam was solidified by oven-drying.Evaporative drying at mild temperature (60 1C) resulted in dry foams with low densities (25–50 kg m3),high porosities (96–99%) and macropores of 150–300 mm in diameter. The foaming and foam stabilizationwere successful for a pH range of 10.4–10.8 for foams containing 55–65 wt% of organosilica inthe dry state. The protonation of AS increased the ionic strength of the dispersion and enhanced theinterparticle interactions with TCNFs and, in turn, the foam viscosity and foam stability upon drying. Theevaporation of water catalyzed the condensation of the AS to form low-molecular linear polymers,which resulted in an increased stiffness and strength of the foam lamella. The crosslinking of the ASpolymeric network with the TCNF matrix allowed lightweight and homogeneous macroporous foams tobe obtained with controlled densities and high amine content (amine content 44.5 mmol g1) using anenvironmentally friendly technique.

We have followed the structural evolution during evaporation-induced self-assembly of sulfonated cellulose nanocrystal (CNC) in the presence of H+ and Li+ counterions by small-angle X-ray scattering. Drying of CNC-H dispersions results in ordered films that could not be readily redispersed, while the CNC-Li films were disordered and prone to reswelling and redispersion. The scaling of the separation distance (d) between CNC particles and the particle concentration (c) shows that the CNC-H dispersions display a unidimensional contraction of the nematic structure (d alpha c(-1)) during drying, while the CNC-Li dispersions consolidate isotropically (d alpha c(-1/3)), which is characteristic for hydrogels with no preferential orientation. Temporal evolution of the structure factor and complementary dynamic light-scattering measurements show that CNC-Li is more aggregated than CNC-H during evaporation-induced assembly. Insights on the structural evolution during CNC assembly and redispersion can promote development of novel and optimized processing routes of nanocellulose-based materials.

Nanocellulose-based lightweight foams are promising alternatives to fossil-based insulation materials for energy-efficient buildings. The properties of cellulose-based materials are strongly influenced by moisture and there is a need to assess and better understand how the thermal conductivity of nanocellulose-based foams depends on the relative humidity and temperature. Here, we report a customized setup for measuring the thermal conductivity of hydrophilic materials under controlled temperature and relative humidity conditions. The thermal conductivity of isotropic foams based on cellulose nanofibrils and a nonionic polyoxamer, and an expanded polystyrene foam was measured over a wide range of temperatures and relative humidity. We show that a previously developed model is unable to capture the strong relative humidity dependence of the thermal conductivity of the hygroscopic, low-density nanocellulose- and nonionic polyoxamer-based foam. Analysis of the moisture uptake and moisture transport was used to develop an empirical model that takes into consideration the moisture content and the wet density of the investigated foam. The new empirical model could predict the thermal conductivity of a foam with a similar composition but almost 3 times higher density. Accurate measurements of the thermal conductivity at controlled temperature and relative humidity and availability of simple models to better predict the thermal conductivity of hygroscopic, low-density foams are necessary for the development of nanocellulose-based insulation materials.

We have investigated the steady-shear and viscoelastic properties of composite dispersions of cellulose nanofibrils (CNFs) with medium or high charge density and two different nanoclays, viz. rodlike sepiolite or plate-like bentonite. Aqueous dispersions of CNFs with medium charge density displayed significantly lower steady-state viscosity and storage modulus but higher gelation threshold compared with CNFs with high charge density. Dynamic light scattering (DLS) results showed that the apparent hydrodynamic radius of bentonite particles increased when CNFs were added, implying that CNFs adsorbed onto the amphoteric edges of the plate-like bentonite particles. The sepiolite network in CNF-sepiolite dispersions was relatively unaffected by addition of small amounts of CNFs, and DLS showed that the hydrodynamic radius of sepiolite did not change when CNFs were added. Addition of CNFs at concentrations above the gelation threshold resulted in drastic decrease of the steady-shear viscosity of the sepiolite dispersion, suggesting that the sepiolite network disintegrates and the rod-like clay particles are aligned also at low shear rate. The relative change in the rheological properties of the clay-based dispersions was always greater on addition of CNFs with high compared with medium charge density. This study provides insight into how the rheology of CNF-nanoclay dispersions depends on both the nanoclay morphology and the interactions between the nanoclay and nanocellulose particles, being of relevance to processing of nanocellulose-clay composites.

We show that unidirectional freezing of nanocellulose dispersions produces cellular foams with high alignment of the rod-like nanoparticles in the freezing direction. Quantification of the alignment in the long direction of the tubular pores with X-ray diffraction shows high orientation of cellulose nanofibrils (CNF) and cellulose nanocrystals (CNC) at particle concentrations above 0.2 wt % (CNC) and 0.08 wt % (CNF). Aggregation of CNF by pH decrease or addition of salt significantly reduces the particle orientation; in contrast, exceeding the concentration where particles gel by mobility constraints had a relatively small effect on the orientation. The dense nanocellulose network formed by directional freezing was sufficiently strong to resist melting. The formed hydrogels were birefringent and displayed anisotropic laser diffraction patterns, suggesting preserved nanocellulose alignment and cellular structure. Nondirectional freezing of the hydrogels followed by sublimation generates foams with a pore structure and nanocellulose alignment resembling the structure of the initial directional freezing.

Aggregation of dispersed rod-like particles like nanocellulose can improve the strength and rigidity of percolated networks but may also have a detrimental effect on the foamability. However, it should be possible to improve the strength of nanocellulose foams by multivalent ion-induced aggregation if the aggregation occurs after the foam has been formed. Lightweight and highly porous foams based on TEMPO-mediated oxidized cellulose nanofibrils (CNF) were formulated with the addition of a nonionic surfactant, pluronic P123, and CaCO3 nanoparticles. Foam volume measurements show that addition of the non-ionic surfactant generates wet CNF/P123 foams with a high foamability. Foam bubble size studies show that delayed Ca-induced aggregation of CNF by gluconic acid-triggered dissolution of the CaCO3 nanoparticles significantly improves the long-term stability of the wet composite foams. Drying the Ca-reinforced foam at 60 degrees C results in a moderate shrinkage and electron microscopy and X-ray tomography studies show that the pores became slightly oblate after drying but the overall microstructure and pore/foam bubble size distribution is preserved after drying. The elastic modulus (0.9-1.4 MPa) of Ca-reinforced composite foams with a density of 9-15 kg/m(3) is significantly higher than commercially available polyurethane foams used for thermal insulation.

The packing of cellulose nanocrystals (CNC) in the anisotropic chiral nematic phase has been investigated over a wide concentration range by small-angle X-ray scattering (SAXS) and laser diffraction. The average separation distance between the CNCs and the average pitch of the chiral nematic phase have been determined over the entire isotropic-anisotropic biphasic region. The average separation distances range from 51 nm, at the onset of the anisotropic phase formation, to 25 nm above 6 vol % (fully liquid crystalline phase) whereas the average pitch varies from approximate to 15 mu m down to approximate to 2 mu m as phi increases from 2.5 up to 6.5 vol %. Using the cholesteric order, we determine that the twist angle between neighboring CNCs increases from about 1 degrees up to 4 degrees as phi increases from 2.5 up to 6.5 vol %. The dependence of the twisting on the volume fraction was related to the increase in the magnitude of the repulsive interactions between the charged rods as the average separation distance decreases.