Soft actuators aim to bridge the gap between rigid machines and soft matter by mimicking the flexibility and compliance of natural muscles and tissues. Stimuli-responsive hydrogels can fit this purpose through their softness and ability for large reversible shape morphing. However, the performance of hydrogel actuators is restricted by their diffusion-limited water transport, which leads to slow responses, and uniform volumetric changes that generate limited actuation forces and strains. Thus, there is a need to develop faster hydrogel actuators that can efficiently convert swelling into actuation force and strain. Anisotropic cellulose nanofibril (CNF) hydrogels offer a route to overcome these limitations by assembling charged fibrils into dense, layered sheets that are reinforced in-plane while remaining compliant in the thickness direction. This architecture redirects water uptake into uniaxial expansion or, under confinement, into high blocking pressure, thereby combining large strain, high force, and rapid response. Here, we establish how the structure and processing of charged CNF networks govern swelling-driven actuation. Specifically, we examine how fibril properties, including aspect ratio and charge density, together with sheet fabrication parameters, including drying conditions and actuator area, control the translation of water uptake into directional strain and force. Optimization of these parameters results in CNF networks that expand uniaxially by 220 times within an hour with initial strain rates of 190–300% s−1, reaching blocking pressures up to 4.9 MPa in less than a minute. These hydrogels are a great step towards hydrogel-based artificial muscles, which have been prevented by the slow response of previously reported stimuli-responsive hydrogels. Further development of fibrillar hydrogel actuators can lead to truly lifelike artificial muscles.

Superabsorbent polymers (SAPs) are essential components in absorption products for food packaging, agriculture, wound dressings, and hygiene. Modern absorption products are designed to rapidly absorb and transport liquids to SAPs, which drains the porous networks and hold liquids under pressure as hydrogels. However, the carbon footprint of these massively used, fossil-based products is high, leading to an urgent need to develop biobased superabsorbents. Although commercial SAPs have an absorption capacity under load that is challenging to surmount, their powder form complicates processing. Thus, biobased alternatives can compete with other advantages, such as intelligently designed self-supporting structures preferably manufactured in sustainable roll-to-roll processes. As a pioneering step, this study presents all-cellulose superabsorbent heterostructures prepared by combining macroporous fiber-based aerogels with highly swelling cellulose nanofibril (CNF) sheets. The aerogel rapidly absorbs 30 g g-1 of liquid, which is rapidly transferred to the CNF sheets with a maximum capacity of 246 g g-1, holding liquids at pressures of up to 0.9 MPa. The heterostructure is also equipped with a simple, sustainable conductometric water-uptake sensor to follow the liquid uptake and saturation level. Using unmodified raw materials from the forest industry in a scalable process with the potential for roll-to-roll manufacturing makes these all-cellulose heterostructures a competitive alternative to commercial SAPs in a carbon-neutral society.

Due to their excellent wetting and liquid-spreading properties, cellulose-based aerogels have shown great potential as absorbent materials in many applications. However, there is still a very limited understanding of how the aerogels should be tailored to optimize liquid spreading and liquid storage properties. The present work focuses on characterizing liquid spreading at short contact times and tailoring the surfaces within the aerogel to increase the spreading properties. Aerogels from periodate oxidized cellulose nano fibrils (CNFs) were freeze-linked to attain wet stability. Subsequently, they were modified with the layer-by-layer (LbL) assembly method using poly(diallyldimethylammonium chloride) (PDADMAC) and well-defined SiO2 nanoparticles to change their surface properties. The morphology of the untreated and treated aerogels, as determined from SEM images, indicates a complete surface coverage of PDADMAC/SiO2 bilayers on the inner surfaces of CNF aerogels, showing that the LbL-treatment can be used to tailor the aerogel, i.e. to increase the specific surface area of the aerogel, by changing the number of bilayers. It has also been shown that the horizontal liquid spreading rate increases significantly after surface modification. In addition, a theoretical analysis of the spreading results indicates that this is due to the increase in the specific surface area of the surface-modified aerogels. Moreover, the spreading rate can be gradually tailored by changing the number of bilayers and the dimensions of the nanoparticles. Furthermore, we provide a new method to calculate the specific surface area of aerogel materials by combining the experimentally determined liquid spreading rate and a version of the well-known Kozeny–Carman equation.

Nanocellulose has emerged as a widely utilized building block in nanostructured materials due to its availability, sustainability, large surface area, and high stiffness and aspect ratio. The wet or dry elastoplastic properties of these materials are determined by the fibrils' stiffness, chemical properties, hemicellulose content, and the number of fibril contacts. However, the specific contributions and relative importance of each factor remain unclear. Therefore, this work was devoted to systematically comparing the material properties of gels, aerogels, and wet and dry sheets prepared from CNFs with different aspect ratios, chemical functionality, and hemicellulose content. The fibrils were prepared by chemical and mechanical processing of different pulps. By preserving the native structure as much as possible, higher aspect ratio fibrils can be obtained, which allows for the development of more mechanically robust materials. The results demonstrate that higher aspect ratios lead to more interconnected networks at a lower solids concentration, resulting in a more evenly distributed stress and longer-range stress transfer, yielding stiffer and more ductile materials. The most important finding was that the aspect ratio influences the network formation, resulting in different network topologies. The results were also compared to earlier published data and integrated into a theoretical beam-bending model for a complete elastoplastic description of the network properties, including the influence of fibril aspect ratio and chemical functionality. This information improves our understanding and description of nanofibril networks for which general models have been missing. It can be used to optimize nanofibril preparation and, hence, the resulting eco-friendly materials.

Highly anisotropic cellulose nanofibrils can solidify liquid water, creating self-supporting structures by incorporating a tiny number of fibrils. These fibrillar hydrogels can contain as much as 99.99 wt% water. The structure and mechanical properties of fibrillar networks have so far not been completely understood, nor how they solidify the bulk water at such low particle concentrations. In this work, the mechanical properties of cellulose fibrillar hydrogels in the dilute regime from a wt% perspective have been studied, and an elastoplastic model describing the network structure and its mechanics is presented. A significant insight from this work is that the ability of the fibrils to solidify water is very dependent on particle stiffness and the number of contact points it can form in the network structure. The comparison between the experimental results and the theoretical model shows that the fibrillar networks in the dilute regime form via a non-stochastic process since the fibrils have the time and freedom to find contact points during network formation by translational and rotational diffusion. The formed, dilute fibrillar network deforms by sliding fibril contacts upon straining the network beyond its elastic limit. Our results also show that before macroscopic failure, the fibril contacts are restored once the load is released. The exceptional properties of this solidified water are exploited to host fluidic channels, allowing directed fluid transportation in water. Finally, the microfluidic channels formed in the hydrogels are tailored by the layer-by-layer technique to be interactive against external stimuli, a characteristic envisioned to be useful in biomedical applications.

Long, slender cellulose nanofibrils (CNF) are unique with their high axial modulus, small diameter, high flexibility, and the possibility of chemical tailoring of, among other things, their surface charge density. The objective of this work has been to elucidate how the hydrogel network properties and how their related deformation mechanisms depend on CNF properties, concentration, and chemical environment. In addition, the influence of CNF characteristics on the formation of the structure and properties of isotropic hydrogels, anisotropic hydrogels, and aerogels has been studied. 

This was done by combining theoretical models describing the CNF network's topology and mechanics with high-resolution experiments to validate the theoretical models. Furthermore, the properties of the fibrils have been characterized in detail and linked to the material properties of materials formed from the fibrils. Finally, the CNF networks in this work have been functionalized in two different ways. In the first case, a flow channel was created within the hydrogel network at extremely low CNF concentrations, that could be surface treated with a Layer-by-layer (LbL) methodology with a consecutive addition of oppositely charged polyelectrolytes/nanoparticles to add new functionalities to the channels. Secondly, wet stable aerogels, prepared at higher concentrations of CNFs, were treated using the LbL methodology to adjust the aerogels' surface structure and surface energy, thereby controlling the liquid spreading rate properties of the formed networks.

The most important findings in this work are that CNF network topology and network mechanics can be described using theoretical, rather non-complicated, elastoplastic models. Furthermore, at lower concentrations of CNFs, the network structure is formed in a more organized way, meaning that the fibrils have the time and freedom to seek their optimal contact points during the network formation from a thermodynamic free energy point of view. It has also been shown that the low-density, wet fibrillar network structures formed by neutralizing the charges of the fibrils deform by sliding in fibril/fibril contacts upon straining the network structure above a critical stress. These fibril/fibril contacts are also shown to be re-established when the stress is released, provided that the networks have not been subjected to a macroscopic collapse. Finally, these cellulose networks show great potential for further functionalization using the LbL modification methodology.

Långa, smala cellulosananofibriller (CNF) är unika med sin höga axiella E-modul, låga diameter, höga flexibilitet och stora möjlighet till kemisk modifiering som bland annat använts för att styra fibrillernas ytladdningstäthet. Syftet med detta arbete har varit att klarlägga hur egenskaperna hos hydrogeler, framställda av nanofibriller, och dess deformationsmekanismer, kan kopplas till olika grundläggande CNF-egenskaper, koncentration och kemisk miljö. Dessutom har vi studerat inverkan av hur CNF-egenskaperna påverkar den bildade nätverksstrukturen och hur de påverkar de slutliga egenskaperna hos isotropa- och anisotropa hydrogeler och aerogeler som formats ifrån de olika fibrillslagen. 

Den strategi som användes, och visade sig mycket framgångsrik, för att nå dessa mål, var att kombinera teoretiska modeller som beskriver CNF-nätverkets topologi och mekanik med specialdesignade experiment för att validera de teoretiska modellerna. Vidare har ett omfattande arbete lagts ned på att karakterisera fibrillernas kemiska, strukturella och morfologiska egenskaper och att koppla dessa till de funktionella materialegenskaperna hos de material som har tillverkats ifrån dessa fibriller. Slutligen har de färdiga CNF-nätverken funktionaliserats på två olika sätt. I det första fallet skapades en stabil flödeskanal i ett hydrogelnätverk, som preparerats vid extremt låg CNF-koncentration, och det visade sig vara möjligt att ytbehandla denna kanal med en lager för lager (LbL) metod där motladdade polyelektrolyter och/eller nanopartiklar användes för att tillföra nya egenskaper till kanalen. I det andra fallet behandlades förtillverkade, våtstabila aerogeler, som preparerats vid högre koncentration av CNF, med en LbL-behandling för att kontrollera ytstruktur och ytkemi hos aerogelerna, och att därigenom kontrollera vätskespridningshastigheten hos nätverken.

De viktigaste resultaten i detta arbete är att CNF-nätverkets topologi och nätverksmekanik kan beskrivas med hjälp av relativt okomplicerade teoretiska elastoplastiska modeller. Vidare, har det varit möjligt att visa att vid lägre CNF koncentrationer så bildas nätverksstrukturen på ett mer organiserat sätt, vilket innebär att fibrillerna har tid och friheten att söka sina kontaktpunkter under nätverksbildningen för att nå en optimal struktur utifrån ett termodynamiskt fritt energiperspektiv. Det har också visats att den våta fibrillära nätverksstrukturen hos hydrogelerna deformeras genom att fibrillkontakterna börjar glida vid en pålagd spänning på nätverksstrukturen som överskrider en viss gränsnivå och att fibrillkontakterna återbildas när den pålagda spänningen tas bort. Detta förutsatt att nätverken inte utsatts för en makroskopisk kollaps. Slutligen har vi lyckats visa hur det är möjligt att funktionalisera både hydrogeler och arogeler med hjälp av den så kallade LbL metoden för att skapa nya egenskaper hos nätverken.

Tunable dynamic networks of cellulose nanofibrils (CNFs) are utilized to prepare high-performance polymer gel electrolytes. By swelling an anisotropically dewatered, but never dried, CNF gel in acidic salt solutions, a highly sparse network is constructed with a fraction of CNFs as low as 0.9%, taking advantage of the very high aspect ratio and the ultra-thin thickness of the CNFs (micrometers long and 2–4 nm thick). These CNF networks expose high interfacial areas and can accommodate massive amounts of the ionic conductive liquid polyethylene glycol-based electrolyte into strong homogeneous gel electrolytes. In addition to the reinforced mechanical properties, the presence of the CNFs simultaneously enhances the ionic conductivity due to their excellent strong water-binding capacity according to computational simulations. This strategy renders the electrolyte a room-temperature ionic conductivity of 0.61 ± 0.12 mS cm−1 which is one of the highest among polymer gel electrolytes. The electrolyte shows superior performances as a separator for lithium iron phosphate half-cells in high specific capacity (161 mAh g−1 at 0.1C), excellent rate capability (5C), and cycling stability (94% capacity retention after 300 cycles at 1C) at 60 °C, as well as stable room temperature cycling performance and considerably improved safety compared with commercial liquid electrolyte systems.

Fibrillar hydrogels are remarkably stiff, low-density networks that can hold vast amounts of water. These hydrogels can easily be made anisotropic by orienting the fibrils using different methods. Unlike the detailed and established descriptions of polymer gels, there is no coherent theoretical framework describing the elastoplastic behavior of fibrillar gels, especially concerning anisotropy. In this work, the swelling pressures of anisotropic fibrillar hydrogels made from cellulose nanofibrils were measured in the direction perpendicular to the fibril alignment. This experimental data was used to develop a model comprising three mechanical elements representing the network and the osmotic pressure due to non-ionic and ionic surface groups on the fibrils. At low solidity, the stiffness of the hydrogels was dominated by the ionic swelling pressure governed by the osmotic ingress of water. Fibrils with different functionality show the influence of aspect ratio, chemical functionality, and the remaining amount of hemicelluloses. This general model describes physically crosslinked hydrogels comprising fibrils with high flexural rigidity - that is, with a persistence length larger than the mesh size. The experimental technique is a framework to study and understand the importance of fibrillar networks for the evolution of multicellular organisms, like plants, and the influence of different components in plant cell walls.