In this work, we present an alternative approach to cellulose nanofibril film (CNF) production, taking inspiration from the wet spinning of fibers to wet spin films. During the spinning process, a CNF suspension is injected into a coagulation bath, where the partially aligned CNF network is locked. The CNF alignment of the dry films is then detected by wide angle X-ray scattering (WAXS). The comparison between the ultimate strengths and strengths at breaks of the films produced with different process parameters, including the suspension injection rate, bath pH, and bath flow rate, indicated no significant change in mechanical properties, suggesting a reliable and constant outcome for large-scale film fabrication. Furthermore, the produced films demonstrated high total light transmittance of 93 % at the wavelength of 550 nm, making them suitable for optoelectronic applications. Polarized optical microscopy revealed that even a low degree of CNF alignment can lead to anisotropic optical properties. Moreover, an anisotropic response to humidity was observed, in which the films preferentially bend in the perpendicular direction of the CNF orientation, thus opening a way for humidity-driven actuators.

This study aimed to develop eco-friendly multifunctional nanocellulose (NC) hybrid films with tailored properties for versatile applications including packaging and photovoltaics. Hybrid films composed by cellulose nanocrystals (CNC) and carboxymethylated cellulose nanofibrils (CNF) were produced at various mass ratio (CNC - 100:0 to 0:100). Montmorillonite clay (MTM) was incorporated (50 % by mass) into the CNC:CNF films. CNC-only films easily dispersed in water, but by adding CNF or MTM, the structural integrity was enhanced. Films with ≥50 % CNF and MTM had a strength reduction of 9-35 % and increased brittleness. The hybrid films presented transmittance above 60 % and haze varying from 5 % to 60 % at 550 nm which can be a beneficial for light management. All films kept color stability over 1000 h of artificial sunlight, a critical packaging feature for long-term storage. CNC: CNF films without MTM showed better potential for optoelectronic applications due to higher transmittance and smoother surfaces, while those with MTM presented UV protection (up to 250 nm) and swelling resistance (28-53 %) which could also benefit optoelectronics increasing their lifespan. Balancing the hybrid films composition is key for optoelectronics, while packaging applications tolerate broader compositions. These findings demonstrate the versatility of NC hybrid films in creating sustainable materials for diverse applications.

This work aims to understand how nanocellulose (NC) processing can modify the key characteristics of NC films to align with the main requirements for high-performance optoelectronics. The performance of these devices relies heavily on the light transmittance of the substrate, which serves as a mechanical support and optimizes light interactions with the photoactive component. Critical variables that determine the optical and mechanical properties of the films include the morphology of cellulose nanofibrils (CNF), as well as the concentration and turbidity of the respective aqueous suspensions. This study demonstrates that achieving high transparency was possible by reducing the grammage and adjusting the drying temperature through hot pressing. Furthermore, the use of modified CNF, specifically carboxylated CNF, resulted in more transparent films due to a higher nanosized fraction and lower turbidity. The mechanical properties of the films depended on their structure, homogeneity (spatial uniformity of local grammage), and electrokinetic factors, such as the presence of electrostatic charges on CNF. Additionally, we investigated the angle-dependent transmittance of the CNF films, since solar devices usually operate under indirect light. This work demonstrates the importance of a systematic approach to the optimization of cellulose films, providing valuable insight into the optoelectronic field. 

Novel printed electronics are projected to grow and be manufactured in the future in large volumes. In many applications, printed electronics are envisaged as sustainable alternatives to conventional (PCB-based) electronics. One such application is in the semi-quantitative drug detection and point-of-care device called ‘GREENSENSE’ that uses paper-based printed electronics. This paper analyses the carbon footprint of GREENSENSE in order to identify and suggest means of mitigating disproportionately high environmental impacts, labeled ‘sustainability hotspots’, from materials and processes used during production which would be relevant in high-volume applications. Firstly, a life cycle model traces the flow of raw materials (such as paper, CNCs, and nanosilver) through the three ‘umbrella’ processes (circuit printing, component mounting, and biofunctionalization) manufacturing different electronic components (the substrate, conductive inks, energy sources, display, etc) that are further assembled into GREENSENSE. Based on the life cycle model, life cycle inventories are modeled that map out the network of material and energy flow throughout the production of GREENSENSE. Finally, from the environmental impact and sustainability hotspot analysis, both crystalline nanocellulose and nanosilver were found to create material hotspots and they should be replaced in favor of lower-impact materials. Process hotspots are created by manual, lab-, and pilot-scale processes with unoptimized material consumption, energy use, and waste generation; automated and industrial-scale manufacturing can mitigate such process hotspots. © 2023 The Author(s).

Nanoscale infrared (IR) spectroscopy and microscopy, enabling the acquisition of IR spectra and images with a lateral resolution of 20 nm, is employed to chemically characterize individual cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) to elucidate if the CNCs and CNFs consist of alternating crystalline and amorphous domains along the CNF/CNC. The high lateral resolution enables studies of the nanoscale morphology at different domains of the CNFs/CNCs: flat segments, kinks, twisted areas, and end points. The types of nanocellulose investigated are CNFs from tunicate, CNCs from cotton, and anionic and cationic wood-derived CNFs. All nano-FTIR spectra acquired from the different samples and different domains of the individual nanocellulose particles resemble a spectrum of crystalline cellulose, suggesting that the non-crystalline cellulose signal observed in macroscopic measurements of nanocellulose most likely originate from cellulose chains present at the surface of the nanocellulose particles. 

From a circular economy perspective, one-pot strategies for the isolation of cellulose nanomaterials at a high yield and with multifunctional properties are attractive. Here, the effects of lignin content (bleached vs unbleached softwood kraft pulp) and sulfuric acid concentration on the properties of crystalline lignocellulose isolates and their films are explored. Hydrolysis at 58 wt % sulfuric acid resulted in both cellulose nanocrystals (CNCs) and microcrystalline cellulose at a relatively high yield (>55%), whereas hydrolysis at 64 wt % gave CNCs at a lower yield (<20%). CNCs from 58 wt % hydrolysis were more polydisperse and had a higher average aspect ratio (1.5-2×), a lower surface charge (2×), and a higher shear viscosity (100-1000×). Hydrolysis of unbleached pulp additionally yielded spherical nanoparticles (NPs) that were <50 nm in diameter and identified as lignin by nanoscale Fourier transform infrared spectroscopy and IR imaging. Chiral nematic self-organization was observed in films from CNCs isolated at 64 wt % but not from the more heterogeneous CNC qualities produced at 58 wt %. All films degraded to some extent under simulated sunlight trials, but these effects were less pronounced in lignin-NP-containing films, suggesting a protective feature, but the hemicellulose content and CNC crystallinity may be implicated as well. Finally, heterogeneous CNC compositions obtained at a high yield and with improved resource efficiency are suggested for specific nanocellulose uses, for instance, as thickeners or reinforcing fillers, representing a step toward the development of application-tailored CNC grades. © 2023 The Authors. 

We examine the influence of surface charge on the percolation, gel-point and phase behavior of cellulose nanocrystal (CNC) suspensions in relation to their nonlinear rheological material response. Desulfation decreases CNC surface charge density which leads to an increase in attractive forces between CNCs. Therefore, by considering sulfated and desulfated CNC suspensions, we are comparing CNC systems that differ in their percolation and gel-point concentrations relative to their phase transition concentrations. The results show that independently of whether the gel-point (linear viscoelasticity, LVE) occurs at the biphasic - liquid crystalline transition (sulfated CNC) or at the isotropic - quasi-biphasic transition (desulfated CNC), the nonlinear behavior appears to mark the existence of a weakly percolated network at lower concentrations. Above this percolation threshold, nonlinear material parameters are sensitive to the phase and gelation behavior as determined in static (phase) and LVE conditions (gel-point). However, the change in material response in nonlinear conditions can occur at higher concentrations than identified through polarized optical microscopy, suggesting that the nonlinear deformations could distort the suspensions microstructure such that for example a liquid crystalline phase (static) suspension could show microstructural dynamics similar to a biphasic system.

Measuring the size of cellulose nanomaterials can be challenging, especially in the case of branched and entangled cellulose nanofibrils (CNFs). The International Organization for Standardization, Technical Committee 6, Task Group 1—Cellulosic Nanomaterials, is exploring opportunities to develop standard methods for the measurement of CNF particle size and particle size distribution. This paper presents a summary of the available measuring techniques, responses from a survey on the measurement needs of CNF companies and researchers, and outcomes from an international workshop on cellulose nanofibril measurement and standardization. Standardization needs differed among groups, with Japanese companies mostly requiring measurements for product specification and production control, and other companies mostly needing measurements for safety/regula-tory purposes and for grade definitions in patents. Among all the companies, average length and width with percen-tiles (D(10), D(50), D(90)) were the most desired measurands. Workshop participants concurred that defining the location(s) on the CNF at which to measure the width and the length is an urgent and complex question. They also agreed that methods are needed for rapid particle size measurement at the nanoscale. Our recommendation within ISO is to start work to revise the definition of CNFs and develop sample preparation and measurement guidelines. It was also recommended that further research be done to reproducibly prepare hierarchical branched CNF structures and characterize them, develop automated image analysis for hierarchical branched CNF structures, and develop a classification system encompassing measurements at multiple size ranges from micro-to nanoscale to fully characterize and distinguish CNF samples. 00327-2022 

In this work a multilayer barrier paperboard was produced in a roll-to-roll process by slot-die coating of nanocellulose (microfibrillated cellulose or carboxymethylated cellulose nanofibrils) followed by extrusion coating of biodegradable thermoplastics (polylactic acid, polybutylene adipate terephthalate and polybutylene succinate). Hyperplaty kaolin pigments were blended in different ratios into nanocellulose to tailor the barrier properties of the multilayer structure and to study their influence on adhesion to the thermoplastic top layer. Influence of a plasticizer (glycerol) on flexibility and barrier performance of the multilayer structure was also examined. Water vapor permeance for the multilayer paperboard was below that of control single-layer thermoplastic materials, and oxygen permeance of the coated structure was similar or lower than that of pure nanocellulose films. Glycerol as a plasticizer further lowered the oxygen permeance and kaolin addition improved the adhesion at the nanocellulose/thermoplastic interface. The results provide insight into the role played by nanocelluloses, thermoplastics, pigments, and plasticizers on the barrier properties when these elements are processed together into multilayer structures, and paves the way for industrial production of sustainable packaging. 

Cellulose is the most abundant organic material on our planet which has a key role in our daily life (e.g., paper, packaging). In recent years, the need for replacing fossil-based materials has expanded the application of cellulose and cellulose derivatives including into electronics and sensing. The combination of nanostructures with cellulose nanofibers (CNFs) is expected to create new opportunities for the development of innovative electronic devices. In this paper, we report on a single-step process for the low temperature (<100 °C), environmentally friendly, and fully scalable CNF-templated highly dense growth of zinc oxide (ZnO) nanorods (NRs). More specifically, the effect of the degree of substitution of the CNF (enzymatic CNFs and carboxymethylated CNFs with two different substitution levels) on the ZnO growth and the application of the developed ZnO NRs/CNF nanocomposites in the development of UV sensors is reported herein. The results of this investigation show that the growth and nature of ZnO NRs are strongly dependent on the charge of the CNFs; high charge promotes nanorod growth whereas with low charge, ZnO isotropic microstructures are created that are not attached to the CNFs. Devices manufactured via screen printing/drop-casting of the ZnO NRs/CNF nanocomposites demonstrate a good photo-sensing response with a very stable UV-induced photocurrent of 25.84 µA. This also exhibits excellent long-term stability with fast ON/OFF switching performance under the irradiance of a UV lamp (15 W).