Phosphorylated cellulosic micro(nano)fibrillated materials are increasingly considered for flame-retardant applications as a biobased alternative to their halogen-based counterparts. Most of the reported cellulose functionalization strategies, however, are realized at low solids contents and/or involve energy-intensive fiber disintegration methods. In this perspective, we propose an alternative concept of phosphorylated microfibrillated cellulose production with notably high (25 wt %) solids content and low (0.6 MWh/t) energy consumption. Here, an enzyme-aided pulp disintegration upon mild mechanical treatment was combined with an effective mixing of the fibrillated material with (NH4)2HPO4 in the presence of urea. Subsequently, the obtained slurry was cured at elevated temperature to enable cellulose phosphorylation, which was redispersed afterward in water. The morphology of the obtained phosphorylated micro(nano)fibrillated cellulose materials was extensively characterized by optical microscopy, a fiber analyzer, SEM, and AFM. The presence of phosphate groups in the cellulose structure was validated by ATR-FTIR as well as 31P and 13C NMR spectroscopy. The casted films prepared from phosphorylated cellulose bearing a charge of 1540 μmol/g, which was the highest among the prepared samples, demonstrated noticeably improved flame retardancy, leaving ∼89% of the material after burning as well as self-extinguishing properties when the samples were subjected to a butane flame for 3 s.
Printed, flexible, and hybrid electronic technologies are advancing rapidly leading to remarkable developments in smart wearables, intelligent textiles, and health monitoring systems. Flexible electronics are typically fabricated on petroleum‐derived polymeric substrates. However, in the light of global environmental concerns regarding fossil raw materials, there is a need to drive the production of flexible electronics devices based on sustainable materials. Additionally, there is a need to reduce the quantity of electronic waste by developing material recovery and recycling technologies. Here, a fully biobased and biodegradable substrate tailored for printed flexible electronic applications is developed. Based on a nanocomposite of cellulose nanofibril (CNF) and hydroxyethyl cellulose (HEC), the substrate shows excellent mechanical and optical properties for printed flexible electronics applications. High‐resolution screen printing of conductive ink and typical electronics assembly processes are possible to realize on the substrate. An electrocardiograph (ECG) device is fabricated on the cellulosic substrate as a technology demonstrator and its performance is confirmed on human volunteers. Last, end‐of‐life scenarios are studied for printed electronic devices where device degradation and subsequent material recovery concepts are presented. This work demonstrates that sustainable plant‐derived materials can play a big role toward a green transition in the electronics industry.
Flexible optoelectronic technologies are becoming increasingly important with the advent of concepts such as smart-built environments and wearable systems, where they have found applications in displays, sensing, healthcare, and energy harvesting. Parallelly, there is also a need to make these innovations environmentally sustainable by design. In the present work, we employ nanocellulose and its excellent film-forming properties as a basis to develop a green flexible photonic device for sensing applications. Cellulose nanofibrils (CNFs) and cellulose nanocrystals (CNCs) were used as matrix materials along with a black thermochromic pigment to prepare thermoresponsive hybrid films. Optical properties of nanocellulose films such as transparency and haze were tuned by varying pigment loading. Nearly 90% transparent CNF and CNC films could be tuned to reduce the transmission to as low as 4 and 17%, respectively. However, the films regained transparency to up to 60% when heated above the thermochromic transition temperature (31 °C). The thermoresponsive behavior of the prepared films was exploited to demonstrate an all-optical modulation device. Continuous infrared light (1300 nm) was modulated by using a 660 nm visible diode laser. The laser intensity was sufficient to cause a localized thermochromic transition in the films. The laser was pulsed at 0.3 Hz and a uniform cyclic modulation depth of 0.3 dB was achieved. The demonstrated application of functional nanocellulose hybrid films as a light switch (modulator) could be harnessed in various thermally stimulated sensing systems such as temperature monitoring, energy-saving, and anti-counterfeiting.
High-consistency processing of fibrillated cellulose materials is attractive for commercial applications due to potential for lowered production costs, energy savings and easier logistics. The current work investigated structure–property relationships of fibrillated cellulose suspensions produced at 20% consistency using VTT HefCel (High-consistency enzymatic fibrillation of cellulose) technology. Morphological examination of the fibrillated materials revealed that enzymatic action on the cellulose substrates was not a direct function of enzyme dosage but rather was dependent on the raw material composition. Furthermore, shear viscosity of the HefCel suspensions was found to decrease with increasing enzyme dosage while the water retention increased. The shear viscosity followed power law relationship with the power law index varying in the range 0.11–0.73. The shear-thinning behavior decreased with increasing consistency. Moreover, suspension viscosity ( $$\upmu$$ ) was found to be highly dependent on the consistency ( $$\mathrm{c})$$ as $$\upmu \sim {\mathrm{c}}^{\mathrm{m}}$$ , with $$\mathrm{m}$$ ranging from 2.75 to 4.31 for different samples. Yield stress (τy) of the HefCel suspensions was measured at 7 and 10% consistencies. The performance of the fibrillated cellulose grades in a typical application was demonstrated by casting films, which were characterized for their mechanical properties.Graphic abstract
8 January 2022 in ACS Applied Materials & Interfaces
Optical fibers are a key component in modern photonics, where conventionally used polymer materials are derived from fossil-based resources, causing heavy greenhouse emissions and raising sustainability concerns. As a potential alternative, fibers derived from cellulose-based materials offer renewability, biocompatibility, and biodegradability. In the present work, we studied the potential of carboxymethyl cellulose (CMC) to prepare optical fibers with a core-only architecture. Wet-spun CMC hydrogel filaments were cross-linked using aluminum ions to fabricate optical fibers. The transmission spectra of fibers suggest that the light transmission window for cladding-free CMC fibers was in the range of 550–1350 nm, wherein the attenuation coefficient for CMC fibers was measured to be 1.6 dB·cm–1 at 637 nm. CMC optical fibers were successfully applied in touch sensing and respiratory rate monitoring. Finally, as a proof-of-concept, we demonstrate high-speed (150 Mbit/s) short-distance signal transmission using CMC fibers (at 1310 nm) in both air and water media. Our results establish the potential of carboxymethyl cellulose-based biocompatible optical fibers for highly demanding advanced sensor applications, such as in the biomedical domain.