There is an increasing demand for lightweight composites reinforced with carbon fibers (CFs). Due to its high availability and carbon content, kraft lignin has gained attention as a potential low-cost CF precursor. CFs with promising properties can be made from flexible dry-jet wet spun precursor fibers (PFs) from blends (70:30) of softwood kraft lignin and fully bleached softwood kraft pulp. This study focused on reducing the stabilization time, which is critical in CF manufacturing. The impact of stabilization conditions on chemical structure, yield, and mechanical properties was investigated. It was possible to reduce the oxidative stabilization time of the PFs from about 16 h to less than 2 h, or even omitting the stabilization step, without fusion of fibers. The main reactions involved in the stabilization stage were dehydration and oxidation. The results suggest that the isothermal stabilization at 250 °C override the importance of having a slow heating rate. For CFs with a commercial diameter, stabilization of less than 2 h rendered in tensile modulus 76 GPa and tensile strength 1070 MPa. Impregnation with ammonium dihydrogen phosphate significantly increased the CF yield, from 31-38 to 46-50 wt %, but at the expense of the mechanical properties.

Carbon fibers (CFs) are gaining increasing importance in lightweight composites, but their high price and reliance on fossil-based raw materials stress the need for renewable and cost-efficient alternatives. Kraft lignin and cellulose are renewable macromolecules available in high quantities, making them interesting candidates for CF production. Dry-jet wet spun precursor fibers (PFs) from a 70/30 w/w blend of softwood kraft lignin (SKL) and fully bleached softwood kraft pulp (KP) were converted into CFs under fixation. The focus was to investigate the effect of carbonization temperature and time on the CF structure and properties. Reducing the carbonization time from 708 to 24 min had no significant impact on the tensile properties. Increasing the carbonization temperature from 600 to 800 °C resulted in a large increase in the carbon content and tensile properties, suggesting that this is a critical region during carbonization of SKL:KP PFs. The highest Young's modulus (77 GPa) was obtained after carbonization at 1600 °C, explained by the gradual transition from amorphous to nanocrystalline graphite observed by Raman spectroscopy. On the other hand, the highest tensile strength (1050 MPa) was achieved at 1000 °C, a decrease being observed thereafter, which may be explained by an increase in radial heterogeneity.

Unbleached lignocellulosic wood fiber materials of low porosity are of great interest as eco-friendly load-bearing materials because their yield is much higher than that for “pure” wood cellulosics. The difference between comparable materials based on lignocellulose fibers or nanocellulose is investigated. The structure, surface area, mechanical properties, moisture sorption, and optical properties of films based on fibers or microfibrillated lignocellulose (MFLC) were characterized as a function of lignin content, and the environmental impact was compared. The modulus and tensile strength of comparable fiber and MFLC films (≈25% porosity) increased up to an optimum lignin content (11−17%) and then decreased at a very high lignin content. Hot-pressed MFLC films with little porosity showed excellent properties, 230−260 MPa strength, 17−20 GPa modulus, and 81 MPa wet strength. The mechanical property values of hot-pressed wood fibers with 25% porosity were also as high as 154 MPa strength and 13.2 GPa modulus, which are higher than those of comparable materials reported in the literature. Because hot-pressed lignocellulose fibers can be readily recycled and show low cumulative energy demand, they are candidates for semistructural engineering materials. MFLC is of great interest for coatings, films, adhesives, and as additives or in high-technology applications. 

Bagasse is an underutilized agro-industrial residue with great potential as raw material for the production of cellulose nanofibrils (CNF) for a range of applications. In this study, we have assessed the suitability of bagasse for production of CNF for three-dimensional (3D) printing. First, pulp fibers were obtained from the bagasse raw material using two fractionation methods, i.e. soda and hydrothermal treatment combined with soda. Second, the pulp fibers were pretreated by TEMPO-mediated oxidation using two levels of oxidation for comparison purposes. Finally, the CNF were characterized in detail and assessed as inks for 3D printing. The results show that CNF produced from fibers obtained by hydrothermal and soda pulping were less nanofibrillated than the corresponding material produced by soda pulping. However, the CNF sample obtained from soda pulp was cytotoxic, apparently due to a larger content of silica particles. All the CNF materials were 3D printable. We conclude that the noncytotoxic CNF produced from hydrothermally and soda treated pulp can potentially be used as inks for 3D printing of biomedical devices. 

Naturally fluorescent polymeric molecules such as collagen, resilin, cutin, suberin, or lignin can serve as renewable sources of bioproducts. Theoretical physics predicts that the fluorescence lifetime of these polymers is related to their chemical composition. We verified this prediction for lignin, a major structural element in plant cell walls that form woody biomass. Lignin is composed of different phenylpropanoid units, and its composition affects its properties, biological functions, and the utilization of wood biomass. We carried out fluorescence lifetime imaging microscopy (FLIM) measurements of wood cell wall lignin in a population of 90 hybrid aspen trees genetically engineered to display differences in cell wall chemistry and structure. We also measured the wood cell wall composition by classical analytical methods in these trees. Using statistical modeling and machine learning algorithms, we identified parameters of fluorescence lifetime that predict the content of S-type and G-type lignin units, the two main types of units in the lignin of angiosperm (flowering) plants. In a first step toward tailoring lignin biosynthesis toward improvement of woody biomass feedstocks, we show how FLIM can reveal the dynamics of lignin biosynthesis in two different biological contexts, including in vivo while lignin is being synthesized in the walls of living cells. © 2021 The Authors.

The present study is about the enzymatic modification of thermomechanical pulp (TMP) fibers for reduction of water uptake and their use in bio-based filaments for 3D printing. Additionally, TMP was used as a fiber reinforcing material and poly(lactic acid) (PLA) as the polymer matrix. The hydrophilic TMP fibers were treated via laccase-assisted grafting of octyl gallate (OG) or lauryl gallate (LG) onto the fiber surface. The modified TMP fibers showed remarkable hydrophobic properties, as demonstrated by water contact angle measurements. Filaments reinforced with OG-treated fibers exhibited the lowest water absorption and the best interfacial adhesion with the PLA matrix. Such higher chemical compatibility between the OG-treated fibers and the PLA enabled better stress transfer from the matrix to the fibers during mechanical testing, which led to the manufacture of strong filaments for 3D printing. All of the manufactured filaments were 3D-printable, although the filaments containing OG-treated fibers yielded the best results. Hence, laccase-mediated grafting of OG onto TMP fibers is a sustainable and environmentally friendly pathway for the manufacture of fully bio-based filaments for 3D printing.

A novel integrated process for recovery of protein-enriched biomasses from 5% presalting brines and spice brines of herring (Clupea harengus) was investigated by combining carrageenan- and/or acid-driven flocculation (F) plus dissolved air flotation (DAF). The F-DAF technique with carrageenan resulted in protein and lipid recoveries from 5% presalting brine of 78 and 38%, respectively. Without flocculation or with only acidification, protein and lipid recoveries in DAF were only 13 and 10%, respectively. Low protein and lipid recoveries, 8-12 and 1.8-8.2%, respectively, were also obtained when spice brine was subjected to only acidification and DAF. The protein content in dry biomasses from 5% presalting brine and spice brine was 36-43 and 13-16%, respectively. The corresponding lipid levels were 23-31 and 9-18%, respectively, with ash levels of 11-20 and 38-45%, respectively. Biomass proteins contained ≤45% essential amino acids, and the lipids had ≤16% long-chain n-3 polyunsaturated fatty acids. Freeze-dried spice brine biomasses were characterized by anchovy- and spice-related sensory attributes. 5% presalting brine biomasses were connected to fish and seafood attributes and showed gel forming capacity. The outlined F-DAF recovery system can thus recover both nutrients and interesting flavors from the herring process waters, which are currently lost from the food chain. © 2023 The Authors.

An important factor in the development of sodium-ion batteries (SIBs) is the use of cheap and sustainable materials. Sodium lignosulfonate, a lignin derivative, is demonstrated here as an attractive, "green", water-soluble, and potentially cost-effective binder for use in hard carbon anodes for SIBs. A comparison of its battery cycling performance is made against other binders including sodium carboxymethyl cellulose and lignin, obtained from the kraft process, as well as sodium alginate, derived from algae. Apart from lignin, which requires processing in N-methyl-2-pyrrolidone, the other three binders are water-soluble. Lignosulfonate shows comparable or better performance, with high capacity retention and stability, when using 1 M NaPF6 in propylene carbonate or ethylene carbonate:diethyl carbonate electrolytes for both half- and full-cells (against a Prussian white cathode). Further improvements are observed when including styrene-butadiene rubber as a co-binder. X-ray photoelectron spectroscopy demonstrates similar solid electrolyte interphase compositions after the initial sodium insertion for both lignosulfonate and carboxymethyl cellulose binders. However, after subsequent cycling, the surface layer composition and thickness are found to be dependent on the binder. For the lignosulfonate-based electrode, the layer appears thicker but comprises a smaller fraction of carbon-oxygen species. © 2021 The Authors.

Sustainable low melting temperature bicomponent polyester fibers that can be circularly recycled were developed. The potentially biobased poly(hexamethylene terephthalate) (PHT), acting as the low melting temperature sheath material in the designed bicomponent fibers, was synthesized in a pilot scale. The obtained PHT with an intrinsic viscosity of 0.47 dL/g showed suitable processability when it was processed together with a poly(butylene terephthalate) (PBT) core in a melt-spinning process of bicomponent fibers. Compared with the commercial low melting temperature terephthalate-isophthalate copolyester LMP-160, PHT showed superior mechanical properties according to DMA analysis. The low melting temperature bicomponent fibers with a ratio of the PBT core and PHT sheath at 70:30 were produced smoothly at 290 °C in a pilot melt-spinning line. Preliminary chemical recycling investigations by methanolysis revealed that PHT/PBT bicomponent fibers were completely depolymerized within 2 h at 200 °C, yielding pure terephthalate, which could be conveniently separated and recycled. This indicated the feasibility of circular recycling, which will greatly improve the sustainability of nonwovens thermally bonded by these new bicomponent fibers. © 2021 The Authors. 

Gliadin and glutenin proteins with 10, 20, 30 and 40% of glycerol were compression molded into films (130 °C) and evaluated for protein polymerization, β-sheet structure and nano-structural morphology. Here, for the first time we show how different amounts of glycerol impact the nano-structure and functional properties of the gliadin and glutenin films. Most polymerized protein was found in the gliadin films with 20 and 30% glycerol, and in all the glutenin films (except 10%), by RP-HPLC. A β-sheet-rich protein structure was found to be high in the 10 and 20% glycerol gliadin films, and in the 20 and 30% glycerol glutenin films by FT-IR. Glycerol content of 20, 30 and 40% impacted the nano-structural morphology of the gliadin glycerol films observed by SAXS, and to a limited extent for 10 and 20% glycerol gliadin films revealed by WAXS. No ordered nano-structure was found for the glutenin glycerol films. The 20%, 30% and 40% glycerol films were the most tunable for specific mechanical properties. For the highest stiffness and strength, the 10% glycerol protein films were the best choice.

Here, we investigated the structure of natural montmorillonite (MMT) and modified Cloisite C15A (MMT pre-intercalated with a dimethyl-dehydrogenated tallow quaternary ammonium surfactant) nanoclays in the wheat gluten-urea matrix in order to obtain a nanocomposite with improved barrier and mechanical properties. Small-angle X-ray scattering indicated that the characteristic hexagonal closed packed structure of the wheat gluten-urea matrix was not found in the C15A system and existed only in the 3 and 5 wt % MMT composites. SAXS/WAXS, TGA, and water vapor/oxygen barrier properties indicated that the dispersion of the C15A clay was somewhat better than the natural MMT clay. Confocal laser scanning microscopy showed MMT clay clusters and C15A clay particles dispersed in the protein matrix, and these were preferentially oriented in the extrusion direction only at 5 wt % of the C15 clay. The water vapor/oxygen barrier properties were improved with the presence of clay. Independent of the clay content used, the stiffness decreased and the extensibility increased in the presence of C15A due to the surfactant induced changes on the protein. The opposite "more expected" clay effect (increasing stiffness and decreasing extensibility) was observed for the MMT composites.

The lubrication of titania surfaces using a series of ionic liquid (IL)-hexadecane mixtures has been probed using nanoscale atomic force microscopy (AFM) and macroscale ball-on-disk tribometer measurements. The IL investigated is trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate, which is miscible with hexadecane in all proportions. At both length scales, the pure IL is a much more effective lubricant than pure hexadecane. At low loads, which are comparable to common industrial applications, the pure IL reduces the friction by 80% compared to pure hexadecane; while the IL-hexadecane mixtures lubricate the titania surface as effectively as the pure IL and wear decreases with increasing IL concentration. At high test loads the adsorbed ion boundary layer is displaced leading to surface contact and high friction, and wear is pronounced for all IL concentrations. Nonetheless, the IL performs better than a traditional zinc-dialkyl-dithophosphate (ZDDP) antiwear additive at the same concentration.

Poly(ϵ-caprolactone) (PCL) is a ductile thermoplastic, which is biodegradable in the marine environment. Limitations include low strength, petroleum-based origin, and comparably high cost. Cellulose fiber reinforcement is therefore of interest although uniform fiber dispersion is a challenge. In this study, a one-step wet compounding is proposed to validate a sustainable and feasible method to improve the dispersion of the cellulose fibers in hydrophobic polymer matrix as PCL, which showed to be insensitive to the presence of the water during the processing. A comparison between unmodified and acetylated cellulosic wood fibers is made to further assess the net effect of the wet feeding and chemical modification on the biocomposites properties, and the influence of acetylation on fiber structure is reported (ATR-FTIR, XRD). Effects of processing on nanofibrillation, shortening, and dispersion of the cellulose fibers are assessed as well as on PCL molar mass. Mechanical testing, dynamic mechanical thermal analysis, FE-SEM, and X-ray tomography is used to characterize composites. With the addition of 20 wt % cellulosic fibers, the Young's modulus increased from 240 MPa (neat PCL) to 1850 MPa for the biocomposites produced by using the wet feeding strategy, compared to 690 MPa showed for the biocomposites produced using dry feeling. A wet feeding of acetylated cellulosic fibers allowed even a greater increase, with an additional 46% and 248% increase of the ultimate strength and Young's modulus, when compared to wet feeding of the unmodified pulp, respectively. 

Wastewater produced during pressurized entrained flow biomass gasification (PEBG) was characterized and cleaned in order to raise the technology readiness level of the PEBG concept. Scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (EDS) and thermogravimetric analysis (TGA) were used to study material found in the water. The material was removed using filtration and the concentration of dissolved organic carbon (DOC), polyaromatic hydrocarbons (PAHs) and metals in filtered water was studied using standardized methods. Water was sampled during operation at three oxygen equivalence ratios (λ) and the results were compared to concentrations of gaseous hydrocarbons in the syngas. As λ increased, the amount of soot in the wastewater and the amount of soot precursors in the syngas was reduced. As a result the concentration of particles in the water was reduced and their composition shifted toward a higher percentage of inorganics (ash). PAH concentration trends in the water and in the syngas correlated and dissolved organic material in the water was reduced with increased λ. A particle removal efficiency of 98-99% was achieved using sedimentation and filtration while the DOC was reduced from ≈2.5 mg L-1 to below detection limit using granular activated carbon (GAC). © 2014 American Chemical Society.

In this study, we combined two wheat proteins, gliadin (Gli)/glutenin (GT), and modified potato starch (MPS) into composites using extrusion. In the Gli/GT-MPS composites, we studied the structural dynamics of proteins and starch, protein-starch interactions, protein properties, and composite morphology in relation to mechanical and barrier properties. Materials with different ratios of Gli/GT and MPS were extruded using either glycerol or glycerol-water at 110 and 130 °C. For the first time, a hierarchical hexagonal structure of Gli proteins was observed in Gli-MPS composite at both extrusion temperatures. The higher temperature (130 °C) induced a higher degree of protein cross-links, an increase in the polymer size, and formation of β-sheets compared to 110 °C. The combination of plasticizers (glycerol and water) favored a micro-structural morphology with improved gelatinization of starch, processability, as well as strength, stiffness, and extensibility of GT-MPS composites. The highest amount of the oxidized proteins was observed in the samples with the highest protein content and at high extrusion temperature. The Gli- and GT-MPS (30/70) samples showed promising oxygen barrier properties under ambient testing conditions. These findings provide in-depth information for tailoring the structural-functional relationship of the Gli/GT-potato starch composites for their promising use in designing various green materials.

Development of sustainable biobased fibers is required to displace their fossil-based counterparts, e.g., in textile, nonwoven, or composite applications. Regenerated protein fibers have a potential in this regard if their mechanical properties are improved. Herein, we study for the first time the use of nanocellulose as reinforcement in regenerated protein fibers produced using wet spinning. The influence of cellulose nanocrystals (CNC) incorporated into regenerated casein fibers is examined in terms of mechanical and morphological properties. The influence of different conditions for fiber chemical cross-linking is also investigated. Incorporation of CNC (up to 37.5 wt %) into spin dopes results in a continuous increase of fiber Young's modulus (up to twofold) in the dry state. Both maximum and breaking tenacity of dry fibers are enhanced by CNC, with a maximum at 7.0-10.5 wt % of CNC. When testing after being wetted, both breaking tenacity and Young's modulus of the composite fibers decrease, likely due to weakening of hydrogen bonds between CNC in the presence of water. We also demonstrate that the presence of salt during chemical cross-linking is crucial to produce intact and separated fibers in the yarn.

The production of cotton and other fibers causes excessive resource use and environmental impacts, and the deployment of these fibers in “fast fashion” is creating large masses of textile waste. Therefore, various industrial researchers are attempting to develop systems to recycle cellulosic materials. This is a challenging undertaking because of the need to handle mixed waste streams. Alkaline hydrolysis has been suggested as a useful textile recycling process, but its sustainability credentials have not been fully examined via life cycle assessment. The aim of this article is to provide such an examination and to guide process developers by scaling up results from recent laboratory work to a small-scale industrial facility. The results indicate that the recycling process is promising from an environmental point of view. The key issue controlling the relative environmental performance of the recycling system in comparison to a single-use benchmark is how the process for converting recovered cotton into a cellulosic fiber is performed. A fully integrated viscose production system or a system that makes one of the newer cellulosic fibers (e.g., lyocell) from the recovered cotton will improve the performance of the recycling system relative to its alternatives.

Carbon fibers (CFs) are fabricated by blending hardwood kraft lignin (HKL) and cellulose. Various compositions of HKL and cellulose in blended solutions are air-gap spun in 1-ethyl-3-methylimidazolium acetate (EMIM OAc), resulting in the production of virtually bead-free quality fibers. The synthesized HKL-cellulose fibers are thermostabilized and carbonized to achieve CFs, and consequently their electrical and mechanical properties are evaluated. Remarkably, fibers with the highest lignin content (65%) exhibited an electrical conductivity of approximately 42 S/cm, surpassing that of cellulose (approximately 15 S/cm). Moreover, the same fibers demonstrated significantly improved tensile strength (∼312 MPa), showcasing a 5-fold increase compared to pure cellulose while maintaining lower stiffness. Comprehensive analyses, including Auger electron spectroscopy and wide-angle X-ray scattering, show a heterogeneous skin-core morphology in the fibers revealing a higher degree of preferred orientation of carbon components in the skin compared to the core. The incorporation of lignin in CFs leads to increased graphitization, enhanced tensile strength, and a unique skin-core structure, where the skin’s graphitized cellulose and lignin contribute stiffness, while the predominantly lignin-rich core enhances carbon content, electrical conductivity, and strength.

Four nonhalogenated ionic liquids (ILs) based on the same phosphonium cation are investigated in terms of the anion suitability for enhancing the lubricity of a biodegradable oil. For all test conditions, typical for industrial machine components, the lubrication is shown to be governed by nonsacrificial films formed by the physisorption of ionic species on the tribo-surfaces. The anionic structure appears to have an important role in the formation of friction modifying films. The orthoborate ILs exhibit the formation of robust ionic boundary films, resulting in reduced friction and better wear protection. On the contrary, the surface adsorption of phosphinate and phosphate ILs appears to antagonistically disrupt the intrinsic lubrication properties of the biodegradable oil, resulting in high friction and wear. Through additional investigations, it is postulated that the higher dissociation of orthoborate ILs in the biodegradable oil allows the formation of hierarchical and electrostatically overscreened layer structures with long-range order, whereas the ILs with phosphate and phosphinate anions exhibit low dissociation in biodegradable oil, possibly due to the ion pairs being surrounded by a hydrocarbon halo, which presumably results in weak adsorption to form a mixed interfacial layer with no long-range order. © 2021 The Authors. 

Nanocelluloses are seen as the basis of high-performance materials from renewable sources, enabling a bio-based sustainable future. Unsurprisingly, research has initially been focused on the design of new material concepts and less on new and adapted fabrication processes that would allow large-scale industrial production and widespread societal impact. In fact, even the processing routes for making nanocelluloses and the understanding on how the mechanical action fibrillates plant raw materials, albeit chemically or enzymatically pre-treated, are only rudimentary and have not evolved significantly during the past three decades. To address the challenge of designing cellulose comminution processes for a reliable and predictable production of nanocelluloses, we engineered a study setup, referred to as Hyper Inertia Microfluidizer, to observe and quantify phenomena at high speeds and acceleration into microchannels, which is the underlying flow in homogenization. We study two different channel geometries, one with acceleration into a straight channel and one with acceleration into a 90° bend, which resembles the commercial equipment for microfluidization. With the purpose of intensification of the nanocellulose production process, we focused on an efficient first pass fragmentation. Fibers are strained by the extensional flow upon acceleration into the microchannels, leading to buckling deformation and, at a higher velocity, fragmentation. The treatment induces sites of structural damage along and at the end of the fiber, which become a source for nanocellulose. Irrespectively on the treatment channel, these nanocelluloses are fibril-agglomerates, which are further reduced to smaller sizes. In a theoretical analysis, we identify fibril delamination as failure mode from bending by turbulent fluctuations in the flow as a comminution mechanism at the nanocellulose scale. Thus, we argue that intensification of the fibrillation can be achieved by an initial efficient fragmentation of the cellulose in smaller fragments, leading to a larger number of damaged sites for the nanocellulose production. Refinement of these nanocelluloses to fibrils is then achieved by an increase in critical bending events, i.e., decreasing the turbulent length scale and increasing the residence time of fibrils in the turbulent flow. © 2022 The Authors.

Cellulose-based membranes have tremendous potential to improve the sustainability and performance of high value applications, such as filters and energy devices, particularly as fluorinated compounds are becoming more regulated. Yet, a deeper understanding of how cellulose films are formed and their structure, in both the wet and dry state, is needed to meet application specific demands and scale-up. We investigated cellulose dewatering using dead-end filtration and the effect of particle size, pressure, temperature, ionic strength, and pH were explored. Dewatering times, filtration cake resistance and compressibility of microfibrillated celluloses (MFCs) and cellulose nanofibrils (CNFs), (and a combination thereof) were measured to understand the role of fibrillation and intermolecular forces during dewatering and forming of membranes. In this fundamental work, dewatering behavior was well described by conventional filtration theory and increasing the pressure from 1 to 4 bar reduced dewatering times by one-half with no significant impact on the mechanical properties. Cake compressibility was found to be directly related to particle size and degree of fibrillation, indicating that finer grades of MFCs and CNFs could be more effectively dewatered at higher pressures. Adjusting pH and ionic strength of cellulose dispersions could similarly reduce dewatering times, yet impacted the wet and dry mechanical properties. This work serves as a basis to better understand the structure-property relationships that develop during dewatering of MFCs and CNFs. 

A rapeseed straw biorefinery process was demonstrated with more than 50% of the straw recovered as products. Xylan with a weight-average molecular weight of 56 760 g/mol was extracted in an alkaline step. The straw residue was subjected to soda pulping, resulting in cellulose-rich fibers and a lignin-rich liquid fraction. The lignin contained syringyl and guaiacyl aromatic structural units in a 1/0.75 ratio. The cellulose pulp was bleached, resulting in a cellulose fraction of 85% purity and a crystallinity index (CI) of 83%. Two grades of nanocellulose, CNF and CNC, were isolated from the bleached pulp. The CNF was very heterogeneous in size with an average diameter of 4 nm and an average length of 1177 nm. The CNC had an average diameter of 6 nm and an average particle length of 193 nm. CNF and CNC had good thermal stability and an aspect ratio of 294 and 32, respectively.

Presented herein is the integral valorization of residual biomass to film composites by their fractionation into building blocks in a multicomponent cascade isolation approach. First, pine cones were subjected to alkaline pretreatment, followed by soda pulping. Two different hemicellulose/lignin-based fractions were recovered from the extractives of these treatments, with a yield of 19%. Then, chloride- and peroxide-based bleaching methods were proposed to treat the soda-pulped samples, obtaining two cellulose-rich fractions with different chemical compositions and recovery yields (32% and 44%, respectively). From these cellulose fractions, two types of nanocelluloses with different lignin contents were obtained: cellulose nanofibrils (CNF), with a lignin content of 1%, and lignocellulose nanofibrils (LCNF), with a lignin content of 16%. The LCNF displayed lower crystallinity and viscosity but greater diameter and thermal stability than the CNF. The reinforcing capability of different amounts of both nanocelluloses on the first hemicellulose/lignin-based fraction (PCA-L) to form films was evaluated. The thermomechanical, barrier, antioxidant, moisture sorption, and mechanical properties were assessed and compared. In general, the LCNF films showed less moisture sorption and better thermomechanical and antioxidant properties than the CNF films. These results reveal LCNF to be a promising reinforcing agent for designing all-lignocellulose-based composite films to be used in food packaging applications. 

The present work demonstrates a simple and straightforward chemical modification of cellulose nanofibril (CNF) films in order to produce CO2 adsorbent materials. The CNF films were obtained from two agricultural residues, i.e. corn husks and oat hulls. CNF from kraft pulp was used for comparison purposes. Controlled surface silylation was conducted on the preformed CNF films in aqueous media under mild conditions using three aminosilanes bearing mono, di, and triamine groups. The success of the grafting of the aminosilanes on the CNF films was demonstrated by Fourier transform infrared and X-ray photoelectron spectroscopy analyses. The results of the contact angle measurements and field emission scanning electron microscopy coupled with energy dispersive spectroscopy showed homogeneous coverage by the amino groups on the surface of the modified CNF films, particularly with the diaminosilane N-[3-(trimethoxysilyl)propyl]ethylenediamine (DAMO). The produced films were thermally stable, and when subjected to 99.9% CO2 flow at 25 °C, these modified films showed good adsorption of CO2. Indeed, after 3 h of exposure the adsorbed concentration of CO2 of the CNF films modified with DAMO was 0.90, 1.27, and 2.11 mmol CO2 g-1 polymer for CNF films from corn husks, oat hulls, and kraft pulp, respectively.

This article describes nanocomposite films with separately grown protein nanofibrils (PNFs) in a nonfibrillar protein matrix from the same protein starting material (whey). Tensile tests on the glycerol-plasticized films indicate an increased elastic modulus and a decreased extensibility with increasing content of PNFs, although the films are still ductile at the maximum PNF content (15 wt %). Infrared spectroscopy confirms that the strongly hydrogen-bonded β-sheets in the PNFs are retained in the composites. The films appear with a PNF-induced undulated upper surface. It is shown that micrometer-scale spatial variations in the glycerol distribution are not the cause of these undulations. Instead, the undulations seem to be a feature of the PNF material itself. It was also shown that, apart from plasticizing the protein film, the presence of glycerol seemed to favor to some extent exfoliation of stacked β-sheets in the proteins, as revealed by X-ray diffraction.