The morphology of cellulose nanofibrils (CNFs), the rheological characteristics of their dispersions, and the corresponding relationships, are fundamental for understanding the properties of the material. This work aims at understanding how the morphological characteristics of the CNFs affect the rheology of the dispersions in the dilute region and to establish a relationship between both properties. A strong relationship was observed between the intrinsic viscosity of the CNF dispersions and their aspect ratio, which can be correlated through the expression ρ[η]=0.051p1.85. When comparing the model obtained in this work to the wormlike chain model, it was possible to verify that these models are independent of the flexibility of the CNFs. Regarding the fibrillation process, the dynamic viscosity only reflects part of the behavior of the morphological properties of the CNFs and does not provide reliable data that would allow these characteristics to be inferred, while the intrinsic viscosity does allow this relationship. 

Cellulose nanofibrils based on wood pulp fibres are most promising for biomedical applications. Bacterial cellulose has been suggested for some medical applications and is presently used as wound dressing. However, cost-efficient processes for mass production of bacterial cellulose are lacking. Hence, fibrillation of cellulose wood fibres is most interesting, as the cellulose nanofibrils can efficiently be produced in large quantities. However, the utilization of cellulose nanofibrils from wood requires a thorough verification of its biocompatibility, especially with fibroblast cells which are important in regenerative tissue and particularly in wound healing. The cellulose nanofibril structures used in this study were based on Eucalyptus and Pinus radiata pulp fibres. The nanofibrillated materials were manufactured using a homogenizer without pre-treatment and with 2,2,6,6-tetramethylpiperidine-1-oxy radical as pre-treatment, thus yielding nanofibrils low and high level of anionic charge, respectively. From these materials, two types of nanofibril-based structures were formed; (1) thin and dense structures and (2) open and porous structures. Cytotoxicity tests were applied on the samples, which demonstrated that the nanofibrils do not exert acute toxic phenomena on the tested fibroblast cells (3T3 cells). The cell membrane, cell mitochondrial activity and the DNA proliferation remained unchanged during the tests, which involved direct and indirect contact between the nano-structured materials and the 3T3 cells. Some samples were modified using the crosslinking agent polyethyleneimine (PEI) or the surfactant cetyl trimethylammonium bromide (CTAB). The sample modified with CTAB showed a clear toxic behaviour, having negative effects on cell survival, viability and proliferation. CTAB is an antimicrobial component, and thus this result was as expected. The sample crosslinked with PEI also had a significant reduction in cell viability indicating a reduction in DNA proliferation. We conclude that the neat cellulose nanostructured materials tested in this study are not toxic against fibroblasts cells. This is most important as nano-structured materials based on nanofibrils from wood pulp fibres are promising as substrate for regenerative medicine and wound healing.

The bio-based economy requires a sustainable utilization of bioresources for production of a range of products, including pulp, paper, chemicals, biofuel and bioplastics. Currently, various types of bioplastics are produced industrially, competing in performance and price with the conventional fossil-oil based plastics. However, there is also a major interest in utilizing non-food crops, such as lignocellulosics, for production of drop-in polymers or new dedicated bioplastics. Lignocellulosic resources have a potential to replace plastics and materials, which have been traditionally based on fossil resources. This is important, as the development of high performance bio-based and renewable materials is one important factor for sustainable growth of the bio-based industry. However, production of bioplastics from forestry biomass requires a dedicated fractionation into the major components, i.e. cellulose, hemicelluloses and lignin, effective purification processes and cost-effective routes for conversion into monomers and platform molecules, utilized as a basis for bioplastics production. These processes are now technologically demanding and not profitable. The intention of this work was thus to review the current advances that have been made during the years within fractionation and purification of lignocelluloses and the processes that may feasible for production of bioplastics, based on wood components.

Biomass-derived oligo- and polysaccharides may act as elicitors, i.e., bioactive molecules that trigger plant immune responses. This is particularly important to increase the resistance of plants to abiotic and biotic stresses. In this study, cellulose nanofibrils (CNF) gels were obtained by TEMPO-mediated oxidation of unbleached and bleached kraft pulps. The molecular structures were characterized with ESI and MALDI MS. Analysis of the fine sequences was achieved by MS and MS/MS of the water-soluble oligosaccharides obtained by acid hydrolysis of the CNF gels. The analysis revealed the presence of two families: one corresponding to homoglucuronic acid sequences and the other composed by alternating glucose and glucuronic acid units. The CNF gels, alone or with the addition of the water-soluble oligosaccharides, were tested on Chili pepper (Capsicum annuum). Based on the characterization of the gene expression with Next Generation Sequencing (NGS) of the C. annuum’s total messenger RNA, the differences in growth of the C. annuum seeds correlated well with the downregulation of the pathways regulating photosynthesis. A downregulation of the response to abiotic factors was detected, suggesting that these gels would improve the resistance of the C. annuum plants to abiotic stress due to, e.g., water deprivation and cold temperatures. 

To commercialize a biomedical product as a medical device, reproducibility of production and time-stability are important parameters. Studies of reproducibility are lacking in the literature. Additionally, chemical pre-treatments of wood fibres to produce highly fibrillated cellulose nanofibrils (CNF) seem to be demanding in terms of production efficiency, being a bottleneck for industrial upscaling. In this study, we evaluated the effect of pH on the dewatering time and washing steps of 2,2,6,6-Tetramethylpiperidinyloxy (TEMPO)-mediated oxidized wood fibres when applying 3.8 mmol NaClO/g cellulose. The results indicate that the method does not affect the carboxylation of the nanocelluloses, and levels of approximately 1390 μmol/g were obtained with good reproducibility. The washing time of a Low-pH sample was reduced to 1/5 of the time required for washing a Control sample. Additionally, the stability of the CNF samples was assessed over 10 months and changes were quantified, the most pronounced were the increase of potential residual fibre aggregates, reduction of viscosity and increase of carboxylic acid content. The cytotoxicity and skin irritation potential were not affected by the detected differences between the Control and Low-pH samples. Importantly, the antibacterial effect of the carboxylated CNFs against S. aureus and P. aeruginosa was confirmed. © 2023 The Authors

Single-use plastic products have been identified as an environmental challenge. When such products are not recycled, they may end up in nature and thus cause, e.g., marine littering. Thermoformed wood pulp fibre products are gaining more interest to replace fossil plastic products. However, beverage caps made of wood pulp fibres are challenging due to the hygroscopic nature of wood fibres, i.e., they absorb water, deform and loose functionality. Hence, the purpose of this study was to develop a fibre-based beverage cap that could replace plastic tethered cap systems. Both unbleached and bleached Kraft pulp and chemo-thermo-mechanical pulp (CTMP) fibres were tested in thermoforming trials, using tailor-made metal moulds. The results showed that Kraft pulp fibres formed denser structures, with more limited water absorption, compared to CTMP. The mechanical properties of thermoformed specimens were suitable for the application, i.e., the strength, modulus and elongation were between 32 and 36 MPa, 4–4.9 GPa and 1.6–1.9%, respectively, depending on the type of pulp fibre. Additionally, in order to secure that the caps were functional in relevant conditions in contact with liquids (water or milk), the caps were surface modified by silylation and esterification to increase the liquid barrier. The results indicate that surface esterification increased the contact angle to 95°. On the other hand, the surface-modified caps could not entirely limit the liquid absorption over longer periods of time (>∼1 h) when the caps were directly exposed to liquid. However, the liquid barrier was satisfactory when the products were exposed to increased relative humidity in refrigerated conditions (relative humidity >76% and temperature <7 °C). 

Nanofibrillated cellulose (NFC) offers a wide range of interesting opportunities and advantages, being biodegradable, renewable and thus environmentally sound. Extensive research has been performed on the effective production and application of NFC. The proposed applications extend from being a component in paper, coatings and composite materials to being applied in bio-medicine as part of wound dressings or in drug delivery systems. Some of the major advantages of NFC are the dimensions and the structural and chemical composition of nanofibrils, which lead to the formation of dense networks with optimized optical and mechanical properties. In this respect, the concept of nanopaper has been introduced. Nanopapers are strong structures, with high light transmittance and smooth surfaces. These characteristics open for novel applications, including the formation of smooth substrates for printing functionality. A recently explored example is the printing of bioactive biomacromolecules and conductive structures on tailor-made nanopapers, which could form the basis for novel biosensors. Additionally, nanobarriers are most promising in novel packaging applications where the self-assembly properties of the material facilitate the formation of dense structures with high barrier against oxygen. However, NFC alone does not seem to be sufficient for the formation of adequate nanobarriers due to the brittle and hygroscopic characteristics of the material. Novel biocomposite concepts need thus closer attention, where the strong and high barrier properties of NFC could be complemented with adequate bioplastics and additives for the formation of ductile films, suitable for conversion processes. From the biomedical point of view, NFC offers several advantages. Depending on the structural and chemical composition of the material and the cross-linking with adequate polymers and particles, micro-porous and elastic gels can be formed. Such gels can hold a considerable amount of water, thus being an excellent material for keeping a moist environment during wound healing and for facilitating the regeneration process of human tissue. Additionally, NFC gels based on oxidized nanofibrils can have pH-sensitive characteristics, a property with potential in drug delivery. With the intention of giving an extensive description of NFC and its modern applications, this presentation will be divided into three main sections; i) production and definition, ii) characterization including structural, chemical and biological aspects and iii) novel applications of NFC from nanopapers to biomedical devices.

Three-dimensional (3D) printing has evolved massively during the last years and is demonstrating its potential in tissue engineering, wound dressings, cell culture models for drug testing, and prosthesis, to name a few [...]

In this study, the suitability of optical devices for quantification of the fibrillation degree of bleached microfibrillated cellulose (MFC) materials has been assessed. The techniques for optical assessment include optical scanner, UV-vis spectrophotometry, turbidity, quantification of the fiber fraction and a camera system for dynamic measurements. The results show that the assessed optical devices are most adequate for quantification of the light transmittance of bleached MFC materials. Such quantification yields an estimation of the fibrillation degree. Films made of poorly fibrillated materials are opaque, while films made of highly fibrillated materials containing a major fraction of nanofibrils are translucent, with light transmittance larger than 90%. Finally, the concept of using images acquired with a CCD camera system, for estimating the fibrillation degree in dynamic conditions was exemplified. Such systems are most interesting as this will widen the applicability of optical methods for quantification of fibrillation degree online in production lines, which is expected to appear in the years to come.

Three-dimensional (3D) printing has rapidly emerged as a new technology with a wide range of applications that includes biomedicine. Some common 3D printing methods are based on the suitability of biopolymers to be extruded through a nozzle to construct a 3D structure layer by layer. Nanocelluloses with specific rheological characteristics are suitable components to form inks for 3D printing. This review considers various nanocelluloses that have been proposed for 3D printing with a focus on the potential advantages, limitations, and requirements when used for biomedical devices and when used in contact with the human body.

In this study the effect of paper structure on ink transfer and cold-set print quality was assessed. A factorial experiment involving 5 factors with two levels was designed. Several sheet structures were constructed. The sheets were made from three basic pulps, thermomechanical pulp (TMP), de-inked pulp (DIP) and stone groundwood (SGW). The designed structures were homogeneous and layered to verify the effect of sheet structure and fines content on print quality. A comprehensive multiscale characterisation of the sheet structures was performed. The analyses comprised scanning electron microscopy (SEM) and mercury porosimetry for bulk structure assessment. Parker Print Surf (PPS), laser profilometry and field-emission scanning electron microscopy (FE-SEM) were applied for giving a detailed description of the surface structure affecting ink transfer. The study revealed that the surface structure affects the ink demand and set-off. Increasing the micro-roughness leads to an increment of ink demand in order to achieve a given print density. The bulk pore structure affects the light scattering coefficients. Small pores are positive for increasing the light scattering and thus for reducing the print-through level. This was confirmed by SEM and mercury porosimetry measurements.

The complementary capabilities of various characterisation methods for micro-structural assessment are demonstrated. The assessed structures were composed of unbleached microfibrillated cellulose (MFC) in combination with bleached and 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO) pre-treated MFC materials. The biodegradable nano-composites were thus characterised in detail, including laser profilometry, scanning electron microscopy (SEM) in high and low vacuum modes, and field-emission SEM. The distribution of the unbleached MFC materials was assessed by staining the unbleached MFC with osmium tetroxide (OsO4), which reacts with CC double bonds encountered in lignin. In addition, some properties of the MFC nano-composite films were tested, i.e. tensile properties, water wettability and oxygen permeability. In general, the group of characteristics of the nano-composite MFC films was better than the properties of the films made of the neat MFC qualities. This indicates that mixing complementary MFC qualities could give synergetic effects that are not exploited completely when using the MFC qualities separately. The study thus confirms the suitability of unbleached MFC materials as a component in multilayer structures, for example biodegradable packaging applications.

Nanopaper is a new material concept composed of nanocellulose, which has been proposed for a series of applications. Recently, the surface of nanopapers has also been emphasized as an important structure to control. This is due to the potential of nanopaper structures as a substrate for printing functionality, which could expand the applicability of nanopaper as a functionalized biomaterial. In this study, we demonstrate how the roughness of nanopaper is affected by the fraction of residual fibres that were not fibrillated into nanofibrils after a homogenization procedure. The topography and morphology were assessed with laser profilometry, atomic force microscopy and scanning (transmission) electron microscopy. The results show a linear correlation between the estimated fraction of residual fibres and the roughness of the assessed nanopapers. Furthermore, the fraction of residual fibres can be reduced by fractionating the nanocellulose, which is demonstrated in the present work. Such knowledge will be valuable for designing nanopaper surfaces with specific structural characteristics.

A composite can be defined as a material composed of two or more components having distinct morphology and chemistry, and giving synergetic effects. In this paper the term biocomposite is used, referring to i) a material having at least one bio-component (e.g. wood pulp fibres and nanofibrils) or ii) biomaterials intended for biomedical applications. The utilization of wood pulp fibres in composite materials has gained major interest during the last years. There are various wood pulp fibres that can be used as reinforcement in composites, e.g. thermo-mechanical pulp (TMP), chemi-thermo-mechanical pulp (CTMP) and kraft pulp fibres. Depending on the pulping process (TMP, CTMP or kraft pulp), the pulp fibres differ greatly with respect to the fibre morphology and chemistry. Kraft pulp fibres have been one of the most used raw materials for producing nanocellulose. Nanocellulose from wood refers to various cellulose nano-materials such as cellulose nanocrystals and nanofibrillated cellulose. Nanofibrillated cellulose is composed of a major fraction of structurally homogeneous nanofibrils having typical widths in the nanometre scale and lengths in the micrometre scale. Wood pulp fibres and nanofibrils have been proposed as reinforcement in composite materials. Some of the major motivations have been the potential improvements by using fibres and nanofibrillated materials with respect to e.g. strength, biodegradability and functionality. The purpose of the present work is to review some advances in biocomposite research and development, including three focus areas; structured biocomposites, flexible biocomposites and biomaterials.

Sugarcane bagasse, an abundant residue, is usually burned as an energy source. However, provided that appropriate and sustainable pulping and fractionation processes are applied, bagasse can be utilized as a main source of cellulose nanofibrils (CNF). We explored in this study the production of CNF inks for 3D printing by direct-ink-writing technology. The CNF were tested against L929 fibroblasts cell line and we confirmed that the CNF from soda bagasse fibers were found not to have a cytotoxic potential. Additionally, we demonstrated that the alginate and Ca 2+ caused significant dimensional changes to the 3D printed constructs. The CNF-alginate grids exhibited a lateral expansion after printing and then shrank due to the cross-linking with the Ca 2+ . The release of Ca 2+ from the CNF and CNF-alginate constructs was quantified thus providing more insight about the CNF as carrier for Ca 2+ . This, combined with 3D printing, offers potential for personalized wound dressing devices, i.e. tailor-made constructs that can be adapted to a specific shape, depending on the characteristics of the wound healing treatment.

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. 

Cellulose nanofibrils (CNFs) were obtained by applying a chemical pretreatment consisting of autoclaving the pulp fibers in sodium hydroxide, combined with 2,2,6,6-tetramethylpiperidinyl-1-oxyl-mediated oxidation. Three levels of sodium hypochlorite were applied (2.5, 3.8, and 6.0 mmol/g) to obtain CNF qualities (CNF_2.5, CNF_3.8, and CNF_6.0) with varying content of carboxyl groups, that is, 1036, 1285, and 1593 μmol/g cellulose. The cytotoxicity and skin irritation potential (indirect tests) of the CNFs were determined according to standardized in vitro testing for medical devices. We here demonstrate that autoclaving (121 °C, 20 min), which was used to sterilize the gels, caused a modification of the CNF characteristics. This was confirmed by a reduction in the viscosity of the gels, a morphological change of the nanofibrils, by an increase of the ultraviolet-visible absorbance maxima at 250 nm, reduction of the absolute zeta potential, and by an increase in aldehyde content and reducing sugars after autoclaving. Fourier-transform infrared spectroscopy and wide-angle X-ray scattering complemented an extensive characterization of the CNF gels, before and after autoclaving. The antibacterial properties of autoclaved carboxylated CNFs were demonstrated in vitro (bacterial survival and swimming assays) on Pseudomonas aeruginosa and Staphylococcus aureus. Importantly, a mouse in vivo surgical-site infection model on S. aureus revealed that CNF_3.8 showed pronounced antibacterial effect and performed as good as the antiseptic Prontosan wound gel.

This study explores the production and surface modification of microfibrillated cellulose (MFC), based on unbleached and bleached Pinus radiata pulp fibres. Unbleached Pinus radiata pulp fibres tend to fibrillate easier by homogenisation without pre-treatment, compared to the corresponding bleached MFC. The resulting unbleached MFC films have higher barrier against oxygen, lower water wettability and higher tensile strength than the corresponding bleached MFC qualities. In addition, it is demonstrated that carboxymethylation can also be applied for production of highly fibrillated unbleached MFC. The nanofibril size distribution of the carboxymethylated MFC is narrow with diameters less than 20 nm, as quantified on high-resolution field-emission scanning electron microscopy images. The carboxymetylation had a larger fibrillation effect on the bleached pulp fibres than on the unbleached one. Importantly, the suitability of hexamethyldisilazane (HMDS) as a new alternative for rendering MFC films hydrophobic was demonstrated. TheHMDS-modifiedfilmsmade of carboxymethylated MFC had oxygen permeability levels better than 0.06 mL mm m-2 day-1 atm-1,which is a good property for some packaging applications.

Wood nanocellulose is a novel biomaterial for wound dressing applications. Wood nanocellulose was produced from never-dried P. radiata pulp fibres. The applied pre-treatment was 2,2,6,6-tetramethylpiperidinyl-1-oxyl  (TEMPO) mediated oxidation. To characterise bacterial growth, P. aeruginosa PAO1 biofilms were grown in Mueller Hinton broth on air-dried films. Various microscopy techniques, including atomic force microscopy (AFM), confocal laser scanning microscopy (CLSM) and field-emission scanning electron microscopy (FESEM), were applied to characterise the nanocellulose material and the bacterial-nanocellulose interactions.   Multiscale assessments, including FESEM and AFM, revealed the effective fibrillation of the fibre wall structure, yielding nanofibrils with diameters less than 20 nm and lengths in the micrometre-scale. Importantly, we have demonstrated that the growth of PAO1 was inhibited in the presence of the nanocellulose suspensions when compared to the control. Additionally, SEM imaging revealed distinct clusters of PAO1 cells growing on the surfaces of nanocellulose films. This work highlights the potential usefulness of novel nanocellulose materials in wound dressings with optimized characteristics.

During the last decades major efforts have been made to produce nanocellulose from wood, where the cellulose fibres are disintegrated into individualized nanofibrils with diameters < 20 nm and lengths in the micrometre scale. Production procedures include various pre-treatments, which yield nanocelluloses with varying chemical and structural properties. One important area of research is nanocellulose as a biomaterial with potential applications within the health sector. As an example, the superior mechanical properties, good moisture retention capability and the ability to form elastic macro-porous structures are advantageous properties for utilizing nanocellulose substrates for wound dressings. However, the utilization of nanocellulose as a substrate for wound dressings requires a thorough assessment of the biocompatibility of the material.  In this respect, it has been demonstrated in-vitro that nanocellulose does not exert acute toxic phenomena on fibroblast cells. However, in addition to in-vitro cytotoxicity testing, in-vivo testing of nanocellulose and the ability of nanocellulose to resist bacterial colonization need a closer attention. This presentation will give an overview of the current research on nanocellulose as a biomaterial for wound dressing applications, considering the morphology of nanocellulose structures, mechanical properties, moisture absorption, cytotoxicity tests and nanocellulose-bacteria interactions.

Nanocelluloses have good rheological properties that facilitate the extrusion of nanocellulose gels in micro-extrusion systems. It is considered a highly relevant characteristic that makes it possible to use nanocellulose as an ink component for 3D bioprinting purposes. The nanocelluloses assessed in this book chapter include wood nanocellulose (WNC), bacterial nanocellulose (BNC), and tunicate nanocellulose (TNC), which are often assumed to be non-toxic. Depending on various chemical and mechanical processes, both cellulose nanofibrils (CNF) and cellulose nanocrystals (CNC) can be obtained from the three mentioned nanocelluloses (WNC, BNC, and TNC). Pre/post-treatment processes (chemical and mechanical) cause modifications regarding surface chemistry and nano-morphology. Hence, it is essential to understand whether physicochemical properties may affect the toxicological profile of nanocelluloses. In this book chapter, we provide an overview of nanotoxicology and safety aspects associated with nanocelluloses. Relevant regulatory requirements are considered. We also discuss hazard assessment strategies based on tiered approaches for safety testing, which can be applied in the early stages of the innovation process. Ensuring the safe development of nanocellulose-based 3D bioprinting products will enable full market use of these sustainable resources throughout their life cycle.

Wood pulp fibres are an important component of environmentally sound and renewable fibre-reinforced composite materials. The high aspect ratio of pulp fibres is an essential property with respect to the mechanical properties a given composite material can achieve. The length of pulp fibres is affected by composite processing operations. This thus emphasizes the importance of assessing the pulp fibre length and how this may be affected by a given process for manufacturing composites. In this work a new method for measuring the length distribution of fibres and fibre fragments has been developed. The method is based on; (i) dissolving the composites, (ii) preparing the fibres for image acquisition and (iii) image analysis of the resulting fibre structures. The image analysis part is relatively simple to implement and is based on images acquired with a desktop scanner and a new ImageJ plugin. The quantification of fibre length has demonstrated the fibre shortening effect because of an extrusion process and subsequent injection moulding. Fibres with original lengths of >1 mm where shortened to fibre fragments with length of <200 μm. The shortening seems to be affected by the number of times the fibres have passed through the extruder, the amount of chain extender and the fraction of fibres in the polymer matrix.

Nanocellulose from wood is a promising material with potential in various technological areas. Within biomedical applications, nanocellulose has been proposed as a suitable nano-material for wound dressings. This is based on the capability of the material to self-assemble into 3D micro-porous structures, which among others have an excellent capacity of maintaining a moist environment. In addition, the surface chemistry of nanocellulose is suitable for various applications. First, OH-groups are abundant in nanocellulose materials, making the material strongly hydrophilic. Second, the surface chemistry can be modified, introducing aldehyde and carboxyl groups, which have major potential for surface functionalization. In this study, we demonstrate the production of nanocellulose with tailor-made surface chemistry, by pre-treating the raw cellulose fibres with carboxymethylation and periodate oxidation. The pre-treatments yielded a highly nanofibrillated material, with significant amounts of aldehyde and carboxyl groups. Importantly, the poly-anionic surface of the oxidized nanocellulose opens up for novel applications, i.e. micro-porous materials with pH-responsive characteristics. This is due to the swelling capacity of the 3D micro-porous structures, which have ionisable functional groups. In this study, we demonstrated that nanocellulose gels have a significantly higher swelling degree in neutral and alkaline conditions, compared to an acid environment (pH 3). Such a capability can potentially be applied in chronic wounds for controlled and intelligent release of antibacterial components into biofilms.

This study explores the suitability of microfibrillated cellulose (MFC) films as a substrate for printing electrically conductive structures and multilayer electronic structures such as organic field effect transistors. Various MFC qualities were tested, including mechanically produced MFC, 2,2,6,6-tetramethylpiperidinyl- 1-oxyl pre-treated MFC and carboxymethylated- MFC. The films differed significantly with respect to the surface structure. In addition, the carboxymethylated-MFC films were surface modified with hexamethyldisilazane (HMDS) to reduce the water-wettability of the films, and thus, improve the print resolution of the inkjet-printed silver (Ag) nanoparticles. The Ag-particles (diameter>50 nm) were printed on the HMDS-modified films, which were mainly composed of nanofibrils with diameters >20 nm. The effect of surface roughness and surface chemical characteristics on the ink spreading and print resolution of the Ag-structures was explored. It was demonstrated that organic transistors operating at low voltages can be fabricated on nano-engineered MFC films.

Side streams were collected from three locations in a flooring factory and their suitability in biocomposite formulations was assessed. The side stream (S3) that contained mainly residues from high-density fibreboards (HDF) was selected for further material testing. The effect of different fractions of S3, thermomechanical pulp (TMP) fibres and polylactic acid (PLA) were assessed in terms of their mechanical, melt flow and thermal properties. A biocomposite made from PLA, 20 wt% TMP fibres and 10 wt% S3 revealed a significant increase in modulus (5800 MPa), compared to the neat PLA (3598 MPa), and a similar melt-flow index (MFI = 4.5). The tensile strength was however somewhat reduced from 66 to 58 MPa. Importantly, numerical modelling and simulations were applied to demonstrate that building a model chair out of biocomposite can potentially reduce the material volume by 12% while maintaining similar load bearing capacity, compared to neat PLA. © 2021 The Author(s)

In this study a commercially liquid silicone rubber was filled with fumed silica particles in different concentrations and evaluated for medical applications. The thermal, morphological and mechanical properties of silicone/silica composite samples were studied before and after aging, flexural tests and immersion in saline environment. Understanding the effect of silica content, aging conditions and thickness (from 0.6 to 2 mm) of the samples on the behavior of these materials in different environments is crucial for applications as implantable devices. Before inducing any mechanical stress, tensile strength was found to increase for samples containing 3 or 5 wt% of fumed silica, depending on the thickness. A similar trend was observed after 106 flexes for tensile strength, storage modulus and hardness at room temperature, which increased with the concentration of fumed silica. Moreover, tensile strength decreased with increasing the thickness of the samples from 0.6 to 2 mm. The thermal degradation was found to start at higher temperature in the case of the composites as compared with neat silicone, however, the glass transition and melting temperatures were only slightly modified by the presence of the silica particles, regardless the mechanical aging. The MTT assay using L929 fibroblasts mouse cells showed a good short-time cytocompatibility for both silicone elastomer and the composite with 3 wt% fumed silica. Similarly, the measurement of the cytokine secretion revealed no inflammatory response.

Photopolymerization is an effective method to covalently cross-link polymer chains that can be shaped into several biomedical products and devices. Additionally, polymerization reaction may induce a fluid-solid phase transformation under physiological conditions and is ideal for in vivo cross-linking of injectable polymers. The photoinitiator is a key ingredient able to absorb the energy at a specific light wavelength and create radicals that convert the liquid monomer solution into polymers. The combination of photopolymerizable polymers, containing appropriate photoinitiators, and effective curing based on dedicated light sources offers the possibility to implement photopolymerization technology in 3D bioprinting systems. Hence, cell-laden structures with high cell viability and proliferation, high accuracy in production, and good control of scaffold geometry can be biofabricated. In this review, we provide an overview of photopolymerization technology, focusing our efforts on natural polymers, the chemistry involved, and their combination with appropriate photoinitiators to be used within 3D bioprinting and manufacturing of biomedical devices. The reviewed articles showed the impact of different factors that influence the success of the photopolymerization process and the final properties of the cross-linked materials.

Xylan is the second most abundant polysaccharide and the most abundant hemicellulose component of soda bagasse pulp. In this study, bleached soda bagasse pulp (SB) and bleached bagasse dissolving pulp (DB) with varying amounts of xylan were fibrillated with a homogenization process. The produced fibrillated materials were used for making nanopaper structures. The surface, physical, mechanical and optical properties of the nanopaper were measured, and the effect of xylan was assessed. Laser profilometry (LP) and field emission scanning electron microscopy were applied to study the degree of the fibrillation. The pulp having the highest xylan content, SB, showed the highest yield of cellulose nanofibrils. Nanopaper produced from SB had a more consolidated structure than that produced from DB. Additionally, SB nanopaper yielded higher tensile strength, lower LP roughness, a higher barrier against oxygen and lower opacity. These results indicate a higher degree of fibrillation of the SB pulp compared to the DB pulp. Hence, the positive effect of xylan for facilitating the fibrillation of the starting pulp fibers was demonstrated.

This study explores the benefits of using bagasse microfibrillated cellulose (MFC) in bagasse paper. Two different types of MFC were produced from DED bleached soda bagasse pulp. The MFC was added to soda bagasse pulp furnishes in different amounts. Cationic polyacrylamide (C-PAM) was selected as retention aid. The results show that addition of MFC increased the strength of paper as expected. Interestingly, 1% MFC in combination with 0.1% C-PAM yielded similar drainage time as the reference pulp, which did not contain MFC. In addition, the samples containing 1% MFC and 0.1% C-PAM yielded (i) a significant increment of the tensile index, (ii) a minor decrease of opacity and (iii) preserved Gurley porosity. Hence, this study proves that small fractions of MFC in combination with adequate retention aids can have positive effects with respect to paper properties, which is most interesting from an industrial point of view.

This work aimed to study the influence of the initial chemical composition (glucans, lignin, xylan, and mannans), intrinsic viscosity, and carboxylate groups of pulps on the production process and final properties of lignocellulosic nanofibers (LCNF). Pulps of pine sawdust, eucalyptus sawdust, and sugarcane bagasse subjected to conventional pulping and highly oxidized processes were the starting materials. The LCNF were obtained by TEMPO mediated oxidation and mechanical fibrillation with a colloidal grinder. The nanofibrillation degree, chemical charge content, rheology, laser profilometry, cristallinity and atomic force microscopy were used to characterize the LCNF. The carboxylate groups, hemicelluloses and lignin of the initial pulps were important factors that affected the production process of LCNF. The results revealed that intrinsic viscosity and carboxylate groups of the initial pulps affected LCNF production process, whereas lignin and hemicelluloses influenced the viscosity of LCNF aqueous suspensions, the roughness of LCNF films, and the carboxylate groups content of LCNF

Previous efforts to acetylate fibers and cellulose nanofibers (CNFs) are methodologically demanding and usually based on organic solvents catalyzed by acids. Hence, the purpose of this study was to introduce an improved method to acetylate unbleached (2 % and 5 % lignin) and bleached fibers (<1% lignin), and the corresponding CNFs, using a one-pot strategy in an aqueous alkaline medium. The lignin content in the pulp fibers (5 %) influenced the morphology of the corresponding fibrillated materials, i.e., increased secondary fines (92 %) and mean fibril area (36 %). Additionally, the pulps and CNFs (0 % and 5 % lignin content) were acetylated and compounded with high-density poly(ethylene) (HDPE). Acetylation improved the mechanical strength from 19 MPa (HDPE) to 30–40 MPa (when including acetylated fibers or CNFs). Finally, acetylation revealed a positive effect on melt-flow-index and elongation at break, and the water absorption of injection molded specimens was reduced to roughly 0.6 % after 10 days of testing. 

Bio-polyethylene (BioPE, derived from sugarcane), sugarcane bagasse pulp, and two compatibilizers (fossil and bio-based), were used to manufacture biocomposite filaments for 3D printing. Biocomposite filaments were manufactured and characterized in detail, including measurement of water absorption, mechanical properties, thermal stability and decomposition temperature (thermo-gravimetric analysis (TGA)). Differential scanning calorimetry (DSC) was performed to measure the glass transition temperature (Tg). Scanning electron microscopy (SEM) was applied to assess the fracture area of the filaments after mechanical testing. Increases of up to 10% in water absorption were measured for the samples with 40 wt% fibers and the fossil compatibilizer. The mechanical properties were improved by increasing the fraction of bagasse fibers from 0% to 20% and 40%. The suitability of the biocomposite filaments was tested for 3D printing, and some shapes were printed as demonstrators. Importantly, in a cradle-to-gate life cycle analysis of the biocomposites, we demonstrated that replacing fossil compatibilizer with a bio-based compatibilizer contributes to a reduction in CO₂-eq emissions, and an increase in CO₂ capture, achieving a CO₂-eq storage of 2.12 kg CO₂ eq/kg for the biocomposite containing 40% bagasse fibers and 6% bio-based compatibilizer.

Nanocelluloses with and without residual lignin were isolated from wheat straw. In addition, the effect of TEMPO-mediated oxidation on the production of lignin-containing nanocellulose was studied. The different nanocelluloses were used as reinforcing agent in Poly(vinyl alcohol) films. The morphology, crystallinity, surface microstructure, barrier properties, light transmittance, mechanical and antioxidant properties were evaluated. The translucency of films was reduced by the addition of nanocellulose, however, the ability to block UV-light increased from 10% for PVA to >50% using lignin-containing nanocellulose, and 30% for lignin-free samples. The mechanical properties increased considerably, however, for loads higher than 5% a negative trend was observed presumptively due to a clustering of nanocellulose components in PVA matrix. The barrier properties of the films were improved with the use of nanocellulose, especially at small amounts (1–3%). The antioxidant capacity of films was increased up to 10% using lignin-containing nanocellulose compared to 4.7% using PVA. © 2019 Elsevier B.V.

2,2,6,6-tetramethylpyperidine-1-oxyl (TEMPO) oxidized cellulose nanofibrils (CNF) were used as ink for three-dimensional (3D) printing of porous structures with potential as wound dressings. Alginate (10, 20, 30 and 40 wt%) was incorporated into the formulation to facilitate the ionic cross-linking with calcium chloride (CaCl₂). The effect of two different concentrations of CaCl₂ (50 and 100 mM) was studied. The 3D printed hydrogels were freeze-dried to produce aerogels which were tested for water absorption. Scanning Electronic Microscopy (SEM) pictures demonstrated that the higher the concentration of the cross-linker the higher the definition of the printed tracks. CNF-based aerogels showed a remarkable water absorption capability. Although the incorporation of alginate and the cross-linking with CaCl₂ led to shrinkage of the 3D printed constructs, the approach yielded suitable porous structures for water and moisture absorption. It is concluded that the 3D printed biocomposite structures developed in this study have characteristics that are promising for wound dressings devices.

Two different series of biobased polyethylene (BioPE) were used for the manufacturing of biocomposites, complemented with thermomechanical pulp (TMP) fibers. The intrinsic hydrophilic character of the TMP fibers was previously modified by grafting hydrophobic compounds (octyl gallate and lauryl gallate) by means of an enzymatic-assisted treatment. BioPE with low melt flow index (MFI) yielded filaments with low void fraction and relatively low thickness variation. The water absorption of the biocomposites was remarkably improved when the enzymatically-hydrophobized TMP fibers were used. Importantly, the 3D printing of BioPE was improved by adding 10% and 20% TMP fibers to the composition. Thus, 3D printable biocomposites with low water uptake can be manufactured by using fully biobased materials and environmentally-friendly processes.