Wood pulp fibres are promising reinforcements for biocomposites due to their renewable resource origin and mechanical properties. An oriented and dense fibre reinforcement structure is beneficial for biocomposite properties. We present a method of modifying fibres (e.g. to increase strain to failure) in pre-formed oriented high-density paper structures intended for biocomposites or as hot-pressed fibre materials. Mildly delignified, well-preserved holocellulose fibres from softwood are used. Cold alkali treatment (hemicellulose removal) and mercerisation (conversion to cellulose II) were carried out successfully on oriented fibre sheets. Controlled anisotropy and sheet density are achieved from untreated and straight fibres in the sheet formation step. High mechanical properties and increased ductility of mercerised sheets were observed, which may be valuable for hot-pressed fibre materials (E ≈ 7.1 GPa, strength of 108 MPa and strain to failure of 5.3%) and biocomposites. In contrast, modified wood pulp fibres were difficult to orient, resulting in higher sheet porosity and weak interfibre bonding.
Nanocomposite films were prepared by the addition of cellulose nanocrystals (CNCs) eventually surfactant modified (s-CNC) and silver (Ag) nanoparticles in the polylactic acid (PLA) matrix using melt extrusion followed by a film formation process. Multifunctional composite materials were investigated in terms of morphological, mechanical, thermal and antibacterial response. The nanocomposite films maintained the transparency properties of the PLA matrix. Thermal analysis showed increased values of crystallinity in the nanocomposites, more evident in the s-CNC based formulations that had the highest tensile Young modulus. The presence of surfactant favoured the dispersion of cellulose nanocrystals in the polymer matrix and the nucleation effect was remarkably enhanced. Moreover, an antibacterial activity against Staphylococcus aureus and Escherichia coil cells was detected for ternary systems, suggesting that these novel nanocomposites may offer good perspectives for food packaging applications which require an antibacterial effect constant over time. (C) 2011 Elsevier Ltd. All rights reserved.
Poly(lactic acid) (PIA) based high performance nanocomposites, were prepared using an innovative combination of nanocrystalline cellulose and silver nanoparticles. Binary and ternary systems were prepared by solvent casting process and their morphological, mechanical and thermal responses were investigated. Pristine (CNC) and surfactant modified cellulose nanocrystals (s-CNC) and silver (Ag) nanoparticles were used, and the effect of cellulose crystal nano-dimension, cellulose modification, and the combination of cellulose nanostructures with silver nanoparticles, was investigated. The important industrial problem of slow crystallization of PIA was addressed by the use of cellulose nanocrystals as biobased nucleating agents and the nonisothermal cold crystallization behaviour of reinforced binary and ternary systems was studied. The presence of surfactant on the nanocrystal surface favoured the dispersion of CNC in the PLA matrix while the thermal investigations and the nonisothermal crystallization studies underlined the ability of s-CNC to act as nucleation agent in both binary and ternary nanocomposites.
In the current study, we have used sodium chlorite and sodium hydroxide as extraction solutions, to remove lignin and hemicelluloses from the Balsa (Ochroma Lagopus) wood tissues, without damaging the wood honeycomb architecture. Surface morphologies are studied using scanning electron microscopy (SEM). In addition, sugars analysis of the chemically extracted wood is reported.
Eco-friendly materials need "green" fire-retardancy treatments, which offer opportunity for new wood nanotechnologies. Balsa wood (Ochroma pyramidale) was delignified to form a hierarchically structured and nanoporous scaffold mainly composed of cellulose nanofibrils. This nanocellulosic wood scaffold was impregnated with colloidal montmorillonite clay to form a nanostructured wood hybrid with high flame-retardancy. The nanoporous scaffold was characterized by scanning electron microscopy and gas adsorption. Flame-retardancy was evaluated by cone calorimetry, whereas thermal and thermo-oxidative stabilities were assessed by thermogravimetry. The location of well-distributed clay nanoplatelets inside the cell walls was confirmed by energy-dispersive X-ray analysis. This unique nanostructure dramatically increased the thermal stability because of thermal insulation, oxygen depletion, and catalytic charring effects. A coherent organic/inorganic charred residue was formed during combustion, leading to a strongly reduced heat release rate peak and reduced smoke generation.
Transparent wood (TW) structures in research studies were either thin and highly anisotropic or thick and isotropic but weak. Here, transparent plywood (TPW) laminates are investigated as load-bearing biocomposites with tunable mechanical and optical performances. Structure-property relationships are analyzed. The plies of TPW were laminated with controlled fiber directions and predetermined stacking sequence in order to control the directional dependence of modulus and strength, which would give improved properties in the weakest direction. Also, the angular dependent light scattering intensities were investigated and showed more uniform distribution. Luminescent TPW was prepared by incorporation of quantum dots (QDs) for potential lighting applications. TPW can be designed for large-scale use where multiaxial load-bearing performance is combined with new optical functionalities.
High modulus, strength and thermal stability make phenol-formaldehyde resins (PFRs) interesting as matrices for nanocomposites. Four PFR matrices synthesized with different formaldehyde (F) to phenol (P) molar ratios were investigated, as well as the influence of thermoplastic modification on their mechanical properties. The effectiveness of a specific curing cycle for obtaining macrovoid- and microvoid-free specimens by controlling the thickness of samples is demonstrated. Fourier transform infrared spectroscopy results reveal that F content increases the presence of oxidized linkages as benzophenones and fully substituted aromatic structures. PFR matrices with highest F content present the highest values of main transition temperature and flexural modulus up to an F/P ratio of 1.8, revealing the achievement of a densely crosslinked and rigid structure. A selected PFR matrix was modified with 5, 10 and 15 wt% of two poly(vinyl butyral) (PVB) thermoplastics of differing molecular weight. Phase separation occurs before gelation in all cases leading to different morphologies, observed using atomic force microscopy and optical microscopy, depending on PVB content: PVB-rich particles in PFR-richmatrix for 5 wt% and co-continuous dual morphology for 10 and 15 wt% for both PVBs. Strength improvement is achieved for PFR matrices modified with 5 wt% of PVB associated with a tailored particulate morphology with a particle size of around 1.2 mu m. Finally, 5 and 10 wt% PVB-modified PFR materials exhibit a very high thermal stability with degradation temperatures very close to those for neat PFR matrix.
A major limitation in the development of highly functional hybrid nanocomposites is brittleness and low tensile strength at high inorganic nanoparticle content. Herein, cellulose nanofibers were extracted from wood and individually decorated with cobalt-ferrite nanoparticles and then for the first time molded at low temperature (<120 degrees C) into magnetic nanocomposites with up to 93 wt % inorganic content. The material structure was characterized by TEM and FE-SEM and mechanically tested as compression molded samples. The obtained porous magnetic sheets were further impregnated with a thermosetting epoxy resin, which improved the load-bearing functions of ferrite and cellulose material. A nanocomposite with 70 wt % ferrite, 20 wt % cellulose nanofibers, and 10 wt % epoxy showed a modulus of 12.6 GPa, a tensile strength of 97 MPa, and a strain at failure of ca. 4%. Magnetic characterization was performed in a vibrating sample magnetometer, which showed that the coercivity was unaffected and that the saturation magnetization was in proportion with the ferrite content. The used ferrite, CoFe2O4 is a magnetically hard material, demonstrated by that the composite material behaved as a traditional permanent magnet. The presented processing route is easily adaptable to prepare millimeter-thick and moldable magnetic objects. This suggests that the processing method has the potential to be scaled-up for industrial use for the preparation of a new subcategory of magnetic, low-cost, and moldable objects based on cellulose nanofibers.
Magnetic nanoparticles are the functional component for magnetic membranes, but they are difficult to disperse and process into tough membranes. Here, cellulose nanofibers are decorated with magnetic ferrite nanoparticles formed in situ which ensures a uniform particle distribution, thereby avoiding the traditional mixing stage with the potential risk of particle agglomeration. The attachment of the particles to the nanofibrils is achieved via aqueous in situ hydrolysis of metal precursors onto the fibrils at temperatures below 100 °C. Metal adsorption and precursor quantification were carried out using Induction Coupled Plasma-Optical Emission Spectroscopy (ICP-OES). FE-SEM was used for high resolution characterization of the decorated nanofibers and hybrid membranes, and TEM was used for nanoparticle size distribution studies. The decorated nanofibers form a hydrocolloid. Large (200 mm diameter) hybrid cellulose/ferrite membranes were prepared by simple filtration and drying of the colloidal suspension. The low-density, flexible and permanently magnetized membranes contain as much as 60 wt% uniformly dispersed nanoparticles (thermogravimetric analysis data). Hysteresis magnetization was measured by a Vibrating Sample Magnetometer; the inorganic phase was characterized by XRD. Membrane mechanical properties were measured in uniaxial tension. An ultrathin prototype loudspeaker was made and its acoustic performance in terms of output sound pressure was characterized. A full spectrum of audible frequencies was resolved.
Nanocomposites based on 10 to 60 vol % cellulose nanofibers (NFC) in a photopolymerizable hyperbranched acrylate matrix were prepared. Unmodified NFC and NFC chemically modified with a silane coupling agent and with ceric ammonium nitrate for direct polymer grafting from the cellulose surface were used. A homogeneous dispersion of NFC in the matrix was obtained in each case, leading to a marked improvement in oxygen barrier (up to nine times) and thermomechanical properties (storage modulus increased up to seven times). The mechanisms involved in the permeability reduction were investigated, revealing non-monotonic trends in the evolution of the solubility and diffusion coefficients with NFC content. Most significantly, the inherent moisture sensitivity of the oxygen permeability of the NFC was found to be drastically reduced when it was dispersed in the polymer matrix, particularly after chemical modification, underlining the promise of the present approach for the production of robust, high barrier organic films.
Wood cellulose nanofibers (CNFs) based on bleached pulp are different from the cellulose microfibrils in the plant cell wall in terms of larger diameter, lower cellulose molar mass, and modified cellulose topochemistry. Also, CNF isolation often requires high-energy mechanical disintegration. Here, a new type of CNFs is reported based on a mild peracetic acid delignification process for spruce and aspen fibers, followed by low-energy mechanical disintegration. Resulting CNFs are characterized with respect to geometry (AFM, TEM), molar mass (SEC), and polysaccharide composition. Cellulose nanopaper films are prepared by filtration and characterized by UV-vis spectrometry for optical transparency and uniaxial tensile tests. These CNFs are unique in terms of high molar mass and cellulose-hemicellulose core-shell structure. Furthermore, the corresponding nanopaper structures exhibit exceptionally high optical transparency and the highest mechanical properties reported for comparable CNF nanopaper structures.
Olive stone is an important biomaterial waste product generated in large amount. As a lignocellulose material, olive stone could be a sustainable resource for biosorbents. In this work, olive stone powder delignification using sodium chlorite (NaClO2) was performed to enhance metal ion adsorption capacity. The influence of the treatment on olive stone powder physical-chemical properties was studied, including specific surface area, surface chemistry, morphology, etc. The white, delignified olive stone powder was applied for metal ions (Fe3+, Cu2+, and Zn2+) adsorption. Olive stone delignification not only increases the accessibility of the olive stone powder but also broadens the applications to materials design with optical functions by the generation of a white powder.
Owing to the hierarchical structure, easy multi-functionalization and favorable mechanical properties, wood could harvest electricity from mechanical energy through piezoelectric behavior. In this work, a scalable method to synthesize wood/ZnO composite with multilayered ZnO morphologies is reported for efficient mechanical energy conversion. The synthesis includes charged wood template fabrication, precursor infiltration, and ZnO hydrothermal growth, resulting in controlled ZnO morphologies and distributions while maintaining the hierarchical structure of the wood. Stereo-digital image correlation (stereo-DIC) investigated the relationship between deformation and piezoelectric performance, which revealed the homogeneous distribution of multilayered ZnO enhance piezoelectric performance. The output voltage of wood/ZnO was 1.5 V under periodic mechanical compression (8–10 N) for 300 cycles, while the output current was 2.91 nA. The scalable synthesis strategy and piezoelectric performance are significant for the design of advanced wood nanocomposites for sustainable and efficient energy conversion systems.
Polymer shape-memory aerogels (PSMAs) are prospects in various fields of application ranging from aerospace to biomedicine, as advanced thermal insulators, actuators, or sensors. However, the fabrication of PSMAs with good mechanical performance is challenging and is currently dominated by fossil-based polymers. In this work, strong, shape-memory bio-aerogels with high specific surface areas (up to 220 m2/g) and low radial thermal conductivity (0.042 W/mK) were prepared through a one-step treatment of native wood using an ionic liquid mixture of [MTBD]+[MMP]−/DMSO. The aerogel showed similar chemical composition similar to native wood. Nanoscale spatial rearrangement of wood biopolymers in the cell wall and lumen was achieved, resulting in flexible hydrogels, offering design freedom for subsequent aerogels with intricate geometries. Shape-memory function under stimuli of water was reported. The chemical composition and distribution, morphology, and mechanical performance of the aerogel were carefully studied using confocal Raman spectroscopy, AFM, SAXS/WAXS, NMR, digital image correlation, etc. With its simplicity, sustainability, and the broad range of applicability, the methodology developed for nanoscale reassembly of wood is an advancement for the design of biobased shape-memory aerogels.
Eco-friendly materials with superior thermal insulation and mechanical properties are desirable for improved energy- and space-efficiency in buildings. Cellulose aerogels with structural anisotropy could fulfill these requirements, but complex processing and high energy demand are challenges for scaling up. Here we propose a scalable, nonadditive, top-down fabrication of strong anisotropic aerogels directly from wood with excellent, near isotropic thermal insulation functions. The aerogel was obtained through cell wall dissolution and controlled precipitation in lumen, using an ionic liquid (IL) mixture comprising DMSO and a guanidinium phosphorus-based IL [MTBD][MMP]. The wood aerogel shows a unique structure with lumen filled with nanofibrils network. In situ formation of a cellulosic nanofibril network in the lumen results in specific surface areas up to 280 m2/g and high yield strengths >1.2 MPa. The highly mesoporous structure (average pore diameter ∼20 nm) of freeze-dried wood aerogels leads to low thermal conductivities in both the radial (0.037 W/mK) and axial (0.057 W/mK) directions, showing great potential as scalable thermal insulators. This synthesis route is energy efficient with high nanostructural controllability. The unique nanostructure and rare combination of strength and thermal properties set the material apart from comparable bottom-up aerogels. This nonadditive synthesis approach is believed to contribute significantly toward large-scale design and structure control of biobased aerogels.
Highly porous, strong aerogels with anisotropicstructural properties are of great interest for multifunctionalmaterials for applications including insulators in buildings,filters for oil cleanup, electrical storage devices,etc. Contem-porary aerogels are mostly extracted from fossil resources andsynthesized from bottom-up techniques, often requiring addi-tional strategies to obtain high anisotropy. In this work, auniversal approach to prepare porous, strong, anisotropicaerogels is presented through exploiting the natural hierarchicaland anisotropic structure of wood. The preparation comprisesnanoscale removal of lignin, followed by dissolution−regener-ation of nanofibers, leading to enhanced cell wall porosity with nanofibrillated networks occupying the pore space in thecellular wood structure. The aerogels retain structural anisotropy of natural wood, exhibit specific surface areas up to 247 m2/g, and show high compression strength at 95% porosity. This is a record specific area value for wood aerogels/foams and evenhigher than most cellulose-based aerogels for its assigned strength. The aerogel can serve as a platform for multifunctionalcomposites including scaffolds for catalysis, gas separation, or liquid purification due to its porous matrix or as binder-freeelectrodes in electronics. To demonstrate the multifunctionality, the aerogels are successfully decorated with metalnanoparticles (Ag) and metal oxide nanoparticles (TiO2)byin situsynthesis, coated by the conductive polymer(PEDOT:PSS), and carbonized to yield conductive aerogels. This approach is found to be a universal way to prepare highlyporous anisotropic aerogels.
Here we investigate the relationship between thermomechanical properties and chemical structure of well-characterized lignin-based epoxy resins. For this purpose, technical lignins from eucalyptus and spruce, obtained from the Kraft process, were used. The choice of lignins was based on the expected differences in molecular structure. The lignins were then refined by solvent fractionation, and three fractions with comparable molecular weights were selected to reduce effects of molar mass on the properties of the final thermoset resins. Consequently, any differences in thermomechanical properties are expected to correlate with molecular structure differences between the lignins. Oxirane moieties were selectively introduced to the refined fractions, and the resulting lignin epoxides were subsequently cross-linked with two commercially available polyether diamines (Mn = 2000 and 400) to obtain lignin-based epoxy resins. Molecular-scale characterization of the refined lignins and their derivatives were performed by 31P NMR, 2D-NMR, and DSC methods to obtain the detailed chemical structure of original and derivatized lignins. The thermosets were studied by DSC, DMA, and tensile tests and demonstrated diverse thermomechanical properties attributed to structural components in lignin and selected amine cross-linker. An epoxy resin with a lignin content of 66% showed a Tg of 79 °C from DMA, Young's modulus of 1.7 GPa, tensile strength of 66 MPa, and strain to failure of 8%. The effect of molecular lignin structure on thermomechanical properties was analyzed, finding significant differences between the rigid guaiacyl units in spruce lignin compared with sinapyl units in eucalyptus lignin. The methodology points toward rational design of molecularly tailored lignin-based thermosets.
The aim of this study was to improve the toughness of EB-cured acrylate thermost resins by using hyperbranched aliphatic polyesters as additives to obtain a liquid-liquid phase-separated resin. The hyperbranched polyester can be considered as a hydroxyl functional scaffold, on which functional groups were reacted by control phase separation and crosslinking. Alkyl chains of different lengths attached to the scaffold controlled phase separation. The amount of crosslinking within the rubbery particle and between the particles and the matrix was set by the percentage of methacrylate groups. A good phase separation was obtained; therefore, T-g decreased only slightly compared to the pure acrylate. The K-IC value of the cured resins was increased by 30%. The phase-separated resins showed stability with time and no significant increase in particle size was noticed after 18 months.
Single-wall carbon nanotubes (SWNTs) can be dispersed with the aid of cellulose nanofibrils (CNF) in aqueous medium. The dispersions have high stability and quality that can be utilized into self-assembly of functional composites having high electrical conductivity and strength. The composites were then carefully analyzed in terms of their mechanical and electrical properties as well as dispersion quality.
Deformation mechanisms are largely unknown for superelastic carbon nanotube (CNT) aerogels, and this hampers materials design efforts. The CNT network in the cell walls is typically crosslinked or connected by a thermoset polymer phase. In order to create a recyclable superelastic aerogel, unmodified single or multi-walled CNTs were dispersed in water by adding to aqueous carboxymethyl cellulose (CMC) solution. Directional freeze-drying was used to form honeycombs with cell walls of random-in-the-plane CNTs in CMC matrix. Cell wall morphology and porosity were studied and related to CNT type and content, as well as elastic or plastic buckling of the cell walls under deformation. CMC acts as a physical crosslinker for the CNTs in a porous cell wall. Aerogel structure and properties were characterized before and after recycling. The conductivity of the composite aerogel with a density of 10 kg/m3, 99% porosity and 50 wt % single-walled CNT exceeds 0.5 S/cm. The potential of these superelastic and conductive aerogels for applications such as mechanoresponsive materials was examined in cyclic conductivity tests at different strains. This opens a new route for recyclable superelastic CNT composite aerogels, avoiding material loss, chemical treatment or addition of other components.
This work presents a route to fabricate micropatterned conductive structures where the conductors are monolithically integrated with nanocellulose-based paper. To fabricate conductive features, microstructures are patterned on filter papers using wax-printing, followed by vacuum filtration of carbon nanotubes (CNTs) or silver nanowires (AgNWs) dispersed in aqueous cellulose nanofibrils (CNFs). These patterns are then laminated onto a pure CNF substrate (both in gel-state) and dried to form cellulose nanopapers with integrated conductive micropatterns. Resolutions of the conductive features are shown down to 400 µm wide, 250 nm thick, and with conductivity values of 115 ± 5 S cm −1 for the CNF–CNT and 3770 ± 230 S cm −1 for the CNF–AgNW micropatterns. The nanopaper and the conductive patterns both constitute random fibrous networks, and they display similar ductility and swelling behavior in water. Thus, the integrated conductive micropatterns can withstand folding, as well as wetting cycles. This stability of the micropatterns makes them useful in various devices based on nanocellulose substrates. As an example, an electroanalytical nanopaper device that operates in wet conditions is demonstrated.
It is challenging to obtain high-quality dispersions of single-wall nanotubes (SWNTs) in composite matrix materials, in order to reach the full potential of mechanical and electronic properties. The most widely used matrix materials are polymers, and the route to achieving high quality dispersions of SWNT is mainly chemical functionalization of the SWNT. This leads to increased cost, a loss of strength and lower conductivity. In addition full potential of colloidal self-assembly cannot be fully exploited in a polymer matrix. This may limit the possibilities for assembly of highly ordered structural nanocomposites. Here we show that nanofibrillated cellulose (NFC) can act as an excellent aqueous dispersion agent for as-prepared SWNTs, making possible low-cost exfoliation and purification of SWNTs with dispersion limits exceeding 40 wt %. The NFC:SWNT dispersion may also offer a cheap and sustainable alternative for molecular self-assembly of advanced composites. We demonstrate semitransparent conductive films, aerogels and anisotropic microscale fibers with nanoscale composite structure. The NFC:SWNT nanopaper shows increased strength at 3 wt % SWNT, reaching a modulus of 133 GPa, and a strength of 307 MPa. The anisotropic microfiber composites have maximum conductivities above 200 S cm(-1) and current densities reaching 1400 A cm(-2).
Transversal shear of softwoods was studied with the single cube apparatus (SCA). Fullfield strain data and FEA were used to validate the device. Once a close to pure shear strainregion was confirmed, the relationship between shear strain and radial density gradient wasobtained; finally an improved FE model was created.
Transversal shear of softwoods was studied with the single cube apparatus (SCA). Full field strain data and FEA were used to validate the device. Once a close to pure shear strain region was confirmed, the relationship between shear strain and radial density gradient was obtained; finally an improved FE model was created.
The design and analysis of wood structures require accurate data for shear properties, where transverse shear in particular has been neglected in the past. The single cube apparatus (SCA) was applied to transverse shear of Norway spruce (Picea Abies), due to the importance of this species in wood structures, such as glulam, and also its allegedly low value of GRT . Full-field strain data and FEA were used to analyze the potential of the method. The presence of a large central region of homogeneous and close to pure shear strain was confirmed. The SCA method is therefore a strong candidate for improved shear test procedures in wood and other materials, where porosity (gripping problems), heterogeneity on mm-scale and polar orthotropy (annual ring curvature) may cause particular difficulties. In contrast to many other shear test studies, the accuracy of the present GRT data is supported by documented large and homogeneous specimen stress- and strain-fields in almost pure shear, direct measurements of strain field, and careful stress analysis based on FEA.
An important failure mechanism in glulam beams is cracking caused by out-of-plane transverse loads. It has been demonstrated that the low transverse shear modulus G(RT) in spruce contributes to large transverse strain inhomogeneities due to the annual ring structure in combination with shear coupling effects. In the present study, improved understanding of annual ring effects is achieved by the development of a micromechanical model. It relates the functional density gradient in spruce annual rings to shear modulus GRT. The geometrical basis is a hexagonal cell model, and in shear it is demonstrated to deform primarily by cell wall bending. Full-field strain measurements by digital speckle photography (DSP) show very strong correlation with predicted shear strains at the annual ring scale. Predictions are obtained by implementation of the micromechanics model in a finite element (FE) model developed for the single cube apparatus shear specimen. The low GRT of spruce is due to the strong dependence of GRT on relative density rho/rho(s)(G(RT) proportional to (rho/rho(s))(3)). This is particularly important in spruce. Even though average density is typically quite high, the functional gradient structure includes local densities as low as 200 kg/m(3).
Films of high Young's modulus and low density are of interest for application as loudspeaker membranes. In the present study nanocomposite films were prepared from microfibrillated cellulose (MFC) and from MFC in combination with melamine formaldehyde (MF). The prepared materials were Studied with respect to structure as well as physical and mechanical properties. Studies in SEM and calculation of porosity showed that these materials have a dense paper-like structure. The moisture sorption isotherms were measured and showed that Moisture content decreased in the presence of ME Mechanical properties were studied by dynamical mechanical thermal measurements as well as by tensile tests. Cellulose films showed an average Young's modulus of 14 GPa while the nanocomposites showed an average Young's modulus as high as 16.6 GPa and average tensile strength as high as 142 M.Pa. By controlling composition and structure, the range of properties of these materials can extend the property range available for existing materials. The combination of comparatively high mechanical damping and high sound propagation velocity is of technical interest.
The present invention relates to a method of producing a cellulose based paper, the paper itself and the use thereof where the paper exhibits enhanced mechanical properties. The method involves providing a suspension of well dispersed modified cellulose at a low concentration. The properties and the chemical structure of the paper make it suitable for in vivo applications such as implant material.
Cellulose nanofibrils offer interesting potential as a native fibrous constituent of mechanical performance exceeding the plant fibers in current use for commercial products. In the present study, wood nanofibrils are used to prepare porous cellulose nanopaper of remarkably high toughness. Nanopapers of different porosities and from nanofibrils of different molar mass are prepared. Uniaxial tensile tests are performed and structure-property relationships are discussed. The high toughness of highly porous nanopaper is related to the nanofibrillar network structure and high mechanical nanofibril performance. Also, molar mass correlates with tensile strength. This indicates that nanofibril fracture controls ultimate strength. Furthermore, the large strain-to-failure means that mechanisms, such as interfibril slippage, also contributes to inelastic deformation in addition to deformation of the nanofibrils themselves.
Cellulosic fibers offer interesting possibilities for good interfacial adhesion due to the high density of hydroxyl groups at the surface. in the present study, the potential of a new nanocomposite concept is investigated, where a porous cellulose nanofiber network is impregnated with a solution of reactive hyperbranched polyester. The polymer is chemically cross-linked to form a solid matrix. The resulting nanocomposite structure is unique. The matrix surrounds a tough nanopaper structure consisting of approximately 20 nm diameter nanofibers with an average interfiber distance of only about 6 nm. The cross-linked polymer matrix shows strongly altered characteristics when it is cross-linked in the confined space within the nanofiber network, including dramatically increased T-g, and this must be due to covalent matrix-nanofiber linkages.
Microfibrillated cellulose nanofibers (MFC) provide strong reinforcement in polymer nanocomposites. In the present study, cellulosic wood fiber pulps are treated by endoglucanases or acid hydrolysis in combination with mechanical shearing in order to disintegrate MFC from the wood fiber cell wall. After successful disintegration, the MFC nanofibers were studied by atomic force microscopy (AFM). Enzyme-treatment was found to facilitate disintegration, and the MFC nanofibers produced also showed higher average molar mass and larger aspect ratio than nanofibers resulting from acidic pretreatment.
High Klason lignin content (23 wt%) cellulose nanofibrils (LCNF) were successfully isolated from eucalyptus pulp through catalyzed chemical oxidation, followed by high-pressure homogenization. LCNFs had a diameter of ca. 13 nm according to AFM evaluation. Dense films were obtained through vacuum filtration (nanopaper) and subjected to different drying methods. When drying under heat and mild vacuum (93 degrees C, 95 kPa) a higher water contact angle, lower roughness and oxygen transmission rate were observed, compared to those drying at room temperature under compression conditions. DSC experiments showed difference in signals associated to T-g of LCNF compared to CNF produced from spruce bleached pulp through enzymatic pre-treatment. The LCNF-based nanopaper showed mechanical properties slightly lower than for those made from cellulose nanofibrils, yet with increased hydrophobicity. In summary, the high-lignin content cellulose nanofibrils proved to be a suitable material for the production of low oxygen permeability nanopaper, with chemical composition close to native wood.
Chemical wood cellulose fiber modification is performed with the purpose to improve compatibility and induce nanofibrillation of fibers during melt compounding of thermoplastic biocomposites. Compounding of well-dispersed cellulose nanocomposites based on biodegradable polymers is challenging and commonly requires separate processes for wood fiber fibrillation into cellulose nanofibrils (CNF), followed by compounding. Here, nanostructured biocomposites based on poly(caprolactone) (PCL) and holocellulose wood fibers (HC) were melt compounded in a single step. Prior to compounding, PCL was grafted from the HC fibers by ring-opening polymerization (ROP) of epsilon CL with three different polymer graft lengths. The grafting was performed by two different methods: the commonly used bulk method and a new approach using acetic acid (AcOH) as the reaction solvent to swell the fiber structure during grafting. Remarkably, AcOH as a swelling solvent resulted in high density of grafts inside the nanostructure and throughout the volume of the HC wood cellulose fibers. As a consequence, more pronounced defibrillation of fibers into CNF during compounding as well as more uniform CNF dispersion in the thermoplastic PCL matrix was observed. In contrast, fibers grafted under bulk conditions showed little grafting and weak reinforcement effects. The Young's modulus and strength of the PCL were improved by almost 60% with the addition of only S wt % fibers, and the toughness was improved by 67%. The results show a close connection between the graft structure and final material properties.
Silk fibroin, a widely used natural biopolymer, presents remarkable flexibility and biodegradability, making it of great interest as a polymer matrix for functional composite materials. Herein, composites of silk nanofibrils and metal-organic framework (MOF) nanosheets were successfully fabricated by a coincubation and coassembly process. Under heat incubation, silk fibroin self-assembled into one-dimensional nanofibrils, while MOF nanosheets simultaneously covered or wrapped on the silk nanofibrils in a water suspension. Transparent composite membranes were obtained from their water suspensions by the solution casting method. The regenerated silk nanofibrils formed a network structure, and the integrated MOF nanosheets (0.1 to 3.0 wt %) endowed the composites with aggregation-induced emission luminogen (AIEgen)-based fluorescence. The fluorescence intensity of the composites was significantly enhanced owing to the interfacial interactions between silk nanofibrils and MOF nanosheets. The composite membranes also offer excellent UV shielding while maintaining optical transparency in the visible spectrum. This work provides an efficient pathway to fabricate luminescent silk protein-based composites for functional materials such as fluorescence sensing and anticounterfeiting.
A concept of transparent “quantum dot glass”(TQDG) is proposed for a combination of a quantum dot(QD)-based glass luminescent solar concentrator (LSC) and itsedge-attached solar cells, as a type of transparent photovoltaics(TPVs) for building-integrated photovoltaics (BIPVs). Differentfrom conventional LSCs, which typically serve as pure opticaldevices, TQDGs have to fulfill requirements as both powergeneratingcomponents and building construction materials. In thiswork, we demonstrate large-area (400 cm2) TQDGs based onsilicon QDs in a triplex glass configuration. An overall powerconversion efficiency (PCE) of 1.57% was obtained with back-reflection for a transparent TQDG (average visible transmittance of84% with a color rendering index of 88 and a low haze ≤3%), contributing to a light utilization efficiency (LUE) of 1.3%, which isamong the top reported TPVs based on the LSC technology with similar size. Most importantly, these TQDGs are shown to havebetter thermal and sound insulation properties compared to normal float glass, as well as improved mechanical performance andsafety, which significantly pushes the TPV technology toward practical building integration. TQDGs simultaneously exhibit favorablephotovoltaic, aesthetic, and building envelope characteristics and can serve as a multifunctional material for the realization of nearlyzero-energy building concepts.
Wood is an eco-friendly and abundant substrate and a candidate for functionalization by large-scale nanotechnologies. Infiltration of nanoparticles into wood, however, is hampered by the hierarchically structured and interconnected fibers in wood. In this work, delignified wood is impregnated with gold and silver salts, which are reduced in situ to plasmonic nanoparticles via microwave-assisted synthesis. Transparent biocomposites are produced from nanoparticle-containing wood in the form of load-bearing materials with structural color. The coloration stems from nanoparticle surface plasmons, which require low size dispersity and particle separation. Delignified wood functions as a green reducing agent and a reinforcing scaffold to which the nanoparticles attach, predesigning their distribution on the surface of fibrous "tubes". The nanoscale structure is investigated using scanning transmission electron microscopy (STEM), energy-dispersive spectroscopy (EDS), and Raman microscopy to determine particle size, particle distribution, and structure-property relationships. Optical properties, including response to polarized light, are of particular interest.
Transparent wood (TW) is an interesting polymer biocomposite with potential for buildings and photonics applications. TW materials need to be eco-friendly and readily processed with few defects, for high optical transmittance and low transmission scattering at wide angles (haze). Two wood templates with different lignin-content are impregnated with a new thiol-ene thermoset system. The more eco-friendly bleached wood template results in transparent wood with high optical transmission and much reduced transmission haze, due to strong reduction of interfacial air gaps. Characterization includes template composition, thiol-ene distribution, and polymerization in wood cell wall by EDX and confocal Raman microscopy, also NMR and DSC, tensile testing and FE-SEM fractography for morphology and wood/thiol-ene interface adhesion assessment. The wood template is a true nanocomposite with thiol-ene polymer located inside the nanoporous wood cell wall. Advanced TW applications require not only appropriate wood template modification and careful polymer matrix selection but also tailoring of the process to impregnation and polymerization mechanisms, in order to reduce optical defects.