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The need for more sustainable printed electronics has emerged in the past years. Due to this, the use of nanocellulose (NC) extracted from cellulose has recently been demonstrated to provide interesting materials such as functional inks and transparent flexible films due to its properties. Its high specific surface area together with the high content of reactive hydroxyl groups provide a highly tailorable surface chemistry with applications in ink formulations as a stabilizing, capping, binding and templating agent. Moreover, NC mechanical, physical and thermal properties (high strength, low porosity and high thermal stability, respectively) provide an excellent alternative for the currently used plastic films. In this work, we present a process for the production of water-based conductive inks that uses NC both as a template for silver nanoparticles (Ag NPs) formation and as an ink additive for ink formulation. The new inks present an electrical conductivity up to 2 × 106 S/m, which is in the range of current commercially available conductive inks. Finally, the new Ag NP/NC-based conductive inks have been tested to fabricate NFC antennas by screen-printing onto NC-coated paper, demonstrating to be operative.
Assuntos
Tinta , Nanopartículas Metálicas , Condutividade Elétrica , Eletrônica , Excipientes , Nanopartículas Metálicas/química , Prata/química , ÁguaRESUMO
Nanocellulose (NC) suspensions can form rigid volume-spanning arrested states (VASs) at very low volume fractions. The transition from a free-flowing dispersion to a VAS can be the result of either an increase in particle concentration or a reduction in interparticle repulsion. In this work, the concentration-induced transition has been studied with a special focus on the influence of the particle aspect ratio and surface charge density, and an attempt is made to classify these VASs. The results show that for these types of systems two general states can be identified: glasses and gels. These NC suspensions had threshold concentrations inversely proportional to the particle aspect ratio. This dependence indicates that the main reason for the transition is a mobility constraint that, together with the reversibility of the transition, classifies the VASs as colloidal glasses. If the interparticle repulsion is reduced, then the glasses can transform into gels. Thus, depending on the preparation route, either soft and reversible glasses or stiff and irreversible gels can be formed.
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The structural properties and aggregation behavior of carboxymethylated cellulose nanocrystals (CNC-COOH) were analyzed with small angle neutron scattering (SANS), transmission electron microscopy (TEM), atomic force microscopy (AFM), and dynamic light scattering (DLS) and compared to sulfuric acid hydrolyzed cellulose nanocrystals (CNC-SO3H). The CNC-COOH system, prepared from single carboxymethylated cellulose nanofibrils, was shown to laterally aggregate into 2D-stacks that were stable both in bulk solution and when adsorbed to surfaces. CNC-SO3H also showed a 2D aggregate structure with similar cross sectional dimensions (a width to height ratio of 8) as CNC-COOH, but a factor of 2 shorter length. SANS and DLS revealed a reversible ordering of the 2D aggregates under semidilute conditions, and a structure peak was observed for both systems. This indicates an early stage of liquid crystalline arrangement of the crystal aggregates, at concentrations below those assessed using birefringence or polarized optical microscopy.
Assuntos
Carboximetilcelulose Sódica/química , Nanopartículas/química , Birrefringência , Floculação , Hidrólise , Nanopartículas/ultraestrutura , Imagem Óptica , Ácidos Sulfúricos/química , ViscosidadeRESUMO
We show that unidirectional freezing of nanocellulose dispersions produces cellular foams with high alignment of the rod-like nanoparticles in the freezing direction. Quantification of the alignment in the long direction of the tubular pores with X-ray diffraction shows high orientation of cellulose nanofibrils (CNF) and cellulose nanocrystals (CNC) at particle concentrations above 0.2 wt % (CNC) and 0.08 wt % (CNF). Aggregation of CNF by pH decrease or addition of salt significantly reduces the particle orientation; in contrast, exceeding the concentration where particles gel by mobility constraints had a relatively small effect on the orientation. The dense nanocellulose network formed by directional freezing was sufficiently strong to resist melting. The formed hydrogels were birefringent and displayed anisotropic laser diffraction patterns, suggesting preserved nanocellulose alignment and cellular structure. Nondirectional freezing of the hydrogels followed by sublimation generates foams with a pore structure and nanocellulose alignment resembling the structure of the initial directional freezing.
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Celulose/química , Hidrogéis/química , Nanofibras/química , Nanopartículas/química , Anisotropia , Congelamento , Tamanho da Partícula , Propriedades de Superfície , Difração de Raios XRESUMO
The packing of cellulose nanocrystals (CNC) in the anisotropic chiral nematic phase has been investigated over a wide concentration range by small-angle X-ray scattering (SAXS) and laser diffraction. The average separation distance between the CNCs and the average pitch of the chiral nematic phase have been determined over the entire isotropic-anisotropic biphasic region. The average separation distances range from 51 nm, at the onset of the anisotropic phase formation, to 25 nm above 6 vol % (fully liquid crystalline phase) whereas the average pitch varies from ≈15 µm down to ≈2 µm as Ï increases from 2.5 up to 6.5 vol %. Using the cholesteric order, we determine that the twist angle between neighboring CNCs increases from about 1° up to 4° as Ï increases from 2.5 up to 6.5 vol %. The dependence of the twisting on the volume fraction was related to the increase in the magnitude of the repulsive interactions between the charged rods as the average separation distance decreases.
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Celulose/química , Cristais Líquidos/química , Nanopartículas/química , Anisotropia , Lasers , Luz , Espalhamento a Baixo Ângulo , Água/química , Difração de Raios XRESUMO
We have chemically modified cellulose nanofibrils (CNF) with furan and maleimide groups, and selectively labeled the modified CNF with fluorescent probes; 7-mercapto-4-methylcoumarin and fluorescein diacetate 5-maleimide, through two specific click chemistry reactions: Diels-Alder cycloaddition and the thiol-Michael reaction. Characterization by solid-state (13)C NMR and infrared spectroscopy was used to follow the surface modification and estimate the substitution degrees. We demonstrate that the two luminescent dyes could be selectively labeled onto CNF, yielding a multicolor CNF that was characterized by UV/visible and fluorescence spectroscopies. It was demonstrated that the multicolor CNF could be imaged using a confocal laser scanning microscope.
Assuntos
Celulose/química , Química Click/métodos , Corantes Fluorescentes/química , Nanopartículas/química , Furanos/química , Maleimidas/química , Madeira/químicaRESUMO
Cellulose is the most abundant organic material on our planet which has a key role in our daily life (e.g., paper, packaging). In recent years, the need for replacing fossil-based materials has expanded the application of cellulose and cellulose derivatives including into electronics and sensing. The combination of nanostructures with cellulose nanofibers (CNFs) is expected to create new opportunities for the development of innovative electronic devices. In this paper, we report on a single-step process for the low temperature (<100 °C), environmentally friendly, and fully scalable CNF-templated highly dense growth of zinc oxide (ZnO) nanorods (NRs). More specifically, the effect of the degree of substitution of the CNF (enzymatic CNFs and carboxymethylated CNFs with two different substitution levels) on the ZnO growth and the application of the developed ZnO NRs/CNF nanocomposites in the development of UV sensors is reported herein. The results of this investigation show that the growth and nature of ZnO NRs are strongly dependent on the charge of the CNFs; high charge promotes nanorod growth whereas with low charge, ZnO isotropic microstructures are created that are not attached to the CNFs. Devices manufactured via screen printing/drop-casting of the ZnO NRs/CNF nanocomposites demonstrate a good photo-sensing response with a very stable UV-induced photocurrent of 25.84 µA. This also exhibits excellent long-term stability with fast ON/OFF switching performance under the irradiance of a UV lamp (15 W).
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Nanocelluloses are anisotropic nanoparticles of semicrystalline assemblies of glucan polymers. They have great potential as renewable building blocks in the materials platform of a more sustainable society. As a result, the research on nanocellulose has grown exponentially over the last decades. To fully utilize the properties of nanocelluloses, a fundamental understanding of their colloidal behavior is necessary. As elongated particles with dimensions in a critical nanosize range, their colloidal properties are complex, with several behaviors not covered by classical theories. In this comprehensive Review, we describe the most prominent colloidal behaviors of nanocellulose by combining experimental data and theoretical descriptions. We discuss the preparation and characterization of nanocellulose dispersions, how they form networks at low concentrations, how classical theories cannot describe their behavior, and how they interact with other colloids. We then show examples of how scientists can use this fundamental knowledge to control the assembly of nanocellulose into new materials with exceptional properties. We hope aspiring and established researchers will use this Review as a guide.
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A new gel polymer electrolyte (GPE) based supercapacitor with an ionic conductivity up to 0.32-0.94 mS cm-2 has been synthesized from a mixture of an ionic liquid (IL) with nanocellulose (NC). The new NC-ionogel was prepared by combining the IL 1-ethyl-3-methylimidazolium dimethyl phosphate (EMIMP) with carboxymethylated cellulose nanofibers (CNFc) at different ratios (CNFc ratio from 1 to 4). The addition of CNFc improved the ionogel properties to become easily printable onto the electrode surface. The new GPE based supercapacitor cell showed good electrochemical performance with specific capacitance of 160 F g-1 and an equivalent series resistance (ESR) of 10.2 Ω cm-2 at a current density of 1 mA cm-2. The accessibility to the full capacitance of the device is demonstrated after the addition of CNFc in EMIMP compared to the pristine EMIMP (99 F g-1 and 14.7 Ω cm-2).
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Cellulose nanofibrils constitute an attractive raw material for carbon-neutral, biodegradable, nanostructured materials. Aqueous suspensions of these nanofibrils are stabilized by electrostatic repulsion arising from deprotonated carboxyl groups at the fibril surface. In the present work, a new model is developed for predicting colloidal stability by considering deprotonation and electrostatic screening. This model predicts the fibril-fibril interaction potential at a given pH in a given ionic strength environment. Experiments support the model predictions that aggregation is induced by decreasing the pH, thus reducing the surface charge, or by increasing the salt concentration. It is shown that the primary mechanism for aggregation upon the addition of salt is the surface charge reduction through specific interactions of counterions with the deprotonated carboxyl groups, and the screening effect of the salt is of secondary importance.
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Celulose/química , Nanoestruturas/química , Água/química , Coloides , Eletricidade , Concentração de Íons de Hidrogênio , Concentração Osmolar , Sais/química , Propriedades de SuperfícieRESUMO
Nanocellulose (NC)-based hybrid coatings and films containing CeO2 and SiO2 nanoparticles (NPs) to impart UV screening and hardness properties, respectively, were prepared by solvent casting. The NC film-forming component (75 wt % of the overall solids) was composed entirely of cellulose nanocrystals (CNCs) or of CNCs combined with cellulose nanofibrils (CNFs). Zeta potential measurements indicated that the four NP types (CNC, CNF, CeO2, and SiO2) were stably dispersed in water and negatively charged at pH values between 6 and 9. The combination of NPs within this pH range ensured uniform formulations and homogeneous coatings and films, which blocked UV light, the extent of which depended on film thickness and CeO2 NP content, while maintaining good transparency in the visible spectrum (â¼80%). The addition of a low amount of CNFs (1%) reduced the film hardness, but this effect was compensated by the addition of SiO2 NPs. Chiral nematic self-assembly was observed in the mixed NC film; however, this ordering was disrupted by the addition of the oxide NPs. The roughness of the hybrid coatings was reduced by the inclusion of oxide NPs into the NC matrix perhaps because the spherical oxide NPs were able to pack into the spaces between cellulose fibrils. We envision these hybrid coatings and films in barrier applications, photovoltaics, cosmetic formulations, such as sunscreens, and for the care and maintenance of wood and glass surfaces, or other surfaces that require a smooth, hard, and transparent finish and protection from UV damage.
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Eco-friendly and cost-effective materials and processes to manufacture functional substrates are crucial to further advance the area of printed electronics. One potential key component in the printed electronics platform is an electrically functionalized paper, produced by simply mixing common cellulosic pulp fibers with high-performance electroactive materials. Herein, an electronic paper including nanographite has been prepared using a standardized and scalable papermaking technique. No retention aid was needed to achieve a conducting nanographite loading as high as 50 wt %. The spontaneous retention that provides the integrity and stability of the nanographite paper, likely originates partially from an observed water-stable adhesion of nanographite flakes onto the fiber surfaces. The resulting paper exhibits excellent electrical characteristics, such as an in-plane conductivity of 107 S/cm and an areal capacitance of 9.2 mF/cm2, and was explored as the back-electrode in printed electrochromic displays.
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Bio-based nanocellulose has been shown to possess impressive mechanical properties and simplicity for chemical modifications. The chemical properties are largely influenced by the surface area and functionality of the nanoscale materials. However, finding the typical cross-sections of nanocellulose, such as cellulose nanofibers (CNFs), has been a long-standing puzzle, where subtle changes in extraction methods seem to yield different shapes and dimensions. Here, we extracted CNFs from wood with two different oxidation methods and variations in degree of oxidation and high-pressure homogenization. The cross-sections of CNFs were characterized by small-angle X-ray scattering and wide-angle X-ray diffraction in dispersed and freeze-dried states, respectively, where the results were analyzed by assuming that the cross-sectional distribution was quantized with an 18-chain elementary microfibril, the building block of the cell wall. We find that the results agree well with a pseudosquare unit having a size of about 2.4 nm regardless of sample, while the aggregate level strongly depends on the extraction conditions. Furthermore, we find that aggregates have a preferred cohesion of phase boundaries parallel to the (110)-plane of the cellulose fibril, leading to a ribbon shape on average.
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Microfibrilas , Madeira , Celulose/química , Estudos Transversais , Difração de Raios XRESUMO
The formation of nematically-ordered cellulose nanofiber (CNF) suspensions with an order parameter fmax≈ 0.8 is studied by polarized optical microscopy, small-angle X-ray scattering (SAXS), and rheological measurements as a function of CNF concentration. The wide range of CNF concentrations, from 0.5 wt% to 4.9 wt%, is obtained using osmotic dehydration. The rheological measurements show a strong entangled network over all the concentration range whereas SAXS measurements indicate that at concentrations >1.05 wt% the CNF suspension crosses an isotropic-anisotropic transition that is accompanied by a dramatic increase of the optical birefringence. The resulting nanostructures are modelled as mass fractal structures that converge into co-existing nematically-ordered regions and network-like regions where the correlation distances decrease with concentration. The use of rapid, upscalable osmotic dehydration is an effective method to increase the concentration of CNF suspensions while partly circumventing the gel/glass formation. The facile formation of highly ordered fibers can result in materials with interesting macroscopic properties.
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We have followed the structural evolution during evaporation-induced self-assembly of sulfonated cellulose nanocrystal (CNC) in the presence of H+ and Li+ counterions by small-angle X-ray scattering. Drying of CNC-H dispersions results in ordered films that could not be readily redispersed, while the CNC-Li films were disordered and prone to reswelling and redispersion. The scaling of the separation distance (d) between CNC particles and the particle concentration (c) shows that the CNC-H dispersions display a unidimensional contraction of the nematic structure (d â c-1) during drying, while the CNC-Li dispersions consolidate isotropically (d â c-1/3), which is characteristic for hydrogels with no preferential orientation. Temporal evolution of the structure factor and complementary dynamic light-scattering measurements show that CNC-Li is more aggregated than CNC-H during evaporation-induced assembly. Insights on the structural evolution during CNC assembly and redispersion can promote development of novel and optimized processing routes of nanocellulose-based materials.
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Assembly of bio-based nano-sized particles into complex architectures and morphologies is an area of fundamental interest and technical importance. We have investigated the assembly of sulfonated cellulose nanocrystals (CNC) dispersed in a shrinking levitating aqueous drop using time-resolved small angle X-ray scattering (SAXS). Analysis of the scaling of the particle separation distance (d) with particle concentration (c) was used to follow the transition of CNC dispersions from an isotropic state at 1-2 vol% to a compressed nematic state at particle concentrations above 30 vol%. Comparison with SAXS measurements on CNC dispersions at near equilibrium conditions shows that evaporation-induced assembly of CNC in large levitating drops is comparable to bulk systems. Colloidal states with d vs. c scalings intermediate between isotropic dispersions and unidirectional compression of the nematic structure could be related to the biphasic region and gelation of CNC. Nanoscale structural information of CNC assembly up to very high particle concentrations can help to fabricate nanocellulose-based materials by evaporative methods.
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Aggregation of dispersed rod-like particles like nanocellulose can improve the strength and rigidity of percolated networks but may also have a detrimental effect on the foamability. However, it should be possible to improve the strength of nanocellulose foams by multivalent ion-induced aggregation if the aggregation occurs after the foam has been formed. Lightweight and highly porous foams based on TEMPO-mediated oxidized cellulose nanofibrils (CNF) were formulated with the addition of a non-ionic surfactant, pluronic P123, and CaCO3 nanoparticles. Foam volume measurements show that addition of the non-ionic surfactant generates wet CNF/P123 foams with a high foamability. Foam bubble size studies show that delayed Ca-induced aggregation of CNF by gluconic acid-triggered dissolution of the CaCO3 nanoparticles significantly improves the long-term stability of the wet composite foams. Drying the Ca-reinforced foam at 60 °C results in a moderate shrinkage and electron microscopy and X-ray tomography studies show that the pores became slightly oblate after drying but the overall microstructure and pore/foam bubble size distribution is preserved after drying. The elastic modulus (0.9-1.4 MPa) of Ca-reinforced composite foams with a density of 9-15 kg/m(3) is significantly higher than commercially available polyurethane foams used for thermal insulation.
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Nanocellulose fibrils are ubiquitous in nature and nanotechnologies but their mesoscopic structural assembly is not yet fully understood. Here we study the structural features of rod-like cellulose nanoparticles on a single particle level, by applying statistical polymer physics concepts on electron and atomic force microscopy images, and we assess their physical properties via quantitative nanomechanical mapping. We show evidence of right-handed chirality, observed on both bundles and on single fibrils. Statistical analysis of contours from microscopy images shows a non-Gaussian kink angle distribution. This is inconsistent with a structure consisting of alternating amorphous and crystalline domains along the contour and supports process-induced kink formation. The intrinsic mechanical properties of nanocellulose are extracted from nanoindentation and persistence length method for transversal and longitudinal directions, respectively. The structural analysis is pushed to the level of single cellulose polymer chains, and their smallest associated unit with a proposed 2 × 2 chain-packing arrangement.
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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 13.3 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).
Assuntos
Celulose/química , Condutividade Elétrica , Nanocompostos/química , Nanofibras/química , Nanotubos de Carbono/química , Água/química , Fenômenos MecânicosRESUMO
Cellulose nanofibrils can be obtained from trees and have considerable potential as a building block for biobased materials. In order to achieve good properties of these materials, the nanostructure must be controlled. Here we present a process combining hydrodynamic alignment with a dispersion-gel transition that produces homogeneous and smooth filaments from a low-concentration dispersion of cellulose nanofibrils in water. The preferential fibril orientation along the filament direction can be controlled by the process parameters. The specific ultimate strength is considerably higher than previously reported filaments made of cellulose nanofibrils. The strength is even in line with the strongest cellulose pulp fibres extracted from wood with the same degree of fibril alignment. Successful nanoscale alignment before gelation demands a proper separation of the timescales involved. Somewhat surprisingly, the device must not be too small if this is to be achieved.