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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
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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The possibility of forming self-organized films using only charge-stabilized dispersions of cellulose I nanofibrils with opposite charges is presented, that is, the multilayers were composed solely of anionically and cationically modified microfibrillated cellulose (MFC) with a low degree of substitution. The build-up behavior and the properties of the layer-by-layer (LbL)-constructed films were studied using a quartz crystal microbalance with dissipation (QCM-D) and stagnation point adsorption reflectometry (SPAR). The adsorption behavior of cationic/anionic MFC was compared with that of polyethyleneimine (PEI)/anionic MFC. The water contents of five bilayers of cationic/anionic MFC and PEI/anionic MFC were approximately 70 and 50%, respectively. The MFC surface coverage was studied by atomic force microscopy (AFM) measurements, which clearly showed a more dense fibrillar structure in the five bilayer PEI/anionic MFC than in the five bilayer cationic/anionic MFC. The forces between the cellulose-based multilayers were examined using the AFM colloidal probe technique. The forces on approach were characterized by a combination of electrostatic and steric repulsion. The wet adhesive forces were very long-range and were characterized by multiple adhesive events. Surfaces covered by PEI/anionic MFC multilayers required more energy to be separated than surfaces covered by cationic/anionic MFC multilayers.
Assuntos
Celulose/química , Nanopartículas/química , Polietilenoimina/química , Quartzo/química , Cristalização , Microscopia de Força Atômica , Espectroscopia Fotoeletrônica , Propriedades de Superfície , Água/químicaRESUMO
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.
Assuntos
Microfibrilas , Madeira , Celulose/química , Estudos Transversais , Difração de Raios XRESUMO
The wetting of two different model cellulose surfaces has been studied; a regenerated cellulose (RG) surface prepared by spin-coating, and a novel multilayer film of poly(ethyleneimine) and a carboxymethylated microfibrillated cellulose (MFC). The cellulose films were characterized in detail using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). AFM indicates smooth and continuous films on a nanometer scale and the RMS roughness of the RG cellulose and MFC surfaces was determined to be 3 and 6 nm, respectively. The cellulose films were modified by coating with various amounts of an anionic fluorosurfactant, perfluorooctadecanoic acid, or covalently modified with pentadecafluorooctanyl chloride. The fluorinated cellulose films were used to follow the spreading mechanisms of three different oil mixtures. The viscosity and surface tension of the oils were found to be essential parameters governing the spreading kinetics on these surfaces. XPS and dispersive surface energy measurements were made on the cellulose films coated with perfluorooctadecanoic acid. A strong correlation was found between the surface concentration of fluorine, the dispersive surface energy and the contact angle of castor oil on the surface. A dispersive surface energy less than 18 mN/m was required in order for the cellulose surface to be non-wetting (theta e>90 degrees ) by castor oil.
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Cellulose nanofibrils (CNF) can be produced in the form of thin, transparent and flexible films. However, the permeability of such materials to oxygen and water vapor is very sensitive to moisture, which limits their potential for a variety of packaging and encapsulation applications. Diffusion barrier coatings were thus developed to reduce the access of water molecules to enzymatically pre-treated and carboxymethylated CNF substrates. The coatings were based on UV curable organic-inorganic hybrids with epoxy, tetraethylorthosilicate (TEOS) and 3-glycidoxypropyltrimethylenesilane (GPTS) precursors and additional vapor formed SiNx layers. A total of 14 monolayer and multilayer coatings with various thickness and hybrid composition were produced and analyzed. The water vapor transmission rate (WVTR) of the bilayer epoxy/CNF film was two times lower compared to that of uncoated CNF film. This was partly due to the water vapor permeability of the epoxy, a factor of two times lower than CNF. The epoxy coating improved the transparency of CNF, however it did not properly wet to the CNF surfaces and the interfacial adhesion was low. In contrast hybrid epoxy-silica coatings led to high adhesion levels owing to the formation of covalent interactions through condensation reactions with the OH-terminated CNF surface. The barrier and optical performance of hybrid coated CNF substrates was similar to that of CNF coated with pure epoxy. In addition, the hybrid coatings provided an excellent planarization effect, with roughness close to 1 nm, one to two orders of magnitude lower than that of the CNF substrates. The WVTR and oxygen transmission rate values of the hybrid coated CNF laminates were in the range 5-10 g/m2/day (at 38°C and 50% RH) and 3-6 cm3/m2/day/bar (at 23°C and 70% RH), respectively, which matches food and pharmaceutical packaging requirements. The permeability to water vapor of the hybrid coatings was moreover found to decrease with increasing the TEOS/GPTS ratio up to 30 wt% and then increase at higher ratio, and to be much lower for thinner coatings due to further UV-induced silanol condensation and faster evaporation of byproducts. The addition of a single 150 nm thick SiNx layer on the hybrid coated CNF improved its water vapor barrier performance by more than 680 times, with WVTR below the 0.02 g/m2/day detection limit.
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Nanocrystalline TiO2 powders of the rutile polymorph, synthesized by a sol-gel method, were treated with water solutions containing, respectively, formic, acetic, and citric acid and glycine in order to study the adsorption properties of these organic species. The samples were characterized by FTIR, Raman, powder XRD, and TEM. It was found that HCOOH, CH3COOH and HOC(COOH)(CH2COOH)2--but not NH2CH2COOH--adsorbed onto TiO2. The adsorption of HCOOH, CH3COOH and NH2CH2COOH onto the (110) surface of rutile was also studied by quantum-chemical periodic density functional theory (DFT) calculations. The organic molecules were from the computations found to adsorb strongly to the surfaces in a bridge-coordinating mode, where the two oxygens of the deprotonated carboxylic acid bind to two surface titanium ions. Surface relaxation is found to influence adsorption geometries and energies significantly. The results from DFT calculations and ab initio molecular-dynamics simulations of formic acid adsorption onto TiO2 are compared and match well with the experimental IR measurements, supporting the bridge-binding geometry of carboxylic-acid adsorption on the TiO2 nanoparticles.
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The layer-by-layer (LbL) deposition method was used for the build-up of alternating layers of nanofibrillated cellulose (NFC) or carboxymethyl cellulose (CMC) with a branched, cationic polyelectrolyte, polyethyleneimine (PEI) on flexible poly (lactic acid) (PLA) substrates. With this procedure, optically transparent nanocellulosic films with tunable gas barrier properties were formed. 50 layer pairs of PEI/NFC and PEI/CMC deposited on PLA have oxygen permeabilities of 0.34 and 0.71 cm(3)·µm/m(2)·day·kPa at 23 °C and 50% relative humidity, respectively, which is in the same range as polyvinyl alcohol and ethylene vinyl alcohol. The oxygen permeability of these multilayer nanocomposites outperforms those of pure NFC films prepared by solvent-casting. The nanocellulosic LbL assemblies on PLA substrates was in detailed characterized using a quartz crystal microbalance with dissipation (QCM-D). Atomic force microscopy (AFM) reveals large structural differences between the PEI/NFC and the PEI/CMC assemblies, with the PEI/NFC assembly showing a highly entangled network of nanofibrils, whereas the PEI/CMC surfaces lacked structural features. Scanning electron microscopy images showed a nearly perfect uniformity of the nanocellulosic coatings on PLA, and light transmittance results revealed remarkable transparency of the LbL-coated PLA films. The present work demonstrates the first ever LbL films based on high aspect ratio, water-dispersible nanofibrillated cellulose, and water-soluble carboxymethyl cellulose polymers that can be used as multifunctional films and coatings with tailorable properties, such as gas barriers and transparency. Owing to its flexibility, transparency and high-performance gas barrier properties, these thin film assemblies are promising candidates for several large-scale applications, including flexible electronics and renewable packaging.
Assuntos
Celulose/química , Ácido Láctico/química , Nanotecnologia/métodos , Polímeros/química , Biodegradação Ambiental , Gases , Teste de Materiais , Microscopia de Força Atômica/métodos , Microscopia Eletrônica de Varredura/métodos , Nanopartículas/química , Óptica e Fotônica , Oxigênio/química , Permeabilidade , Poliésteres , Álcool de Polivinil/química , Propriedades de SuperfícieRESUMO
A novel, technically and economically benign procedure to combine vermiculite nanoplatelets with nanocellulose fibre dispersions into functional biohybrid films is presented. Nanocellulose fibres of 20 nm diameters and several micrometers in length are mixed with high aspect ratio exfoliated vermiculite nanoplatelets through high-pressure homogenization. The resulting hybrid films obtained after solvent evaporation are stiff (tensile modulus of 17.3 GPa), strong (strength up to 257 MPa), and transparent. Scanning electron microscopy (SEM) shows that the hybrid films consist of stratified nacre-like layers with a homogenous distribution of nanoplatelets within the nanocellulose matrix. The oxygen barrier properties of the biohybrid films outperform commercial packaging materials and pure nanocellulose films showing an oxygen permeability of 0.07 cm(3) µm m(-2) d(-1) kPa(-1) at 50% relative humidity. The oxygen permeability of the hybrid films can be tuned by adjusting the composition of the films. Furthermore, the water vapor barrier properties of the biohybrid films were also significantly improved by the addition of nanoclay. The unique combination of excellent oxygen barrier behavior and optical transparency suggests the potential of these biohybrid materials as an alternative in flexible packaging of oxygen sensitive devices such as thin-film transistors or organic light-emitting diode displays, gas storage applications and as barrier coatings/laminations in large volume packaging applications.
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Silicatos de Alumínio/química , Celulose/química , Oxigênio/química , Vapor , Argila , Umidade , Microscopia Eletrônica , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Nanotecnologia/métodos , Oxigênio/análise , Tamanho da Partícula , Permeabilidade , Maleabilidade , Pressão , Estresse MecânicoRESUMO
Structured silicon surfaces, possessing hierarchical porous characteristics consisting of micrometer-sized cavities superimposed upon a network of nanometer-sized pillars or wires, have been fabricated by a plasma-etching process. These surfaces have superoleophobic properties, after being coated with fluorinated organic trichlorosilanes, on intrinsically oleophilic surfaces. By comparison with flat silicon surfaces, which are oleophilic, it has been demonstrated that a combination of low surface energy and the structured features of the plasma-etched surface is essential to prevent oil from penetrating the surface cavities and thus induce the observed macroscopic superoleophobic phenomena with very low contact-angle hysteresis and low roll-off angles. The structured silicon surfaces were coated with cellulose nanocrystals using the polyelectrolyte multilayer technique. The cellulose surfaces prepared in this way were then coated with a monolayer of fluorinated trichlorosilanes. These porous cellulose films displayed highly nonwetting properties against a number of liquids with low surface tension, including alkanes such as hexadecane and decane. The wettability and chemical composition of the cellulose/silicon surfaces were characterized with contact-angle goniometry and X-ray photoelectron spectroscopy, respectively. The nano/microtexture features of the cellulose/silicon surfaces were also studied with field-emission scanning electron microscopy. The highly oleophobic structured cellulose surfaces are very interesting model surfaces for the development of biomimetic self-cleaning surfaces in a vast array of products, including green constructions, packaging materials, protection against environmental fouling, sports, and outdoor clothing, and microfluidic systems.
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A systematic study of the degree of molecular ordering and swelling of different nanocellulose model films has been conducted. Crystalline cellulose II surfaces were prepared by spin-coating of the precursor cellulose solutions onto oxidized silicon wafers before regeneration in water or by using the Langmuir-Schaefer (LS) technique. Amorphous cellulose films were also prepared by spin-coating of a precursor cellulose solution onto oxidized silicon wafers. Crystalline cellulose I surfaces were prepared by spin-coating wafers with aqueous suspensions of sulfate-stabilized cellulose I nanocrystals and low-charged microfibrillated cellulose (LC-MFC). In addition, a dispersion of high-charged MFC was used for the buildup of polyelectrolyte multilayers with polyetheyleneimine on silica with the aid of the layer-by-layer (LbL) technique. These preparation methods produced smooth thin films on the nanometer scale suitable for X-ray diffraction and swelling measurements. The surface morphology and thickness of the cellulose films were characterized in detail by atomic force microscopy (AFM) and ellipsometry measurements, respectively. To determine the surface energy of the cellulose surfaces, that is, their ability to engage in different interactions with different materials, they were characterized through contact angle measurements against water, glycerol, and methylene iodide. Small incidence angle X-ray diffraction revealed that the nanocrystal and MFC films exhibited a cellulose I crystal structure and that the films prepared from N-methylmorpholine-N-oxide (NMMO), LiCl/DMAc solutions, using the LS technique, possessed a cellulose II structure. The degree of crystalline ordering was highest in the nanocrystal films (approximately 87%), whereas the MFC, NMMO, and LS films exhibited a degree of crystallinity of about 60%. The N,N-dimethylacetamide (DMAc)/LiCl film possessed very low crystalline ordering (<15%). It was also established that the films had different mesostructures, that is, structures around 10 nm, depending on the preparation conditions. The LS and LiCl/DMAc films are smooth without any clear mesostructure, whereas the other films have a clear mesostructure in which the dimensions are dependent on the size of the nanocrystals, fibrillar cellulose, and electrostatic charge of the MFC. The swelling of the films was studied using a quartz crystal microbalance with dissipation. To understand the swelling properties of the films, it was necessary to consider both the difference in crystalline ordering and the difference in mesostructure of the films.
Assuntos
Celulose/química , Nanopartículas/química , Água/química , Cristalização , Microscopia de Força Atômica , Modelos Biológicos , Propriedades de Superfície , Difração de Raios XRESUMO
Polyethyleneimine (PEI) and Microfibrillated cellulose (MFC) have been used to buildup polyelectrolyte multilayers (PEM) on silicone oxide and silicone oxynitride surfaces at different pH values and with different electrolyte and polyelectrolyte/colloid concentrations of the components. Consecutive adsorption on these surfaces was studied by in situ dual-polarization interferometry (DPI) and quartz crystal microbalance measurements. The adsorption data obtained from both the techniques showed a steady buildup of multilayers. High pH and electrolyte concentration of the PEI solution was found to be beneficial for achieving a high adsorbed amount of PEI, and hence of MFC, during the buildup of the multilayer. On the other hand, an increase in the electrolyte concentration of the MFC dispersion was found to inhibit the adsorption of MFC onto PEI. The adsorbed amount of MFC was independent of the bulk MFC concentration in the investigated concentration range (15-250 mg/L). Atomic force microscopy measurements were used to image a MFC-treated silicone oxynitride chip from DPI measurements. The surface was found to be almost fully covered by randomly oriented microfibrils after the adsorption of only one bilayer of PEI/MFC. The surface roughness expressed as the rms-roughness over 1 microm2 was calculated to be 4.6 nm (1 bilayer). The adsorbed amount of PEI and MFC and the amount of water entrapped by the individual layers in the multilayer structures were estimated by combining results from the two analytical techniques using the de Feijter formula. These results indicate a total water content of ca. 41% in the PEM.