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1.
Biomacromolecules ; 20(10): 3924-3932, 2019 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-31525970

RESUMO

Many polymers, including polyethylene, feature a relatively low melting point and hence must be cross-linked to make them viable for applications that demand a high stiffness and creep resistance at elevated temperatures. The resulting thermoset plastics cannot be recycled, and therefore alternative materials with a reconfigurable internal network structure are in high demand. Here, we establish that such a thermoset-like yet recyclable material can be realized through the addition of a nanocellulose reinforcing agent. A network consisting of cellulose nanocrystals, nano- or microfibrils imparts many of the characteristics that are usually achieved through chemical cross-linking. For instance, the addition of only 7.5 wt % of either nanocellulose material significantly enhances the melt stiffness of an otherwise molten ethylene-acrylate copolymer by at least 1 order of magnitude. At the same time, the nanocellulose network reduces the melt creep elongation to less than 10%, whereas the neat molten matrix would rupture. At high shear rates, however, the molten composites do not display a significantly higher viscosity than the copolymer matrix, and therefore retain the processability of a thermoplastic material. Repeated re-extrusion at 140 °C does not compromise the thermomechanical properties, which indicates a high degree of recyclability. The versatility of dynamic nanocellulose networks is illustrated by 3D printing of a cellulose composite, where the high melt stiffness improves the printability of the resin.

2.
ACS Nano ; 13(6): 6409-6420, 2019 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-31083978

RESUMO

A molecularly engineered water-borne reactive compatibilizer is designed for tuning of the interface in melt-processed thermoplastic poly(caprolactone) (PCL)-cellulose nanocomposites. The mechanical properties of the nanocomposites are studied by tensile testing and dynamic mechanical analysis. The reactive compatibilizer is a statistical copolymer of 2-(dimethylamino)ethyl methacrylate and 2-hydroxy methacrylate, which is subsequently esterified and quaternized. Quaternized ammonium groups in the reactive compatibilizer electrostatically match the negative surface charge of cellulose nanofibrils (CNFs). This results in core-shell CNFs with a thin uniform coating of the compatibilizer. This promotes the dispersion of CNFs in the PCL matrix, as concluded from high-resolution scanning electron microscopy and atomic force microscopy. Moreover, the compatibilizer "shell" has methacrylate functionalities, which allow for radical reactions during processing and links covalently with PCL. Compared to the bio-nanocomposite reference, the reactive compatibilizer (<4 wt %) increased Young's modulus by about 80% and work to fracture 10 times. Doubling the amount of peroxide caused further improved mechanical properties, in support of effects from higher cross-link density at the interface. Further studies of interfacial design in specific nanocellulose-based composite materials are warranted since the detrimental effects from CNFs agglomeration may have been underestimated.

3.
ACS Appl Mater Interfaces ; 11(22): 20465-20472, 2019 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-31062954

RESUMO

Functional load-bearing materials based on phase-change materials (PCMs) are under rapid development for thermal energy storage (TES) applications. Mesoporous structures are ideal carriers for PCMs and guarantee shape stability during the thermal cycle. In this study, we introduce transparent wood (TW) as a TES system. A shape-stabilized PCM based on polyethylene glycol is encapsulated into a delignified wood substrate, and the TW obtained is fully characterized, also in terms of nano- and mesoscale structures. Transparent wood for thermal energy storage (TW-TES) combines large latent heat (∼76 J g-1) with switchable optical transparency. During the heating process, optical transmittance increases by 6% and reaches 68% for 1.5 mm thick TW-TES. Characterization of the thermal energy regulation performance shows that the prepared TW-TES composite is superior to normal glass because of the combination of good heat-storage and thermal insulation properties. This makes TW-TES composites interesting candidates for applications in energy-saving buildings.

4.
Nanoscale ; 11(22): 11001-11011, 2019 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-31140534

RESUMO

Chitin nanofibrils (ChNF) are interesting high-value constituents for nanomaterials due to the enormous amount of waste from the seafood industry. So far, the reported ChNFs are substantially modified and chemically degraded (shortened) during extraction from the organisms. Here, highly individualized and long native-state ß-chitin nanofibrils from Illex argentinus squid pens are prepared. A mild treatment was developed to preserve the molar mass, aspect ratio, degree of acetylation and crystallite structure. The fibrils show a uniform diameter of 2-7 nm, very high aspect ratio (up to 750), high degree of acetylation (DA = 99%), and high molar mass (843 500 dalton). The powder X-ray diffraction analysis showed the preserved crystallite structure after protein removal. These "high quality" ChNFs were used to prepare nanostructured films via vacuum filtration from stable hydrocolloids. The effects of well-preserved "native" fibrils on morphology, and film properties (mechanical and optical), were studied and compared with earlier results based on coarser and shorter, chemically degraded chitin fibrils.

5.
ACS Appl Mater Interfaces ; 11(10): 10310-10319, 2019 Mar 13.
Artigo em Inglês | MEDLINE | ID: mdl-30762342

RESUMO

Ecofriendly materials based on well-preserved and nanostructured wood cellulose fibers are investigated for the purpose of load-bearing applications, where optical transmittance may be advantageous. Wood fibers are subjected to mild delignification, flow orientation, and hot-pressing to form an oriented material of low porosity. The biopolymer composition of the fibers is determined. Their morphology is studied by scanning electron microscopy, cellulose orientation is quantified by X-ray diffraction, and the effect of beating is investigated. Hot-pressed networks are impregnated by a methyl methacrylate monomer and polymerized to form thermoplastic wood fiber/poly(methyl methacrylate) biocomposites. Tensile tests are performed, as well as optical transmittance measurements. Structure-property relationships are discussed. High-density molded fibers from holocellulose have mechanical properties comparable with nanocellulose materials and are recyclable. The thermoplastic matrix biocomposites showed superior mechanical properties (Young's modulus of 20 GPa and ultimate strength of 310 MPa) at a fiber volume fraction of 52%, with high optical transmittance of 90%. The study presents a scalable approach for strong, stiff, and transparent molded fibers/biocomposites.

6.
Biomacromolecules ; 2018 Aug 17.
Artigo em Inglês | MEDLINE | ID: mdl-30047261

RESUMO

A critical aspect in materials design of polymer nanocomposites is the nature of the nanoparticle/polymer interface. The present study investigates the effect of manipulation of the interface between cellulose nanofibrils (CNF) and poly(methyl methacrylate) (PMMA) on the optical, thermal, and mechanical properties of the corresponding nanocomposites. The CNF/PMMA interface is altered with a minimum of changes in material composition so that interface effects can be analyzed. The hydroxyl-rich surface of CNF fibrils is exploited to modify the CNF surface via an epoxide-hydroxyl reaction. CNF/PMMA nanocomposites are then prepared with high CNF content (∼38 wt %) using an approach where a porous CNF mat is impregnated with monomer or polymer. The nanocomposite interface is controlled by either providing PMMA grafts from the modified CNF surface or by solvent-assisted diffusion of PMMA into a CNF network (native and modified). The high content of CNF fibrils of ∼6 nm diameter leads to a strong interface and polymer matrix distribution effects. Moisture uptake and mechanical properties are measured at different relative humidity conditions. The nanocomposites with PMMA molecules grafted to cellulose exhibited much higher optical transparency, thermal stability, and hygro-mechanical properties than the control samples. The present modification and preparation strategies are versatile and may be used for cellulose nanocomposites of other compositions, architectures, properties, and functionalities.

7.
ACS Nano ; 2018 Jun 08.
Artigo em Inglês | MEDLINE | ID: mdl-29882658

RESUMO

We report on a sustainable route to protective nanocomposite coatings, where one of the components, nanocellulose fibrils, is derived from trees and the glass matrix is an inexpensive sol-gel organic-inorganic hybrid of zirconium alkoxide and an epoxy-functionalized silane. The hydrophilic nature of the colloidal nanocellulose fibrils is exploited to obtain a homogeneous one-pot suspension of the nanocellulose in the aqueous sol-gel matrix precursors solution. The mixture is then sprayed to form nanocomposite coatings of a well-dispersed, random in-plane nanocellulose fibril network in a continuous organic-inorganic glass matrix phase. The nanocellulose incorporation in the sol-gel matrix resulted in nanostructured composites with marked effects on salient coating properties including optical transmittance, hardness, fracture energy, and water contact angle. The particular role of the nanocellulose fibrils on coating fracture properties, important for coating reliability, was analyzed and discussed in terms of fibril morphology, molecular matrix, and nanocellulose/matrix interactions.

8.
Biomacromolecules ; 19(7): 3020-3029, 2018 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-29757614

RESUMO

To expand the use of renewable materials, paper products with superior mechanical and optical properties are needed. Although beating, bleaching, and additives are known to improve industrially produced Kraft pulp papers, properties are limited by the quality of the fibers. While the use of nanocellulose has been shown to significantly increase paper properties, the current cost associated with their production has limited their industrial relevance. Here, using a simple mild peracetic acid (PAA) delignification process on spruce, we produce hemicellulose-rich holocellulose fibers (28.8 wt %) with high intrinsic strength (1200 MPa for fibers with microfibrillar angle smaller than 10°). We show that PAA treatment causes less cellulose/hemicellulose degradation and better preserves cellulose nanostructure in comparison to conventional Kraft pulping. High-density holocellulose papers with superior mechanical properties (Young's modulus of 18 GPa and ultimate strength of 195 MPa) are manufactured using a water-based hot-pressing process, without the use of beating or additives. We propose that the preserved hemicelluloses act as "glue" in the interfiber region, improving both mechanical and optical properties of papers. Holocellulose fibers may be affordable and applicable candidates for making special paper/composites where high mechanical performance and/or optical transmittance are of interest.

9.
Biomacromolecules ; 19(7): 2567-2579, 2018 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-29688710

RESUMO

Macromolecular dynamics in biological systems, which play a crucial role for biomolecular function and activity at ambient temperature, depend strongly on moisture content. Yet, a generally accepted quantitative model of hydration-dependent phenomena based on local relaxation and diffusive dynamics of both polymer and its adsorbed water is still missing. In this work, atomistic-scale spatial distributions of motional modes are calculated using molecular dynamics simulations of hydrated xyloglucan (XG). These are shown to reproduce experimental hydration-dependent 13C NMR longitudinal relaxation times ( T1) at room temperature, and relevant features of their broad distributions, which are indicative of locally heterogeneous polymer reorientational dynamics. At low hydration, the self-diffusion behavior of water shows that water molecules are confined to particular locations in the randomly aggregated XG network while the average polymer segmental mobility remains low. Upon increasing water content, the hydration network becomes mobile and fully accessible for individual water molecules, and the motion of hydrated XG segments becomes faster. Yet, the polymer network retains a heterogeneous gel-like structure even at the highest level of hydration. We show that the observed distribution of relaxations times arises from the spatial heterogeneity of chain mobility that in turn is a result of heterogeneous distribution of water-chain and chain-chain interactions. Our findings contribute to the picture of hydration-dependent dynamics in other macromolecules such as proteins, DNA, and synthetic polymers, and hold important implications for the mechanical properties of polysaccharide matrixes in plants and plant-based materials.

10.
Biomacromolecules ; 19(7): 2423-2431, 2018 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-29620880

RESUMO

Although research on nanopaper structures from cellulose nanofibrils (CNFs) is well established, the mechanical behavior is not well understood, especially not when CNF is combined with hard nanoparticles. Cationic CNF (Q-CNF) was prepared and successfully decorated by anionic nanodiamond (ND) nanoparticles in hydrocolloidal form. The Q-CNF/ND nanocomposites were filtered from a hydrocolloid and dried. Unlike many other carbon nanocomposites, the Q-CNF/ND nanocomposites were optically transparent. Reinforcement effects from the nanodiamond were remarkable, such as Young's modulus (9.8 → 16.6 GPa) and tensile strength (209.5 → 277.5 MPa) at a content of only 1.9% v/v of ND, and the reinforcement mechanisms are discussed. Strong effects on CNF network deformation mechanisms were revealed by loading-unloading experiments. Scratch hardness also increased strongly with increased addition of ND.

11.
Biomacromolecules ; 19(7): 2341-2350, 2018 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-29577729

RESUMO

Cellulose nanocomposites can be considered for semistructural load-bearing applications where modulus and strength requirements exceed 10 GPa and 100 MPa, respectively. Such properties are higher than for most neat polymers but typical for molded short glass fiber composites. The research challenge for polymer matrix biocomposites is to develop processing concepts that allow high cellulose nanofibril (CNF) content, nanostructural control in the form of well-dispersed CNF, the use of suitable polymer matrices, as well as molecular scale interface tailoring to address moisture effects. From a practical point of view, the processing concept needs to be scalable so that large-scale industrial processing is feasible. The vast majority of cellulose nanocomposite studies elaborate on materials with low nanocellulose content. An important reason is the challenge to prevent CNF agglomeration at high CNF content. Research activities are therefore needed on concepts with the potential for rapid processing with controlled nanostructure, including well-dispersed fibrils at high CNF content so that favorable properties are obtained. This perspective discusses processing strategies, agglomeration problems, opportunities, and effects from interface tailoring. Specifically, preformed CNF mats can be used to design nanostructured biocomposites with high CNF content. Because very few composite materials combine functional and structural properties, CNF materials are an exception in this sense. The suggested processing concept could include functional components (inorganic clays, carbon nanotubes, magnetic nanoparticles, among others). In functional three-phase systems, CNF networks are combined with functional components (nanoparticles or fibril coatings) together with a ductile polymer matrix. Such materials can have functional properties (optical, magnetic, electric, etc.) in combination with mechanical performance, and the comparably low cost of nanocellulose may facilitate the use of large nanocomposite structures in industrial applications.

12.
ACS Nano ; 12(3): 2222-2230, 2018 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-29412639

RESUMO

Tremendous efforts have been dedicated to developing effective and eco-friendly approaches for separation of oil-water mixtures. Challenges remain in terms of complex processing, high material cost, low efficiency, and scale-up problems. Inspired by the tubular porosity and hierarchical organization of wood, a strong, mesoporous, and hydrophobic three-dimensional wood structure is created for selective oil/water separation. A delignified wood template with hydrophilic characteristics is obtained by removal of lignin. The delignified wood template is further functionalized by a reactive epoxy-amine system. This wood/epoxy biocomposite reveals hydrophobic/oleophilic functionality and shows oil absorption as high as 15 g/g. The wood/epoxy biocomposite has a compression yield strength and modulus up to 18 and 263 MPa, respectively, at a solid volume fraction of only 12%. This is more than 20 times that of cellulose-based foams/aerogels reconstructed from cellulose nanofibrils. The favorable performance is ascribed to the natural hierarchical honeycomb structure of wood. Oil can be selectively absorbed not only from below but also from above the water surface. High oil/water absorption capacity of both types of wood structures (delignified template and polymer-modified biocomposite) allows for applications in oil/water separation.

13.
Adv Mater ; 30(19): e1704285, 2018 May.
Artigo em Inglês | MEDLINE | ID: mdl-29468736

RESUMO

It is a challenging task to realize the vision of hierarchically structured nanomaterials for large-scale applications. Herein, the biomaterial wood as a large-scale biotemplate for functionalization at multiple scales is discussed, to provide an increased property range to this renewable and CO2 -storing bioresource, which is available at low cost and in large quantities. The Progress Report reviews the emerging field of functional wood materials in view of the specific features of the structural template and novel nanotechnological approaches for the development of wood-polymer composites and wood-mineral hybrids for advanced property profiles and new functions.

14.
Carbohydr Polym ; 181: 256-263, 2018 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-29253970

RESUMO

The mechanical properties of cellulose nanofibrils network structure are essential for their applications in functional materials. In this work, an adhesive peptide consisting of just 11 amino acid residues with a hydrophobic core sequence of FLIVI (F - phenylalanine, L - leucine, I - isoleucine, V - valine) flanked by three lysine (K) residues was adsorbed to 2,2,6,6-Tetramethyl-1-piperidinyloxy radical (TEMPO) oxidized cellulose nanofibrils (TO-CNF). Composite films were prepared by solution casting from water suspensions of TO-CNF adsorbed with the adhesive peptide. The nanofibrils network structure of the composite was characterized by atomic force microscopy (AFM). The structure of the peptide in the composites and the interactions between TO-CNF and the peptide were studied by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The mechanical properties of the composites were characterized by tensile tests and dynamic mechanical analysis (DMA). With 6.3wt.% adhesive peptide adsorbed onto TO-CNF, the composite showed a modulus of 12.5±1.4GPa, a tensile strength of 344.5±(15.3)MPa, and a strain to failure of 7.8±0.4%, which are 34.4%, 48.8%, and 23.8% higher than those for neat TO-CNF, respectively. This resulted in significantly improved toughness (work to fracture) for the composite, 77% higher than that for the neat TO-CNF.


Assuntos
Adesivos/farmacologia , Celulose/química , Teste de Materiais , Nanofibras/química , Peptídeos/farmacologia , Adesivos/química , Adsorção , Sequência de Aminoácidos , Celulose/ultraestrutura , Óxidos N-Cíclicos/química , Microscopia de Força Atômica , Nanofibras/ultraestrutura , Oxirredução , Peptídeos/química , Espectroscopia de Infravermelho com Transformada de Fourier , Temperatura Ambiente , Resistência à Tração , Difração de Raios X
15.
Biomacromolecules ; 18(12): 4405-4410, 2017 Dec 11.
Artigo em Inglês | MEDLINE | ID: mdl-29135235

RESUMO

We report the mechanical strength of native chitin nanofibrils. Highly crystalline α-chitin nanofibrils were purified from filaments produced by a microalgae Phaeocystis globosa, and two types of ß-chitin nanofibrils were purified from pens of a squid Loligo bleekeri and tubes of a tubeworm Lamellibrachia satsuma, with relatively low and high crystallinity, respectively. These chitin nanofibrils were fully dispersed in water. The strength of individualized nanofibrils was estimated using cavitation-induced tensile fracture of nanoscale filaments in a liquid medium. Both types of ß-chitin nanofibrils exhibited similar strength values of approximately 3 GP; in contrast, the α-chitin nanofibrils exhibited a much lower strength value of 1.6 GPa. These strength estimates suggest that the tensile strength of chitin nanofibrils is governed by the molecular packing modes of chitin rather than their crystallinity.


Assuntos
Quitina/química , Nanofibras/química , Animais , Decapodiformes/química , Microalgas/química , Sonicação/métodos , Resistência à Tração , Água/química
16.
ACS Appl Mater Interfaces ; 9(41): 36154-36163, 2017 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-28825295

RESUMO

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.

17.
ACS Appl Mater Interfaces ; 9(23): 20169-20178, 2017 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-28530799

RESUMO

The interfacial adhesion design between "mortar" and "bricks" is essential for mechanical and barrier performance of nanocellulose-based nacre-mimetic nanocomposites, especially at high moisture conditions. To address this fundamental challenge, dopamine (DA) has been conjugated to cellulose nanofibrils (CNFs) and subsequently assembled with montmorillonite (MTM) to generate layered nanocomposite films inspired by the strong adhesion of mussel adhesive proteins to inorganic surfaces under water. The selective formation of catechol/metal ion chelation and hydrogen bonding at the interface between MTM platelets and CNFs bearing DA renders transparent films with strong mechanical properties, particularly at high humidity and in wet state. Increasing the amount of conjugated DA on CNFs results in nanocomposites with increased tensile strength and modulus, up to 57.4 MPa and 1.1 GPa, respectively, after the films are swollen in water. The nanocomposites also show excellent gas barrier properties at high relative humidity (95%), complementing the multifunctional property profile.

18.
ACS Appl Mater Interfaces ; 9(7): 6453-6461, 2017 Feb 22.
Artigo em Inglês | MEDLINE | ID: mdl-28155270

RESUMO

Clay aerogels are foam-like materials with potential to combine high mechanical performance with fire retardancy. However, the compression strength of these aerogels is much lower than theoretically predicted values. High-strength aerogels with more than 95% porosity were prepared from a ternary material system based on poly(vinyl alcohol), montmorillonite clay platelets, and cellulose nanofibrils. A hydrocolloidal suspension of the three components was subjected to freeze-drying so that a low-density aerogel foam was formed. Cell structure was studied by field-emission scanning electron microscopy. Interactions at the molecular scale were observed by X-ray diffraction and Fourier transform infrared spectroscopy. Cross-linking was carried out using glutaraldehyde or borax, and moisture stability was investigated. These biobased ternary aerogels showed compression strength much better than that of previously studied materials and also showed strength higher than that of high-performance sandwich foam cores such as cross-linked polyvinyl chloride foams.

19.
ChemSusChem ; 9(9): 989-95, 2016 05 10.
Artigo em Inglês | MEDLINE | ID: mdl-27061912

RESUMO

Chitin nanofibers of unique structure and properties can be obtained from crustacean and fishery waste. These chitin nanofibers have roughly 4 nm diameters, aspect ratios between 25-250, a high degree of acetylation and preserved crystallinity, and can be potentially applied in hydrogels. Hydrogels with a chitin nanofiber content of 0.4, 0.6, 0.8, 1.0, 2.0, and 3.0 wt % were successfully prepared. The methodology for preparation is new, environmentally friendly, and simple as gelation is induced by neutralization of the charged colloidal mixture, inducing precipitation and secondary bond interaction between nanofibers. Pore structure and pore size distributions of corresponding aerogels are characterized using auto-porosimetry, revealing a substantial fraction of nanoscale pores. To the best of our knowledge, the values for storage (13 kPa at 3 wt %) and compression modulus (309 kPa at 2 wt %) are the highest reported for chitin nanofibers hydrogels.


Assuntos
Quitina/química , Hidrogéis/química , Nanofibras/química , Força Compressiva , Estrutura Molecular , Porosidade
20.
Nanoscale ; 7(42): 17957-63, 2015 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-26465589

RESUMO

All-cellulose nanocomposite films containing crystalline TEMPO-oxidized cellulose nanofibrils (TOCNs) of 0-1 wt% were fabricated by mixing aqueous TOCN dispersions with alkali/urea/cellulose (AUC) solutions at room temperature. The mixtures were cast on glass plates, soaked in an acid solution, and the regenerated gel-like films were washed with water and then dried. The TOCN did not form agglomerates in the composites, and had the structure of TOCN-COOH, forming hydrogen bonds with the hydroxyl groups of the regenerated cellulose molecules. X-ray diffraction analysis revealed that the matrix cellulose molecules increased the cellulose II crystal size upon incorporation of TOCN. As a result, the TOCN/AUC composite films had high Young's modulus, tensile strength, thermal stability and oxygen-barrier properties. The TOCN/AUC composite films are promising all-cellulose nanocomposites for versatile applications as new bio-based materials.

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