Reference
Nanoparticle polymer composites: Where two small worlds meet
bstract
The mixing of polymers and nanoparticles is opening pathways for engineering flexible composites that exhibit advantageous electrical, optical, or mechanical properties. Recent advances reveal routes to exploit both enthalpic and entropic interactions so as to direct the spatial distribution of nanoparticles and thereby control the macroscopic performance of the material. For example, by tailoring the particle coating and size, researchers have created self-healing materials for improved sustainability and self-corralling rods for photovoltaic applications. A challenge for future studies is to create hierarchically structured composites in which each sublayer contributes a distinct function to yield a mechanically integrated, multifunctional material.
Effect of reaction conditions on the properties and behavior of wood cellulose nanocrystal suspensions
Abstract
Sulfuric acid hydrolysis of native cellulose fibers produces stable suspensions of cellulose nanocrystals. Above a critical concentration, the suspensions spontaneously form an anisotropic chiral nematic liquid crystal phase. We have examined the effect of reaction time and acid-to-pulp ratio on nanocrystal and suspension properties for hydrolyzed black spruce acid sulfite pulp. Longer hydrolysis times produced shorter, less polydisperse black spruce cellulose nanocrystals and slightly increased the critical concentration for anisotropic phase formation. Increased acid-to-pulp ratio reduced the dimensions of the nanocrystals thus produced; the critical concentration was increased and the biphasic range became narrower. A suspension made from a bleached kraft eucalyptus pulp gave very similar properties to the softwood nanocrystal suspension when prepared under similar hydrolysis conditions. © 2005 American Chemical Society.
Processing of cellulose nanofiber-reinforced composites
Abstract
Cellulose nanofibers are obtained from various sources such as flax bast fibers, hemp fibers, kraft pulp, and rutabaga, by chemical treatments followed by innovative mechanical techniques. The nanofibers thus obtained have diameters between 5 and 60 nm. The ultrastructure of cellulose nanofibers is investigated by atomic force microscopy and transmission electron microscopy. The cellulose nanofibers are also characterized in terms of crystallinity. Reinforced composite films comprising 90% polyvinyl alcohol and 10% nanofibers are also prepared. The comparison of the mechanical properties of these composites with those of pure PVA confirmed the superiority of the former. © 2005 Sage Publications.
Optimization of the isolation of nanocrystals from microcrystalline cellulose by acid hydrolysis
Abstract
The objective of this work was to find a rapid, high-yield process to obtain an aqueous stable colloid suspension of cellulose nanocrystals/ whiskers. Large quantities are required since these whiskers are designed to be extruded into polymers in the production of nano-biocomposites. Microcrystalline cellulose (MCC), derived from Norway spruce (Picea abies), was used as the starting material. The processing parameters have been optimized by using response surface methodology. The factors that varied during the process were the concentration of MCC and sulfuric acid, the hydrolysis time and temperature, and the ultrasonic treatment time. Responses measured were the median size of the cellulose particles/whiskers and yield. The surface charge as calculated from conductometric titration, microscopic examinations (optical and transmission electron microscopy), and observation of birefringence were also investigated in order to determine the outcome (efficiency) of the process. With a sulfuric acid concentration of 63.5% (w/w), it was possible to obtain cellulose nanocrystals/whiskers with a length between 200 and 400 nm and a width less than 10 nm in approximately 2 h with a yield of 30% (of initial weight). © Springer Science+Business Media, Inc. 2006.
Mechanically-induced chemical changes in polymeric materials
Abstract
Mechanically-induced chemical changes in polymeric materials were studied. Polymeric materials exhibit an extraordinary range of mechanical responses, which depend on the chemical and physical structure of the polymer chains. The mechanical response of thermoplastic polymers is highly influenced by the molecular mass, chain entanglements, chain alignment, and degree of crystallinity. The mechanical properties of these amorphous polymers depend on the molecular mass and the cross-link density. The ability to predict the behavior and limitations of polymers in response to mechanical stress is important for determining their performance in a variety of applications. Quantum mechanical calculations and simulations have been used to predict the energy required to break bonds in small molecules and polymers and to predict which bonds are most likely to be cleaved. Mechanophores that undergo cross-linking reactions triggered by a mechanical field could provide a mechanism for modulating material properties in response to an external force field.
Novel process for isolating fibrils from cellulose fibers by high-intensity ultrasonication. II. fibril characterization
Abstract
High-intensity ultrasonication with a batch process was used to isolate fibrils from several cellulose sources, and a mixture of microscale and nanoscale fibrils was obtained. The geometrical characteristics of the fibrils were investigated with polarized light microscopy, scanning electron microscopy, and atomic force microscopy. The results show that small fibrils with diameters ranging from about 30 nm to several micrometers were peeled from the fibers. Some fibrils were isolated from the fibers, whereas some were still on the fiber surfaces. The lengths of untreated and treated cellulose fibers were investigated by a fiber size analyzer. The crystallinities of some cellulose fibers were evaluated by wide-angle X-ray diffraction and Fourier transform infrared spectroscopy. The high-intensity ultrasonication technique is an environmentally benign method and a simplified process that conducts fiber isolation and chemical modification simultaneously and helps significantly reduce the production cost of cellulose nanofibers and their composites. © 2009 Wiley Periodicals, Inc.
Physical and mechanical properties of polyvinyl alcohol and polypropylene composite materials reinforced with fibril aggregates isolated from regenerated cellulose fibers
Abstract
Natural fibers in micro and nano scales may be a potential alternative for man-made fibers because of the comparable mechanical properties to those of glass, carbon, and aramid fibers. Cellulose fibril and fibril aggregate are generally prepared by physical treatments, e.g., high-pressure homogenizer, or chemical treatments, e.g., acid hydrolysis. In this study, fibril aggregates were generated from a regenerated cellulose fiber by a novel mechanical treatment. The geometrical characteristics of the fibers and the fibril aggregates were investigated using scanning electron microscopy (SEM) and polarized light microscopy (PLM), and its crystallinity was investigated by wide angle X-ray diffraction (WAXD). The degree of fibrillation of the fibers was indirectly evaluated by water retention value (WRV). Nano-biocomposites reinforced with fibril aggregates were prepared by film casting and compression molding and evaluated by tensile test. The morphological characteristics of the nanocomposites were investigated with SEM and PLM. As reference, commercial microfibrillated cellulose was also used to reinforce biodegradable polymer. © Springer Science+Business Media B.V. 2007.
Green chemistry: The sonochemical approach
Abstract
Although the applications of ultrasound have long been known in both industry and academy, the "green" value of the non-hazardous acoustic radiation has been recognised by synthetic and environmental chemists only recently. The chemical and physical effects of ultrasound arise from the cavitational collapse which produce extreme conditions locally and thus induce the formation of chemical species not easily attained under conventional conditions, driving a particular radical reactivity. This rationale, accessible in a non-mathematical manner, anticipates the advantages of using this technology in a variety of processes that include milder reactions with improved yields and selectivities, easy generation of reactive species and catalysts or replacement of hazardous reagents. Sonication enables the rapid dispersion of solids, decomposition of organics including biological components, as well as the formation of porous materials and nanostructures. This review summarises how ultrasound can be harnessed to develop an alternative and mild chemistry, which parallels the ability of acoustic waves to induce homolytic bond cleavage.
Cellulose crystallites
Abstract
This article discusses advances in understanding the structural and physicochemical characteristics of suspensions of cellulose crystallites prepared by acid hydrolysis of natural cellulose fibres. Consideration of recent developments in visualization of crystallite ultrastructure may provide clues to suspension behavior. In addition, novel applications in a diverse range of fields are presented, from iridescent pigments to biomolecular NMR studies.
Fiber-reinforced cellulosic thermoplastic composites
Abstract
Steam-exploded fibers from Yellow poplar (Liriodendron tulipifera) wood were assessed in terms of their thermal stability characteristics, their impact on torque during melt processing of a thermoplastic cellulose ester (plasticized CAB) matrix, their fiber-matrix adhesion and dispersion in composites, and their mechanical properties under tension. Fibers included water-extracted steam-exploded fibers (WEF), alkali extracted fibers (AEF), acetylated fibers (AAEF), and a commercial milled oat fib
Reference
Nanoparticle polymer composites: Where two small worlds meet
bstract
The mixing of polymers and nanoparticles is opening pathways for engineering flexible composites that exhibit advantageous electrical, optical, or mechanical properties. Recent advances reveal routes to exploit both enthalpic and entropic interactions so as to direct the spatial distribution of nanoparticles and thereby control the macroscopic performance of the material. For example, by tailoring the particle coating and size, researchers have created self-healing materials for improved sustainability and self-corralling rods for photovoltaic applications. A challenge for future studies is to create hierarchically structured composites in which each sublayer contributes a distinct function to yield a mechanically integrated, multifunctional material.
Effect of reaction conditions on the properties and behavior of wood cellulose nanocrystal suspensions
Abstract
Sulfuric acid hydrolysis of native cellulose fibers produces stable suspensions of cellulose nanocrystals. Above a critical concentration, the suspensions spontaneously form an anisotropic chiral nematic liquid crystal phase. We have examined the effect of reaction time and acid-to-pulp ratio on nanocrystal and suspension properties for hydrolyzed black spruce acid sulfite pulp. Longer hydrolysis times produced shorter, less polydisperse black spruce cellulose nanocrystals and slightly increased the critical concentration for anisotropic phase formation. Increased acid-to-pulp ratio reduced the dimensions of the nanocrystals thus produced; the critical concentration was increased and the biphasic range became narrower. A suspension made from a bleached kraft eucalyptus pulp gave very similar properties to the softwood nanocrystal suspension when prepared under similar hydrolysis conditions. © 2005 American Chemical Society.
Processing of cellulose nanofiber-reinforced composites
Abstract
Cellulose nanofibers are obtained from various sources such as flax bast fibers, hemp fibers, kraft pulp, and rutabaga, by chemical treatments followed by innovative mechanical techniques. The nanofibers thus obtained have diameters between 5 and 60 nm. The ultrastructure of cellulose nanofibers is investigated by atomic force microscopy and transmission electron microscopy. The cellulose nanofibers are also characterized in terms of crystallinity. Reinforced composite films comprising 90% polyvinyl alcohol and 10% nanofibers are also prepared. The comparison of the mechanical properties of these composites with those of pure PVA confirmed the superiority of the former. © 2005 Sage Publications.
Optimization of the isolation of nanocrystals from microcrystalline cellulose by acid hydrolysis
Abstract
The objective of this work was to find a rapid, high-yield process to obtain an aqueous stable colloid suspension of cellulose nanocrystals/ whiskers. Large quantities are required since these whiskers are designed to be extruded into polymers in the production of nano-biocomposites. Microcrystalline cellulose (MCC), derived from Norway spruce (Picea abies), was used as the starting material. The processing parameters have been optimized by using response surface methodology. The factors that varied during the process were the concentration of MCC and sulfuric acid, the hydrolysis time and temperature, and the ultrasonic treatment time. Responses measured were the median size of the cellulose particles/whiskers and yield. The surface charge as calculated from conductometric titration, microscopic examinations (optical and transmission electron microscopy), and observation of birefringence were also investigated in order to determine the outcome (efficiency) of the process. With a sulfuric acid concentration of 63.5% (w/w), it was possible to obtain cellulose nanocrystals/whiskers with a length between 200 and 400 nm and a width less than 10 nm in approximately 2 h with a yield of 30% (of initial weight). © Springer Science+Business Media, Inc. 2006.
Mechanically-induced chemical changes in polymeric materials
Abstract
Mechanically-induced chemical changes in polymeric materials were studied. Polymeric materials exhibit an extraordinary range of mechanical responses, which depend on the chemical and physical structure of the polymer chains. The mechanical response of thermoplastic polymers is highly influenced by the molecular mass, chain entanglements, chain alignment, and degree of crystallinity. The mechanical properties of these amorphous polymers depend on the molecular mass and the cross-link density. The ability to predict the behavior and limitations of polymers in response to mechanical stress is important for determining their performance in a variety of applications. Quantum mechanical calculations and simulations have been used to predict the energy required to break bonds in small molecules and polymers and to predict which bonds are most likely to be cleaved. Mechanophores that undergo cross-linking reactions triggered by a mechanical field could provide a mechanism for modulating material properties in response to an external force field.
Novel process for isolating fibrils from cellulose fibers by high-intensity ultrasonication. II. fibril characterization
Abstract
High-intensity ultrasonication with a batch process was used to isolate fibrils from several cellulose sources, and a mixture of microscale and nanoscale fibrils was obtained. The geometrical characteristics of the fibrils were investigated with polarized light microscopy, scanning electron microscopy, and atomic force microscopy. The results show that small fibrils with diameters ranging from about 30 nm to several micrometers were peeled from the fibers. Some fibrils were isolated from the fibers, whereas some were still on the fiber surfaces. The lengths of untreated and treated cellulose fibers were investigated by a fiber size analyzer. The crystallinities of some cellulose fibers were evaluated by wide-angle X-ray diffraction and Fourier transform infrared spectroscopy. The high-intensity ultrasonication technique is an environmentally benign method and a simplified process that conducts fiber isolation and chemical modification simultaneously and helps significantly reduce the production cost of cellulose nanofibers and their composites. © 2009 Wiley Periodicals, Inc.
Physical and mechanical properties of polyvinyl alcohol and polypropylene composite materials reinforced with fibril aggregates isolated from regenerated cellulose fibers
Abstract
Natural fibers in micro and nano scales may be a potential alternative for man-made fibers because of the comparable mechanical properties to those of glass, carbon, and aramid fibers. Cellulose fibril and fibril aggregate are generally prepared by physical treatments, e.g., high-pressure homogenizer, or chemical treatments, e.g., acid hydrolysis. In this study, fibril aggregates were generated from a regenerated cellulose fiber by a novel mechanical treatment. The geometrical characteristics of the fibers and the fibril aggregates were investigated using scanning electron microscopy (SEM) and polarized light microscopy (PLM), and its crystallinity was investigated by wide angle X-ray diffraction (WAXD). The degree of fibrillation of the fibers was indirectly evaluated by water retention value (WRV). Nano-biocomposites reinforced with fibril aggregates were prepared by film casting and compression molding and evaluated by tensile test. The morphological characteristics of the nanocomposites were investigated with SEM and PLM. As reference, commercial microfibrillated cellulose was also used to reinforce biodegradable polymer. © Springer Science+Business Media B.V. 2007.
Green chemistry: The sonochemical approach
Abstract
Although the applications of ultrasound have long been known in both industry and academy, the "green" value of the non-hazardous acoustic radiation has been recognised by synthetic and environmental chemists only recently. The chemical and physical effects of ultrasound arise from the cavitational collapse which produce extreme conditions locally and thus induce the formation of chemical species not easily attained under conventional conditions, driving a particular radical reactivity. This rationale, accessible in a non-mathematical manner, anticipates the advantages of using this technology in a variety of processes that include milder reactions with improved yields and selectivities, easy generation of reactive species and catalysts or replacement of hazardous reagents. Sonication enables the rapid dispersion of solids, decomposition of organics including biological components, as well as the formation of porous materials and nanostructures. This review summarises how ultrasound can be harnessed to develop an alternative and mild chemistry, which parallels the ability of acoustic waves to induce homolytic bond cleavage.
Cellulose crystallites
Abstract
This article discusses advances in understanding the structural and physicochemical characteristics of suspensions of cellulose crystallites prepared by acid hydrolysis of natural cellulose fibres. Consideration of recent developments in visualization of crystallite ultrastructure may provide clues to suspension behavior. In addition, novel applications in a diverse range of fields are presented, from iridescent pigments to biomolecular NMR studies.
Fiber-reinforced cellulosic thermoplastic composites
Abstract
Steam-exploded fibers from Yellow poplar (Liriodendron tulipifera) wood were assessed in terms of their thermal stability characteristics, their impact on torque during melt processing of a thermoplastic cellulose ester (plasticized CAB) matrix, their fiber-matrix adhesion and dispersion in composites, and their mechanical properties under tension. Fibers included water-extracted steam-exploded fibers (WEF), alkali extracted fibers (AEF), acetylated fibers (AAEF), and a commercial milled oat fib
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