The successful development of advanced nanocomposites depends primarily on the sophisticated use of well-dispersed fillers and reinforcements such as nanocelluloses, nanotubes, nanoplatelets, nanofibers, etc. Such nanofillers can enhance the mechanical, electrical, thermal, barrier, optical, tribological, and flame-retardant properties of corresponding nanocomposites when they are homogeneously dispersed into continuous matrices to provide high aspect ratios and large surface area-to-volume ratios.
Fillers and Reinforcements for Advanced Nanocomposites is not limited to the dominant field in polymer nanocomposites. It also covers the wider range of advanced composite topics such as nanoparticle-reinforced metal matrix composites, concrete-based nanocomposites, and bionanocomposites with the use of natural renewable and biodegradable reinforcements. From the perspective of fillers and reinforcements, relatively new nanofillers such as halloysite nanotubes HNTs , bamboo nanocharcoals, and carbon nanopapers CNPs are introduced in addition to popular carbon nanotubes CNTs , nanoclays, graphene oxides GOs , and nanosilica.
Despite the general route of nanocomposite fabrication using in situ polymerization, solution casting, and melt compounding, this book also highlights the development of electrospinning technique to generate ultra-thin nanocomposite fibers as potential fillers and reinforcements.
In Part One, Chapter 1 introduces the fundamentals of nanocellulose and conducting polyaniline and further investigates the synthesis and properties of electrically conductive nanocellulose-based composite films. The effects of concentration of aqueous nanocellulose suspension on the structure and properties of composites are also discussed. The incorporation of CNWs at the low filler loading can significantly increase the tensile strength of composites, which is contrary to MCC at the similar loading with the decrease of tensile strength.
Chapter 3 reviews cellulose nanofiber-based composites with the focus of natural reinforcements such as cellulose and chitin. Nanofiber properties and relevant extraction processes, composite fabrication, and nanofiber dispersibility in polymer matrices are explicitly covered. The effects of HNTs with or without the modifier 3-aminopropyltriethoxysilane on fiber diameter, morphological structure, thermal properties, crystalline structures, and degree of crystallinity, as well as the intermolecular interaction of electrospun nanocomposite fibers, are thoroughly studied to provide the appropriate guidance to the controlled drug release associated with fibrous structures.
Chapter 5 deals with the synthesis and characterization of CNT hybrid fillers via chemical vapor deposition CVD technique for polymer nanocomposites. Optimized synthesis parameters are presented and comparative studies are also conducted between chemical hybrid-filled and physical hybrid-filled polymer nanocomposites in terms of their typical applications. In particular, the impacts of interactions between biopolymer matrices and clays on the structural, mechanical, and thermal properties as well as the biodegradability of currently available bio-based polymer nanocomposites are evaluated, along with the summary of future trends for such bio-nanocomposites.
Chapter 7 elaborates on the recent research progress in graphene-based polymer nanocomposites, which consists of the graphene synthesis method, its surface modification, and fabrication techniques as well as applications of graphene-reinforced nanocomposites.
Chapter 8 works on the production of multifunctional nanocomposite films using reduced GO and poly methyl methacrylate PMMA via electrospinning and compression molding. With exceptional electrical conductivity and gas barrier properties, such nanocomposite films are proven to be highly suitable for applications in food and beverage packaging and chemical processing plants.
Chapter 9 studies the effect of exfoliated GO on the processing characteristics of glass composites by the resin-infusion process. The rheological behavior and cure kinetics of GO as well as the flexural properties of composites are determined to assess the influence of GO content on important resin-infusion processing parameters. Such nanocomposites are detected to exhibit much greater flame retardancy than neat epoxy, which is ascribed to the synergistic effect among silicon, phosphorous, and GNOs.
In Part Four, Chapter 11 offers the effectiveness of calcium carbonate nanoparticles on the improvements of compressive strength and durability of high-volume fly ash concrete. These resulting properties are further correlated with relevant microstructure and crystalline phases by means of X-ray diffraction, mercury intrusion porosimetry, differential thermal analysis, and thermal gravimetric analysis. Chapter 12 reviews current research and relevant techniques for the manufacture and application of amorphous carbon and its nanocomposites. Various applications for the textile, plastic, and health-care industries, as well as in the fields of gas and water filtering, electrical applications, and food packaging, are also discussed based on the superior and unique properties of these materials.
The effect of coupling agent, preparation process, and nanofiller content on the structural, mechanical, and thermal properties of composite films is investigated, which confirms that the incorporation of silica nanofillers can enhance the overall material performance of polyimide. Chapter 14 reviews the recent trends on nanoparticle-reinforced metal matrix composites and related critical issues.
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The main challenge is stated to retain the nanosize of reinforced particles in metal matrices after material processing in order to improve fracture toughness, creep resistance, thermal shock resistance, wear resistance, and dimensional stability at high temperatures for nanocomposites. In Part Five, Chapter 15 offers the fabrication strategies of CNPs as a promising candidate material for device areas and engineering, which consists of CVD and solution-based deposition. Widespread applications are also briefly illustrated, such as transistor, transparent electrode, flexible display, flame retardancy, de-icing, and lightning strike protection, on the basis of the electrical, optical, and mechanical properties of CNPs.
Chapter 16 addresses various principles of energy-harvesting techniques, selected fillers and polymer matrices, and processing possibilities as crucial parameters for energy storage. Moreover, mechanical and thermal properties of advanced nanocomposites in relation to energy-harvesting performance are evaluated. Chapter 17 summarizes the fracture toughness of epoxy resin modified with silica nanoparticles in terms of particle size and concentration effects to establish the structure—property relationship in a nanosilica-reinforced epoxy composite system.
Chapter 18 investigates the effect of micro- and nanofillers as reinforcements and curing cycle on curing-induced shrinkage of epoxy resins. Such study lays a solid foundation for measuring shrinkage-induced effects on strengths of resins and resulting micro- and nanocomposites. Chapter 19 assesses the impact behavior of glass fiber-reinforced polymer composites with various concentrations of nanoclays and hollow glass microspheres. Chapter 20 describes the latest research achievements of the contributors' group on the tribological performance of polytetrafluoroethylene nanocomposites reinforced with nanoserpentine powders and lamellar nanostructure-expanded graphite.
Perspectives for future directions, challenges, and possible avenues for the further enhancement of nanocomposite gel properties are finally mentioned. This book gathers a wide spectrum of fillers and reinforcements to be used for the fabrication and synthesis of advanced nanocomposites, which cannot be achieved without the dedication and excellent work from chapter contributors. Furthermore, it presents multidisciplinary work in relation to material engineering, polymer chemistry and physics, material processing, organic synthesis, and industrial design and applications.
It also demonstrates systematic approaches and investigations from processing material characterization to properties of advanced nanocomposites to establish their important nexus as the essential guideline for end-user applications. This book is expected to become a very useful reference and technical book for composite material research and development sectors, university academics, postgraduate students at the master's and PhD levels, and industrialists for material commercialization.
We would like to show our sincere gratitude to all chapter contributors for their persistence and professionalism to timely complete this important edited book after rigorous scholarly peer review and numerous modifications for each of contributed chapters. We appreciate any comments and feedback from peers and industries to improve the overall quality of this book.
We anticipate that the book contents can shed light on the prospect of effective utilization of fillers and reinforcements for advanced nanocomposites. Nanocellulose is attracting more and more attention from the scientists due to its high mechanical strength and environmental sustainability. Nanocellulosebased conducting composite film shows promise in the application of nanopaper-based sensors, flexible electrodes, and conducting adhesives. This chapter first briefly introduces the fundamentals of nanocellulose and conducting polymer polyaniline PANI.
Then, it describes the synthesis and properties of electrically conductive nanocellulose-based composite films. PANI was used as electrical function component. The effects of the concentration of aqueous nanocellulose suspension on the structures and properties of the composites are discussed. Cellulose fibers have been widely used due to their sustainability and good mechanical properties. The term nanocellulose usually refers to the cellulose materials having at least one dimension in the nanometer range.
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Cellulose nanowhiskers, also called cellulose nanocrystals CNC or nanocrystalline cellulose, are usually produced by the acid hydrolysis of natural cellulosic material after removing noncellulosic substance including dewaxing, hemicelluloses, and lignin. Most show a high crystallinity index and a lower aspect ratio; therefore, we expect that the CNWs extracted from tunicates exhibit a high aspect ratio of 38 Eichhorn, The degree of crystallinity, size, and morphology depend on the source of raw materials and preparation methods.
Nanocellulose can be prepared from a variety of sources, such as wood pulp, plant fibers e. Three methods are available for producing nanocellulose, namely, chemical acid hydrolysis, chemical treatment in combination with mechanical refining, and the enzymatic method. Nanocellulose can be extracted from numerous raw natural materials on the Earth. It shows potentials in nanocomposites, paper making, coating additives, food packing, cosmetics, and gas barrier fields.
However, producing nanocellulose in an economic and environmental way and exploring its functional products are the tasks for the researchers. It will promote the development of nanocellulose-based hybrid nanostructures.
Fillers And Reinforcements For Advanced Nanocomposites
Polyaniline PANI , as an intrinsically conducting polymer, is a very promising material because of its ease of synthesis, low-cost monomer, tunable properties, and high environmental stability. PANI can be produced through chemical or electrochemical polymerization methods. The aniline reacts with an excess amount of an oxidant in a suitable solvent, such as acid. The polymerization takes place spontaneously and requires constant stirring. Electrochemical polymerization involves placing both counter and reference electrodes such as platinum into the solution containing diluted monomer and electrolyte the dopant in a solvent.
After applying a suitable voltage, the polymer film immediately starts to form on the working electrolyte. Chemical polymerization has large possibility of mass production at a reasonable cost Toshima and Hara, However, the commercial applications of PANI have been limited due to harsh chemical conditions in the synthesis and purification procedure that often lead to an inflexible polymer. However, the electrical conductivity of the composite was not improved effectively; in particular, the composites become more brittle due to the addition of PANI.
Combining cellulose nanowhiskers and PANI is promising for developing green functional-polymer nanocomposites. Nanocellulose has good film formability because of strong hydrogen bonds between the whiskers, which facilitates the film-forming ability of the composites. The combination of nanocellulose and PANI gives good conductivity and excellent mechanical properties to the nanocomposites. In this chapter, nanocellulose is selected as the film-forming and reinforcing agent for the composite films. Bleached-flax yarns were purchased from Jayashree Textiles, Kolkata, India.
The chemicals were used as received without further purification. Then the suspension was centrifuged and diluted with deionized water. The suspension was freeze-dried prior to being redispersed in deionized water. Aniline HCl powders 0. Aniline HCl solution was added into cellulose nanowhiskers aqueous suspension 0. The weight ratios of aniline HCl monomer and nanocellulose were , , and The mixture was cast directly onto Petri dishes.
The composite film was peeled off after water fully evaporated at room temperature. The samples were sputter coated with gold prior to SEM observation. A droplet of the diluted suspension was allowed to float on, and eventually flow through, a copper grid covered with a carbon film. The samples were then stained by allowing the grids to float in a 2. A four-probe conductivity apparatus Keithley , USA was used for the electrical conductivity test.
The dispersion of nanocellulose in aqueous solutions requires the presence of electrostatic repulsion among individual rigid cellulose nanowhiskers. This electrostatic repulsion is able to be achieved by sulfuric acid hydrolysis, which introduces negatively charged sulfate groups on the whisker surfaces. No large PANI particles were seen at the bottom of the flask.
PANI particles bond well with nanocellulose even though several centrifugation treatments were used to remove unpolymerized monomers. Treating cellulose fibers with sulfuric acid involves esterification of hydroxyl groups by sulfate ions Yao, Introduction of sulfate groups along the surface of the crystallites will result in a negative charge of the surface.
However, upon drying, the crystalline fragments were rodlike and reaggregated to some extent. The aggregation might have resulted from the formation of hydrogen bonds from the hydroxyl groups and the high surface energy of the nanocellulose. The amorphous parts were selectively hydrolyzed, and the crystalline parts remained unaffected. It is usually believed that the nanofibers formed during the oxidative chemical polymerization and then the nanofibers served as scaffolds for further growth of PANI and finally evolved to particle form Huang and Kaner, During the synthesis of PANI, the aniline hydrochloride molecules could be absorbed on the cellulose nanowhisker surfaces via attractive forces, for example, hydrogen bonding between the hydroxyl groups of the cellulose macromolecules and the amine groups of aniline, which ensures uniform distribution and strong adhesion of aniline monomers.
This method is environmentally friendly without any chemical solvent being involved for the synthesis of composite films. The surface of the film is smooth, and no free PANI powders are seen under low magnification. The randomly oriented nanowhiskers overlapping each other are clearly seen.
However, the tiny particles of PANI are observed on the surface of cellulose nanowhiskers at higher magnification, indicating that tiny PANI particles have been preferably polymerized on the surfaces of cellulose nanowhiskers. PANI nanoparticles formed a thin densely packed layer on the whiskers. The diameters of the whiskers increase due to the coating of PANI powders.
A larger diameter of the whisker is clearly seen due to the PANI coating layer. However, the broad halo peak represents the amorphous structure of PANI.
Fillers and Reinforcements for Advanced Nanocomposites
The relative peak intensity of cellulose decreases with an increase in aqueous nanocellulose concentration from 0. The reason for the low crystallinity of PANI formed on nanocellulose is not yet understood. For the spectra of composite films, three peaks are apparently different from those of their components. The first absorption bands are flat and distorted due to the overlapping of the two peaks for the HCl-doped PANI solution.
The thermal properties are critical for many applications, including the use of nanocellulose for the reinforcements in polymer composites under the thermal-blending process. Thus, it is important to evaluate the behavior of the composite at elevated temperature. In: Nanoclay reinforced polymer composites. Pavlidou S, Papaspyrides C A review on polymer—layered silicate nanocomposites.
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