Showing papers on "Nanocomposite published in 2007"

New Directions for Low-Dimensional Thermoelectric Materials**

Abstract: Many of the recent advances in enhancing the thermoelectric figure of merit are linked to nanoscale phenomena found both in bulk samples containing nanoscale constituents and in nanoscale samples themselves. Prior theoretical and experimental proof-of-principle studies on quantum-well superlattice and quantum-wire samples have now evolved into studies on bulk samples containing nanostructured constituents prepared by chemical or physical approaches. In this Review, nanostructural composites are shown to exhibit nanostructures and properties that show promise for thermoelectric applications, thus bringing together low-dimensional and bulk materials for thermoelectric applications. Particular emphasis is given in this Review to the ability to achieve 1) a simultaneous increase in the power factor and a decrease in the thermal conductivity in the same nanocomposite sample and for transport in the same direction and 2) lower values of the thermal conductivity in these nanocomposites as compared to alloy samples of the same chemical composition. The outlook for future research directions for nanocomposite thermoelectric materials is also discussed.

Ultrastrong and Stiff Layered Polymer Nanocomposites

Abstract: Nanoscale building blocks are individually exceptionally strong because they are close to ideal, defect-free materials. It is, however, difficult to retain the ideal properties in macroscale composites. Bottom-up assembly of a clay/polymer nanocomposite allowed for the preparation of a homogeneous, optically transparent material with planar orientation of the alumosilicate nanosheets. The stiffness and tensile strength of these multilayer composites are one order of magnitude greater than those of analogous nanocomposites at a processing temperature that is much lower than those of ceramic or polymer materials with similar characteristics. A high level of ordering of the nanoscale building blocks, combined with dense covalent and hydrogen bonding and stiffening of the polymer chains, leads to highly effective load transfer between nanosheets and the polymer.

Flexible energy storage devices based on nanocomposite paper

Abstract: There is strong recent interest in ultrathin, flexible, safe energy storage devices to meet the various design and power needs of modern gadgets. To build such fully flexible and robust electrochemical devices, multiple components with specific electrochemical and interfacial properties need to be integrated into single units. Here we show that these basic components, the electrode, separator, and electrolyte, can all be integrated into single contiguous nanocomposite units that can serve as building blocks for a variety of thin mechanically flexible energy storage devices. Nanoporous cellulose paper embedded with aligned carbon nanotube electrode and electrolyte constitutes the basic unit. The units are used to build various flexible supercapacitor, battery, hybrid, and dual-storage battery-in-supercapacitor devices. The thin freestanding nanocomposite paper devices offer complete mechanical flexibility during operation. The supercapacitors operate with electrolytes including aqueous solvents, room temperature ionic liquids, and bioelectrolytes and over record temperature ranges. These easy-to-assemble integrated nanocomposite energy-storage systems could provide unprecedented design ingenuity for a variety of devices operating over a wide range of temperature and environmental conditions.

Enhanced ethanol production inside carbon-nanotube reactors containing catalytic particles

Abstract: Carbon nanotubes (CNTs) have well-defined hollow interiors and exhibit unusual mechanical and thermal stability as well as electron conductivity1. This opens intriguing possibilities to introduce other matter into the cavities2,3,4,5, which may lead to nanocomposite materials with interesting properties or behaviour different from the bulk6,7,8. Here, we report a striking enhancement of the catalytic activity of Rh particles confined inside nanotubes for the conversion of CO and H2 to ethanol. The overall formation rate of ethanol (30.0 mol mol−1Rh h−1) inside the nanotubes exceeds that on the outside of the nanotubes by more than an order of magnitude, although the latter is much more accessible. Such an effect with synergetic confinement has not been observed before in catalysis involving CNTs. We believe that our discovery may be of a quite general nature and could apply to many other processes. It is anticipated that this will motivate theoretical and experimental studies to further the fundamental understanding of the host–guest interaction within carbon and other nanotube systems.

How Nano Are Nanocomposites

Abstract: Composite materials loaded with nanometer-sized reinforcing fillers are widely believed to have the potential to push polymer mechanical properties to extreme values Realization of anticipated properties, however, has proven elusive The analysis presented here traces this shortfall to the large-scale morphology of the filler as determined by small-angle X-ray scattering, light scattering, and electron imaging We examine elastomeric, thermoplastic, and thermoset composites loaded with a variety of nanoscale reinforcing fillers such as precipitated silica, carbon nanotubes (single and multiwalled), and layered silicates The conclusion is that large-scale disorder is ubiquitous in nanocomposites regardless of the level of dispersion, leading to substantial reduction of mechanical properties (modulus) compared to predictions based on idealized filler morphology

A Novel Hydrogel with High Mechanical Strength: A Macromolecular Microsphere Composite Hydrogel

Abstract: The industrial and biomedical applications of hydrogels made from either natural or synthetic sources are strongly limited by their poor mechanical properties. A normal structure (NS) hydrogel breaks under low stress because there are very few energy dissipation mechanisms to slow crack propagation. In addition, as their crosslinking points are distributed irregularly and the polymer chains between the crosslinking points have different lengths, the stress cannot be evenly distributed between the polymer chains, and crack initiation is facile. Many efforts have been focused on increasing the mechanical strength of hydrogels, but the robustness still remains unsatisfactory. In recent years, three kinds of novel hydrogels with unique structures and high mechanical strength have been developed. Topological (TP) gels have figure-ofeight crosslinkers that can slide along polymer chains. The gel swells to about 500 times its original weight and can be stretched to nearly 20 times its original length. The nanocomposite (NC) hydrogel is made from specific polymers with a water-swellable inorganic clay. Most of the macromolecules are grafted onto nanoparticles, indicating that the nanoparticle clay acts as a highly multifunctional crosslinking agent. We believe that the high mechanical strength of this material has its origin in the very high functionality of the rigid crosslinked points and the lack of short chains between crosslinked components, as every active chain has to stretch between nanoparticles. The extension degree of a chain before breakage is controlled by the relationship between its relaxed end-to-end distance and its contour length, which is low for short chains. When a short chain in an NS hydrogel breaks, its load is thrown onto just one or two other adjacent chains, which dramatically increases their load. Hence, multiple chain fractures occur, causing voids and microcracks. However, in an NC hydrogel with large, rigid crosslinking points, the load from a single broken chain will be spread over many other chains, and the material is less likely to form the microcracks and voids responsible for initiating bulk failure. Gong et al. have reported a new method of obtaining strong and tough hydrogels by making double-network (DN) materials with a high molar ratio of the second network to the first network. In this case, the first network is highly crosslinked and the second network is loosely crosslinked. These DN hydrogels demonstrate extremely high mechanical strength. By adding a third component to a DN gel, either a weakly crosslinked network or noncrosslinked linear chains, gels with high-strength and low-frictional coefficients were obtained. Macromolecular microspheres (MMSs) have become an important structure in polymeric materials. The hydrogel microspheres on the microor nanoscale are known as microgels or nanogels, respectively. They are usually environmentally sensitive and are mainly used in drug delivery and other biomedical applications. However, it is difficult to form bulk hydrogels (macrogels) with these microgels, and when formed, the macrogels do not exhibit high mechanical strength. Very little work has been done on incorporating other kinds of microspheres into bulk hydrogel structures, and the improvement in mechanical strength is far less than for the three hydrogels mentioned above. Here, we report a new way of synthesizing hydrogels with a novel, well-defined network structure and high mechanical strength. In this method, a peroxidized MMS acts as both an initiator and a crosslinker. The mechanism for the formation of the peroxide and the initiation of polymerization, as well as for the formation of a hydrogel, are proposed in Scheme 1. The new hydrogel is a macromolecular microsphere composite (MMC) hydrogel. When the MMS emulsion is irradiated with Co c-rays in oxygen, peroxides (POOR and POOH; here P is the macromolecule that comprises the MMS, and R is a short alkyl group) are formed on the surface and possibly, to a certain extent, in the inner part of the MMS. The formation of peroxides on the MMS was proven with iodometry, which is the common method used to verify their formation and determine the amount formed in the polymers. Potassium iodide and isopropyl alcohol were added to the irradiated MMS emulsion, and as the solution was heated and refluxed for 30 min, it gradually became yellow, which indicates the formation of I2 and further establishes the presence of peroxides on the MMS. The peroxides decomposed under heat to form the free radicals PO , OR , and OH . PO initiated the grafting of C O M M U N IC A TI O N

Dominant role of tunneling resistance in the electrical conductivity of carbon nanotube-based composites

Abstract: The effect of nanotube/nanotube contact resistance on the electrical conductivity of carbon nanotube–based nanocomposites is studied. The tunneling resistance due to an insulating film of matrix material between crossing nanotubes is calculated by assuming a rectangular potential barrier in the insulating film. Monte Carlo simulations indicate that the tunneling resistance plays a dominant role in the electrical conductivity of composites, and the maximum tunneling distance is found to be about 1.8nm. Electrical conductivities of composites with inplane random distributions of carbon nanotubes follow the scaling law and the critical exponent depends on the level of contact resistance.

Phosphonic Acid-Modified Barium Titanate Polymer Nanocomposites with High Permittivity and Dielectric Strength

Abstract: Materials with high dielectric permittivity are important in electronic components such as capacitors, gate dielectrics, memories, and power-storage devices. Conventional highpermittivity materials such as barium titanate (BT) can be processed into thin films by using chemical solution deposition yielding a relative permittivity (er) of about 2500 and relatively low dielectric loss but require high-temperature sintering, which is not compatible with many substrate materials. Polymer-based dielectrics, such as biaxially oriented polypropylene (BOPP), have good processability with high dielectric strengths (∼ 640 V lm) suitable for high-energy-density capacitors, but the storage capacity (ca. 1–1.2 J cm) is limited by the low er (ca. 2.2) of these materials. [6] Various approaches to high-er materials based on nanocomposites containing metal particles or other conductive materials have been pursued. Such nanocomposites have afforded huge er values but the resulting materials are limited by the high-temperature processing required, high dielectric loss, or low dielectric strength. Polymer/ceramic nanocomposites in which high-er metal oxide nanoparticles such as BT and lead magnesium niobate–lead titanate (PMN–PT) are incorporated into a polymer host are of significant current interest. The combination of high-er nanoparticles with high-dielectric-strength polymer hosts offers the potential to obtain processable highperformance dielectric materials. Simple solution processing of BT particles in a polymer host generally results in poor film quality and inhomogeneities, which are mainly caused by agglomeration of the nanoparticles. Addition of surfactants, such as phosphate esters and oligomers thereof, can improve the dispersion of BT nanoparticles in host polymers and consequently the overall nanocomposite film quality. However, in such systems, residual free surfactant can lead to high leakage current and dielectric loss. Thus, approaches to bind surface modifiers to BT nanoparticles via robust chemical bonds are highly desirable. Ramesh et al. have reported on the use of trialkoxysilane surface modifiers for the dispersion of BT nanoparticles in epoxy polymer hosts resulting in nanocomposites with reasonably high er, up to 45. [12] With the objective of identifying ligands that can form stable bonds to a BT surface through coordination or condensation, we have investigated a series of different ligand functionalities. In this Communication, we report that phosphonic acid ligands effect robust surface modification of BT and related nanoparticles and that the use of particles modified with suitable phosphonic acid ligands leads to well-dispersed BT nanocomposite films with high er and high dielectric strength. We have investigated the binding of a variety of ligands to the surface of BT nanoparticles, as the stability of the binding on the surface is vital to effective surface modification. We examined the following set of ligands, each bearing an aliphatic octyl chain with a different terminal binding group: C8H17-X, where X = PO(OH)2 (OPA), SO2ONa (OSA), Si(OCH3)3 (OTMOS), and CO2H (OCA). Trialkoxysilanes are widely used surface modifiers for silicate, indium tin oxide, and other metal oxide surfaces. Phosphonic acids have been reported to modify TiO2, ZrO2, and indium tin oxide surfaces and are thought to couple to the surface of metal oxides either by heterocondensation with surface hydroxyl groups or coordination to metal ions on the surface. Carboxylic acid and sulfonic acid groups may also bind to the surface in a similar manner. A sample of each ligand was mixed with BT nanoparticles (30–50 nm, 0.5 mmol ligand/ g BT) in an ethanol/water solution and stirred at 80 °C, followed by extensive washing with ethanol or water and centrifugation to remove excess and/or physisorbed ligand. The treated BT nanoparticles were dried and characterized by using Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA). Figure 1a shows a comparison of FTIR spectra in the C–H stretching region for the BT nanoparticles treated with the ligands described above, followed by washing. These results C O M M U N IC A IO N

Functional inorganic nanofillers for transparent polymers

Abstract: The integration of inorganic nanoparticles into polymers has been used for the functionalization of polymer materials with great success. Whereas in traditional polymer composites, micron sized particles or agglomerates typically cause significant light scattering hampering optical applications, in nanocomposites the particle dimensions are small enough for the production of highly transparent composites. A challenge for the generation of such materials is to develop an integrated synthesis strategy adapting particle generation, surface modification and integration inside the polymer. Surface grafting using polymerizable surfactants or capping agents allows for linking the particles to the polymer. Novel techniques such as in situ polymerization and in situ particle processing are beneficial to avoid aggregation of inorganic particles inside the polymer matrix. The functions associated with inorganic fillers are widespread. Layered silicates and related materials are nowadays commercially available for improving mechanical and barrier properties in packaging. With the availability of highly transparent materials, the focus has shifted towards optical functions such as luminescence and UV-protection in transparent polymers. IR-active fillers are used in laser-holography for transparent poly(methyl methacrylate) (PMMA) nanocomposites. Refractive index modulation and ultrahigh refractive index films were developed based on inorganic materials such as PbS. The integration of magnetic nanoparticles has a great potential for applications such as electromagnetic interference shielding and magneto-optical storage.This tutorial review will summarize functions associated with the integration of inorganic nanofillers in polymers with a focus on optical properties.

Strong isotropic flux pinning in solution-derived YBa2Cu3O7-x nanocomposite superconductor films.

Abstract: Strong isotropic flux pinning in solution-derived YBa 2 Cu 3 O 7− x nanocomposite superconductor films

Monitoring oxidation of multiwalled carbon nanotubes by Raman spectroscopy

Abstract: Multiwalled carbon nanotubes (MWCNTs) were oxidized in air and acids while varying the treatment time and/or temperature. The goal of this approach was to create the highest density of carboxyl groups with moderate sample loss, which is necessary for nanocomposite applications. In situ Raman experiments allowed real-time observation of the structural changes in MWCNTs upon oxidation. The ratio of the Raman intensities of the D and G bands was used to estimate the concentration of defects. It was found that while an oxidation for 6 h in H2SO4/HNO3 provided the strongest effect, a ‘flash oxidation’ in air (15 min at 550 °C) also leads to an efficient functionalization in a cost-effective and environmentally friendly way. Transmission electron microscopy, Fourier-transform infrared (FTIR) spectroscopy, thermogravimetric analysis and electrophoretic mobility analysis were used to study the oxidized nanotubes. Copyright © 2007 John Wiley & Sons, Ltd.

Surface modification and functionalization of nanoscale metal-organic frameworks for controlled release and luminescence sensing.

Abstract: We describe in this paper a general method for synthesizing a new class of nanocomposites with a nanoscale metal-organic framework (NMOF) core and a silica shell. Silica shells of variable thickness were deposited on the NMOFs that had been surface-modified with polyvinylpyrrolidone (PVP) using a sol−gel procedure. The NMOF core of the nanocomposite could be completely removed (via dissolution) at low pH to afford hollow silica shells with varied thickness and aspect ratios. We also showed that the silica shell of such nanocomposites significantly stabilized the NMOF core against dissolution, thus demonstrating the ability to control the release of metal constituents from such silica-coated NMOFs. The silica shell was further functionalized with a silylated Tb-EDTA monoamide derivative for the luminescence sensing of dipicolinic acid (DPA), which is a major constituent of many pathogenic spore-forming bacteria. Owing to the tunability of NMOF composition and morphology, the present approach should allow f...

Polymer Nanocomposites: The “Nano” Effect on Mechanical Properties

Abstract: Polymer nanocomposites offer significant potential in the development of advanced materials for numerous applications These novel materials benefit from the synergy between filler particles and polymer chains that are on similar length scales and the large quantity of interfacial area relative to the volume of the material Although enhanced properties of these materials have been demonstrated by numerous researchers, our fundamental knowledge of the “nano” effect in terms of mechanical properties is not fully developed In this article, we discuss the important properties of three components in a general polymer nanocomposite: the polymer matrix, the nanoscale filler, and the interfacial region We highlight theory and experimental observations from several different fields to help guide the future research and development of understanding in this critical field

Novel Nanoparticle‐Reinforced Metal Matrix Composites with Enhanced Mechanical Properties

Abstract: This paper summarizes and reviews the state-of-the-art processing methods, structures and mechanical properties of the metal matrix composites reinforced with ceramic nanoparticles. The metal matrices of nanocomposites involved include aluminum and magnesium. The processing approaches for nanocomposites can be classified into ex-situ and in-situ synthesis routes. The ex-situ ceramic nanoparticles are prone to cluster during composite processing and the properties of materials are lower than the theoretical values. Despite the fact of clustering, ex-situ nanocomposites reinforced with very low loading levels of nanoparticles exhibit higher yield strength and creep resistance than their microcomposite counterparts filled with much higher particulate content. Better dispersion of ceramic nanoparticles in metal matrix can be achieved by using appropriate processing techniques. Consequently, improvements in both the mechanical strength and ductility can be obtained readily in aluminum or magnesium by adding ceramic nanoparticles. Similar beneficial enhancements in mechanical properties are observed for the nanocomposites reinforced with in-situ nanoparticles.

3D Flowerlike Ceria Micro/Nanocomposite Structure and Its Application for Water Treatment and CO Removal

Abstract: A simple and economical route based on ethylene glycol mediated process was developed to synthesize three-dimensional (3D) flowerlike ceria micro/nanocomposite structure using cerium chloride as a reactant. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were adopted to investigate the evolution process of ceria precursor, and a two-stage growth process was identified during the morphology evolution. Ceria with the same flowerlike micro/nanocomposite structure was readily obtained by calcination of the ceria precursor. This novel micro/nanocomposite structure held the advantages of both microstructure and nanostructure. Therefore, the as-obtained ceria can be used as not only an effective sorbent for the removal of pollutants in water treatment but also as an excellent support for gold nanoparticles to remove CO by catalytic oxidation, demonstrating a promising potential in environmental remediation.

Poly(vinylpyrrolidone)-modified graphite carbon nanofibers as promising supports for PtRu catalysts in direct methanol fuel cells.

Abstract: Carbon nanomaterials, including herringbone graphite carbon nanofibers (GNFH), multiwalled carbon nanotubes (MWCNT), and carbon black, were surface-modified by a new poly(vinylpyrrolidone) (PVP) grafting process as well as by the conventional acid-oxidation (AO) process, and characterized by FTIR, TGA, Raman, HRTEM, XRD, and XPS measurements. Pt nanoparticles of 1.8 nm were evenly deposited on all PVP-grafted carbon nanomaterials. The effects of the two surface modification processes on the dispersion, average Pt nanoparticle sizes, the electrocatalytic performance, and electrical conductivities of Pt-carbon nanocomposites in direct methanol oxidation were systematically studied and compared. It was found that the PVP-grafted carbon nanomaterials have much less loss in the electric conductivity and thus better electrocatalytic performance, 17-463% higher, than their corresponding acid oxidation-treated nanocomposites. The electrocatalytic performance of the Pt-carbon nanocomposites decreases in the following order: Pt-PVP-GNFH > Pt-PVP-MWCNTarc > Pt-AO-MWCNTarc > Pt-PVP-MWCNTCVD > Pt-AO-MWCNTCVD > Pt-XC-72R > Pt-AO-GNFH, with the Pt-PVP-GNFH nanocomposite having approximately 270% higher performance than that of the Pt-Vulcan XC-72R nanocomposite. In addition, PtRu-PVP-GNFH shows even better (50% higher) electrocatalytic activity than the Pt-PVP-GNFH nanocomposite at a 0.6 V applied voltage.

Preparation of Nanocomposites of Metals, Metal Oxides, and Carbon Nanotubes via Self-Assembly

Abstract: Carbon nanotubes (CNTs)-based composites have attracted significant research interest in recent years, owing to their important applications in various technological fields. In this investigation, we describe a general approach to make CNTs-based nanocomposites via self-assembly. The method allows one to prepare binary composites as well as complex systems such as ternary or even quaternary composites where nanoparticles of active phases (e.g., metals and metal oxides) are used as primary building blocks. Six different kinds of binary, ternary, and quaternary nanocomposites, TiO2/CNTs, Co3O4/CNTs, Au/CNTs, Au/TiO2/CNTs, TiO2/Co3O4/CNTs, and Co/CoO/Co3O4/CNTs, have been reported herein in order to draw common features for various assembly schemes. To understand the interconnectivity between the active phases and CNTs, we have devised a range of experiments and examined the resultant samples with many instrumental techniques. On the basis of this work, we demonstrate that highly complex inorganic-organic nanohybrids with good controls in particle shape, size, and distribution can be fabricated from presynthesized nanobuilding units. Concerning their workability, we further show that self-assembled TiO2/CNTs are sufficiently robust and the electrochemical performance of TiO2 is significantly enhanced when it is used as a cathode material in Li-battery application.