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The polymer as a significant independent variable in the mechanical performance of polymer–clay nanocomposites
Chavarria and Paul [1] performed a complete evaluation of a comparison of the significant variables that relate to the successful exfoliation of organomontmorillonite in nylon 6 with the utility of these variables in the preparation of organomontmorillonite–nylon 6,6 polymer nanocomposites. The equipment and protocol for these evaluations were identical to those found in reference [1] with nylon 11 and 12. The same nylon 6 was evaluated (B135WP). The molecular weight of the nylon 6 was measured to be Mn = 29 300 by intrinsic viscosity. This is slightly different from the reported viscosity, Mn = 31 100, in reference [1]. The same organomontmorillonite (montmorillonite exchanged with octadecytrimethyl quaternary ammonium ion at 95 meq/100 g of montmorillonite) was employed in both studies. The nylon 6,6 was produced by DuPont, Zytel 42A. The molecular weight was not reported.
The production of nylon 6,6 is significantly different from the ring opening polymerization of ε-caprolactam to produce nylon 6. Hexanedioic acid (adipic acid) is neutralized with hexamethylenediamine in a 50% aqueous solution. The pH is carefully monitored in order to ensure the proper stoichiometry of dicarboxylic acid and diamine.
In order for nanocomposites to be useful, they must be thermodynamically stable. It is therefore critical to ensure that clay nanoparticles have surfaces that interact with polymer in a way that yields exfoliated structures that do not spontaneously phase separate. Although some intercalated–exfoliated systems may yield useful improvements in properties, the exfoliated state is still the ultimate goal in producing a nanocomposite with the ultimate property enhancements.
The rate at which intercalation/exfoliation occurs is also of some importance in ensuring that a nanocomposite can be made on a timescale that is commercially viable. Since the level of exfoliation is critical in order that the maximum change in properties in nanocomposites is reached, the ability to measure the level of exfoliation is of paramount importance.
In this chapter, the thermodynamics of intercalation/exfoliation will be discussed in detail, including surface modification of clays, processing strategies, and the enthalpic and entropic components of the intercalation/exfoliation process. In addition, the kinetics related to intercalation/exfoliation will be presented. Finally, a critical evaluation of the analytical methods utilized commonly to determine the level of intercalation/exfoliation will be given.
Clay surface compatibility with polymers
Smectite clay structure
The discussion of clay surface compatibility with polymers in this section will focus primarily on montmorillonite as the example clay. The characteristics discussed will only vary by degree for other smectic clays.
Complexity of polyolefin–montmorillonite nanocomposites
Preparing polyolefin–montmorillonite nanocomposites presents another challenge in relation to the preparation of block copolymer–montmorillonite nanocomposites found in Chapter 6. An excellent example of the complexity of exfoliating organomontmorillonite into a pure hydrocarbon polymer is found in the work by Hotta and Paul [1]. Linear low-density polyethylene (LLDPE; Dowlex 2032 manufactured by Dow Chemical) was melt blended with two different organomontmorillonites (Cloisite 20A and montmorillonite exchanged with trimethyl hydrogenated tallow quaternary ammonium ion). The importance of blending maleic anhydride grafted LLDPE (LLDPE–g–MA; 0.9 wt. % MA content; Fusabond MB266D produced by DuPont, Canada) with LLDPE as regards achieving exfoliation was determined in this study.
The procedures and equipment that were employed in this work were identical to those utilized by Fornes and Paul in the preparation of melt-blended nylon 6–montmorillonite nanocomposites described in Chapter 5. As one may anticipate from the studies in Chapters 5 and 6, the more hydrophobic Cloisite 20A was more efficient in producing exfoliated composites. The presence of the LLDPE–g–MA in the polymer blend further encouraged the exfoliation of Cloisite 20A. When the weight ratio of LLDPE–g–MA to Cloisite 20A is increased to 4 and subsequently to 11, the WAXS indicated good exfoliation with a loading of 4.6 and 4.9 wt.%, respectively, of montmorillonite (determined by incineration of the polymer composite in an oven). The TEM for the composite with a ratio of 11 at 4.9% montmorillonite indicated good exfoliation.
A combined melt-spinning and spark-plasma-sintering (SPS) procedure has proven to be effective in preparing high-performance (Bi,Sb)2Te3 thermoelectric (TE) nanocomposites via creating and optimizing their resulting multiscale microstructures. (Bi,Sb)2Te3 possesses a highly anisotropic crystal structure; therefore, it is important to investigate any potential correlation between the SPS conditions, the as-formed microstructures, and the resulting TE properties. In this work, we investigate the correlation between the SPS pressure, the microstructure texture, and the anisotropy of the total thermal conductivity in these melt-spun spark-plasma-sintered (Bi,Sb)2Te3 compounds. The thermal conductivity has been measured in directions that are both perpendicular and parallel to the pressing (or force) direction by rearranging the sample geometry as described in the text. The results show that the anisotropy of thermal conductivity is ∼0, 2–3, 6–7, and 13–15% for the samples sintered at pressures of 20, 30, 45, and 60 MPa, respectively. These results are consistent with an increasing degree of orientation observed by x-ray diffraction and electron microscopy.
Effect of a low-voltage pulsed magnetic field (LVPMF) on the solidified microstructure of Mg–Al–Zn alloy has been investigated. Experimental results show that the solidified structure of Mg–Al–Zn alloy can be remarkably refined and that the morphology of α-Mg is transformed from developed dendrite to fine rosette with the application of LVPMF. Magnetization of the solute and solvent in the diffusion layer cannot account for the formation of the rosette α-Mg under LVPMF. A model for the formation of rosette α-Mg under LVPMF has been developed by analyzing the growth behavior of α-Mg dendrite. Morphology change of α-Mg dendrite under LVPMF is caused by Joule heat concentrated on the dendrite tip. Accumulation of Joule heat on the dendrite tip melts the local dendrite tip and increases the radius of curvature. The increased radius of curvature at the dendrite tip lowers the growth rate and results in the formation of rosette α-Mg.
The morphology of semiconducting nanowires, including kinked and branched wires, must be controlled in order to produce functional devices. Here, we describe some of the experimental and theoretical work involving complex morphologies of Au-catalyzed Si nanowires grown using the vapor–liquid–solid technique. Although there is a broad parameter space to explore, experiments have highlighted the importance of the precursor and impurity partial pressures on kinking behavior. Theoretical and modeling work has indicated that the stability of and transitions in droplet configuration are important for growth direction changes that can lead to complex morphologies. We describe recent phase-field simulations of nanowire growth that address the dynamics of liquid droplets during vapor–liquid–solid growth, as well as the implications of these results for the formation of wires with complex morphology.
Epitaxially oriented silicon nanowires (SiNWs) were grown on (111) Si substrates by the vapor–liquid–solid technique in an atmospheric-pressure chemical vapor deposition (APCVD) system using Au as the catalyst and SiCl4 as the source gas. The dependencies of SiNW growth rate on the growth temperature and SiCl4 partial pressure (PSiCl4) were investigated, and the experimental results were compared with calculated supersaturation curves for Si obtained from a gas phase equilibrium model of the SiCl4–H2 system. The SiNW growth rate was found to be weakly dependent on temperature but strongly dependent on the PSiCl4, exhibiting a maximum value qualitatively similar to that predicted from the equilibrium model. The results indicate that SiNW growth from SiCl4 is limited by gas phase chemistry and transport of reactant species to the growth surface under APCVD conditions. The experimental results are discussed within the context of a gas phase mass transport model that takes into account changes in equilibrium partial pressure due to curvature-related Gibbs–Thomson effects.
Effects of the precipitated phase and the ordered phase domain of an Fe-6.5 wt%Si alloy before and after heat treatment on the bending properties were investigated in this study. The results showed that original needle-like phases were spheroidized after the heat treatment at 900 °C for 1 h followed by slow or rapid cooling. Compared with the directional solidified sample, the slow cooling sample had a higher order degree, whereas the rapid cooling samples had a lower order degree. After rapid cooling heat treatment, the fracture deflection of the sample was increased by 73.8%. Fracture analysis showed that transition from quasi-cleavage fracture to tear pit-like fracture took place in the rapid cooling sample. The bending properties of the Fe-6.5 wt%Si alloy were improved mainly due to the changes in morphology and amount of the precipitated phase as well as the reduction of order degree.
Device and sensor miniaturization has enabled extraordinary functionality and sensitivity enhancements over the last decades while considerably reducing fabrication costs and energy consumption. The traditional materials and process technologies used today will, however, ultimately run into fundamental limitations. Combining large-scale directed assembly methods with high-symmetry low-dimensional carbon nanomaterials is expected to contribute toward overcoming shortcomings of traditional process technologies and pave the way for commercially viable device nanofabrication. The purpose of this article is to review the guided dielectrophoretic integration of individual single-walled carbon nanotube (SWNT)- and graphene-based devices and sensors targeting continuous miniaturization. The review begins by introducing the electrokinetic framework of the dielectrophoretic deposition process, then discusses the importance of high-quality solutions, followed by the site- and type-selective integration of SWNTs and graphene with emphasis on experimental methods, and concludes with an overview of dielectrophoretically assembled devices and sensors to date. The field of dielectrophoretic device integration is filled with opportunities to research emerging materials, bottom–up integration processes, and promising applications. The ultimate goal is to fabricate ultra-small functional devices at high throughput and low costs, which require only minute operation power.
Reducing our dependence on fossil fuels increases the demand for energy storage. Lithium-ion batteries have transformed portable electronics and will continue to be important but cannot deliver the step change in energy density required in the longer term in markets such as electric vehicles and the storage of electricity from renewables. There are a few alternatives. Here we describe two: Li-air and Li-sulfur batteries. We compare the energy densities of Li-ion, Li-air, and Li-S and discuss their differences and the challenges facing Li-air and Li-S, many of which are materials related.
High-energy cathode materials with high working potential and/or high specific capacity are desired for future electrification of vehicles. In this article, we provide a general overview of advanced high-energy cathode materials using different approaches such as core-shell, concentration-gradient materials, and the effects of nanocoatings at the particle level to improve both electrochemical performance and safety. We also summarize the methods used to prepare these materials. Special attention is placed on the co-precipitation process for making dense, spherical particles for the purpose of improving the powder packing density and increasing the electrode energy density.
Nonequilibrium phase composition in multiphase systems affects physical properties of many materials. Development of phase composition is controlled by external conditions and material characteristics. Based on the model presented in the Part I [A. Ziabicki and B. Misztal-Faraj, J. Mater. Res. 26(13), (2011)], rates of phase transitions in a three-phase model monotropic system composed of an amorphous (liquid) phase and two solid polymorphs have been analyzed. Effects of material characteristics including activation energy of molecular mobility, heat and entropy of the transitions, interface tensions, and concentration of predetermined nuclei have been discussed.
Ongoing technological advances in such disparate areas as consumer electronics, transportation, and energy generation and distribution are often hindered by the capabilities of current energy storage/conversion systems, thereby driving the search for high-performance power sources that are also economically viable, safe to operate, and have limited environmental impact. Electrochemical capacitors (ECs) are a class of energy-storage devices that fill the gap between the high specific energy of batteries and the high specific power of conventional electrostatic capacitors. The most widely available commercial EC, based on a symmetric configuration of two high-surface-area carbon electrodes and a nonaqueous electrolyte, delivers specific energies of up to ∼6 Whkg–1 with sub-second response times. Specific energy can be enhanced by moving to asymmetric configurations and selecting electrode materials (e.g., transition metal oxides) that store charge via rapid and reversible faradaic reactions. Asymmetric EC designs also circumvent the main limitation of aqueous electrolytes by extending their operating voltage window beyond the thermodynamic 1.2 V limit to operating voltages approaching ∼2 V, resulting in high-performance ECs that will satisfy the challenging power and energy demands of emerging technologies and in a more economically and environmentally friendly form than conventional symmetric ECs and batteries.