The properties of nanostructured films can be tailored by many factors such as composition, structure, preferred orientation, microstructure, interphase interface and grain boundaries. Compositional control of magnetic properties of recording media depends on the miscibility of constituent elements. However, for nanostructured materials with a large surface-to-volume ratio of atoms, the miscibility at the nanoscale may not necessarily follow the prediction of conventional phase diagram that does not consider the effects of surface and interface. This limitation further complicates the prediction of phase separation at grain boundaries and interphase interface. Using anomalous x-ray scattering, the alloying and composition of a specific long range order of textured nanostructured films has been investigated. Such information may not be readily available from conventional characterization techniques.

Modeling of strengthening by nanocrystalline materials need consideration of dislocation interactions and sliding due to Coble creep, both of which may be acting simultaneously. Such a mechanism is considered in this paper. It is shown that a model based on using Coble creep (with a threshold stress) for finer grains and conventional Hall-Petch strengthening for larger grains, appears to be most successful in explaining experimental results provided care is taken to incorporate into the analysis the effect of grain size distribution occurring in most specimens. A generalized expression relating yield stress to grain size is also proposed.

Electrodeposition method was employed to produce freestanding Ni-W alloy foils. The foils consist of nanograins. The structure of the foil, e.g. texture, grain morphology, size distribution, and the nature of grain boundaries, were characterized using X-ray diffraction and high-resolution electron microscopy. The deposited foils exhibit an equiaxed nanocrystalline structure having a grain size value of about 6 nm. Two types of grain boundary structure were observed. One type of grain boundary is essentially one atomic layer thin and another type consists of a structureless layer of about 0.5–1 nm in thickness. Angular dark field (Z-contrast) image of the deposited foils showed an inhomogeneous distribution of W solutes. In some local regions, the W content actually exceeds the equilibrium solid solution limit. Many grain boundaries with a structureless layer of about 0.5–1 nm are probably a result of local supersaturation of W.

The expanded ensemble Monte Carlo (EEMC) simulation method has been applied to calculation of the chemical potential of nanocolloidal particles in the presence of polymeric surface modifiers. Two general classes of surface modifiers have been studied – nonadsorbing and freely-adsorbing. For both systems, the infinite dilution colloid chemical potential was calculated as a function of the colloid diameter and the modifier chain length. The colloid chemical potential was found to decrease with increasing modifier chain length for both types of modifiers, albeit for different reasons. Empirical power-law scaling relationships were found to represent the simulation results well. A physical interpretation was proposed for the power law exponents obtained in the case of adsorbing modifiers.

Noble metal clusters (Ag, Au) were formed in a silica aerogel matrix by gamma irradiation of hydrogel precursors loaded with aqueous solutions containing Ag+ or [AuCl4]- ions. Hydrogels exposed to gamma rays assumed the color expected for colloidal suspensions of Ag (respectively Au) clusters. The hydrogels were subsequently washed and supercritically dried, without any evident change in color, indicating that the metal clusters were not removed during drying. Typical gamma ray doses were between 3 and 3.5 kGy, and achieved complete reduction of hydrogels containing metal ion concentrations in the 10-4-10-3 M range. Metal clusters in the aerogel monoliths were characterized with optical absorption, transmission electron microscopy, X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy. These techniques have shown that the clusters have a crystalline fcc structure. Au clusters consist of pure Au, while surface oxidation of Ag clusters was observed with XPS.

A thermal treatment was applied with CO2 and air for the development of a porous structure. Adsorption isotherms of nitrogen were measured on well-characterized Ni-C nanoparticles. The thermal treatment with CO2 increased the total surface area and micropore volume. In addition, the thermal treatment with CO2 increased the hydrogen adsorption.

The study of organic-inorganic nanocomposites has become relevant in recent years since these materials exhibit synergistic properties derived from the two components. Thermosetting polymers like epoxies that have high mechanical properties provide a baseline for further improvement with the addition of nanoclay particles. These nanocomposites can be used as the matrix of a fiber reinforced composite and lead to higher matrix dominated mechanical properties including elastic modulus, strength and fracture toughness. This study concentrates on the mechanical and thermoviscoelastic properties in the glassy regime of nanocomposites prepared by direct mixing. The elastic modulus of the nanocomposites was found to improve with respect to the pure epoxy modulus at the expense of both tensile strength and ductility regardless of clay content. The glass transition temperature was also found to decrease as well. The morphology of the nanocomposites was studied and correlated with the aforementioned properties.

Novel materials in which modified inorganic-organic hybrid silica aerogels are attached to polymer chains have been synthesized. The aerogels are based on chitosan, a bioderived polymer from chitin, and they contain silica. The first stage of the modifications includes attachment of isocyanate, amine onto the chitosan chains embedded within the aerogel. These groups are employed in the second stage to develop the reactions required to “string” aerogel particles along functionalized linear polymers or to employ these polymers to crosslink the composite aerogels. The initial chitosan-silica aerogel particles have an ultimate size of about 2nm, and their functionally modified forms were reacted at sizes up to 1 m. These aerogels can take up and hold dyes and water-soluble drugs. The chemistry to synthesize polyamino-siloxane based aerogel composite was discussed. In addition, two approaches to synthesize PHEMA aerogel hybrid were studied.

Neat Fibers of HiPco single wall carbon nanotubes extruded from strong acid suspensions exhibit preferred orientation along fiber axes. We characterize the extrusion-induced alignment using x-ray fiber diagrams and polarized Raman scattering, using a model which allows for some fraction of the sample to remain completely unaligned. We show that both x-ray and Raman data are required for a complete texture analysis of SWNT fibers.

The microstructure and mechanical properties consisting of tensile behavior and hardness of bulk nanocrystalline Al-7.5Mg alloy were investigated. Grain refinement was achieved by cryomilling of atomized Al-7.5Mg powders, and then nanocrystalline powders blended with 15% and 30% coarse-grained Al-7.5Mg powders were consolidated by hot isostatic pressing (HIP) followed by extrusion to produce bulk nanocrystalline Al-7.5Mg alloys. Bimodal structures, which enhance ductility and toughness of nanocrystalline metals, were produced that consisted of nanocrystalline grains and elongated coarse-grain bands. Examination of indentation revealed unusual deformation mechanisms and interactions between the coarse-grain bands and nanocrystalline regions. The ductile coarse-grain bands underwent extensive plastic deformation near indentation, while nanocrystalline regions exhibited limited deformation.

We are exploring the synthesis and properties of structured vanadium oxides mainly nanotubes and nanorods. Nanotubes initially formed with surfactant templates have been readily exchanged with simple cations without change of the basal-plane structure. These compounds contain d-like vanadium oxide layers with the vanadium in VO6 octahedra. This structure is particularly suitable for redox reactions. In this paper we report on synthesis of vanadium oxide, (NH4)xV2O5-d·nH2O rods using organic polymer as template. This compound has been synthesized by sol-gel reaction and subsequent hydrothermal treatment. TGA, SEM, XRD and FTIR were used to characterize this compound. Thermal analysis of this compound shows that the fibrous morphology is maintained when it is heated in nitrogen and oxygen above 300 °C. However, in both cases the size of the fibers decreases. Performance of this compound as cathode material in secondary electrolyte has been investigated using LiPF6 as electrolyte. A capacity of 140 mAh/g was obtained which remained fairly constant with up to at least 10 cycles. We also investigated electrochemical behavior of thermal products.

A plasma-assisted concurrent Rf sputtering technique for fabrication of biocompatible, functionally graded CaP-based interlayer on Ti-6Al-4V orthopedic alloy is reported. Each layer in the coating is designed to meet a specific functionality. The adherent to the metal layer features elevated content of Ti and supports excellent ceramic-metal interfacial stability. The middle layer features nanocrystalline structure and mimics natural bone apatites. The technique allows one to reproduce Ca/P ratios intrinsic to major natural calcium phosphates. Surface morphology of the outer, a few to few tens of nanometers thick, layer, has been tailored to fit the requirements for the bio-molecule/protein attachment factors. Various material and surface characterization techniques confirm that the optimal surface morphology of the outer layer is achieved for the process conditions yielding nanocrystalline structure of the middle layer. Preliminary cell culturing tests confirm the link between the tailored nano-scale surface morphology, parameters of the middle nanostructured layer, and overall biocompatibility of the coating.

Ceramic composites containing 2 and 5vol. % of nanosized commercially available TiN and SiC particles in alumina were prepared via a water based slurry processing route followed by spark plasma sintering (SPS) at 75 MPa in the temperature range 1200–1600°C. Some of the samples could be fully densified by use of SPS already after five minutes at 1200°C and 75 MPa. The aim was to control the alumina grain growth and thus obtain different nano-structure types. The microstructures have been correlated to some mechanical properties; e.g. hardness and fracture toughness.

Fluorinated Single Wall Nanotubes (f-SWNTs) have been processed in polyethylene by an incipient wetting technique to achieve a well dispersed nanocomposite for radiation protection. In some cases, samples were further processed using the rapid prototyping method of extrusion freeform fabrication. Composites were exposed to 40 MeV proton radiation with a flux of about 1.7×107 protons/cm2/sec to a total fluence of 3×1010 protons/cm2.This exposure is consistent with a long-term space mission in low earth orbit. The samples were evaluated by means of Raman spectroscopy and thermogravimetric analysis (TGA). These results were compared to the unexposed composite and unfilled polymer samples. This study has focused on the stability of the nanotube composites when exposed to radiation and prior to hydrogen exposure. It was shown that the stability of the functional group is not constant with SWNTs produced by different processes and that radiation exposure is capable of defluorinating SWNTs in polyethylene.

Carbon nanotubes (CNTs) were grown by electroless Ni-P plated on silicon substrate in a microwave heating chemical vapor deposition (CVD) system with methane gas at 700 °C. The CNTs grown on Ni–P catalyst showed random orientation and small diameter around 15–30 nm. Field emission test results indicated that the Ni–P catalyzed-CNTs exhibited excellent field emission properties. The turn-on field was about 0.56 V/μm with an emission current density 10 μA/cm2 and the threshold field was 4.4 V/μm with an emission current density 10 mA/cm2. These excellent field emission properties may be attributed to the random orientation and small diameter of CNTs.

Catalytic decomposition of methane has been used to grow bamboo-structured carbon tubes at temperatures ranging from 1233 K to 1291 K. No tube growth was observed at temperatures less than 1233 K, whilst above 1291 K pyrocarbon was the dominant product. It is shown that the average size of the copper catalyst particles was influenced by the reaction temperature, with the reciprocal of the maximum size of the copper particle decreasing linearly with temperature. This is consistent with the idea that the melting point can be reduced by surface energy effects. Observations show that under the conditions here the catalyst particle penetrates into the carbon fibre and a mechanism is proposed for development of the bamboo structure based upon the energy changes that take place.

Powder compacts made from microwave-plasma-synthesized iron (Fe) nanopowder (Materials Modification Inc., Fairfax, VA) were sintered under hydrogen (H2). Results showed that without the application of pressure, the powder could not be sintered to full density. In subsequent experiments, the powder was consolidated to final densities near 80% of the theoretical full density, using plasma pressure compaction (P2C). To provide an explanation for the difficulty in attaining full densification, the precursor powder and compacted pellet characteristics were examined by several methods. These included residual porosity by mercury pycnometry, surface area measurement by Brunauer, Emmett, and Teller (BET) analysis, and structural change by x-ray diffraction (XRD) and scanning electron microscopy (SEM). It was observed that the nanosized primary particles were aggregated into micrometer-sized dendritic structures, with the appearance of tumbleweeds. The observed limitations in the densification and associated porous microstructures of the pressureless-sintered and P2C-densified compacts were rationalized in terms of the behavior of the dendritic aggregate structures rather than that of the nanosized primary particles.

Mechanical behavior of the surface-nanocrystallized material fabricated by the ultrasonic shot peening method is investigated experimentally and theoretically. In the experimental research, based on microscopic observations, the compressive specimens are designed and machined considering the material features, and the compressive experiments are performed. Furthermore the compressive stress-strain curves are measured. In the theoretical research, a microstructure cell model is presented considering the material microscopic organization observed from experiments, and the compressive stress-strain relations are simulated. Both experimental and theoretical results display the strong size effect on the material behavior.

A carbon nanotube pulling through a polyethylene matrix was simulated using molecular dynamics. The interfacial sliding was characterized in terms of a nanoscale friction model, which is parametrized from the molecular dynamics simulation, and involves determining the critical pull-out force on the nanotube and the effective viscosity at the nanotube/polymer interface. Comparison was made of the pull-out behavior of non-bonded and functionalized nanotube composites. Chemical bonds between the polymer and the nanotube increased the critical pullout force, the resistance to interfacial sliding, and the interfacial viscosity.

A model polymeric material filled with spherical nanoparticles is considered in this work. Monte Carlo simulations are performed to determine the polymer chain conformations in the vicinity of the curved interface with the filler. Several discrete models of increasing complexity are considered: the athermal system with excluded volume interactions only, the system in which entropic and energetic interactions take place while the filler is a purely repulsive sphere, and the system in which both filler-polymer and polymer-polymer energetic interactions are accounted for. The total density, chain end density, chain segment preferential orientation and chain size and shape variation with the distance from the filler wall are determined. The structure is graded, with the thickness of the transition region being dependent on the property and scale considered. Hence, the polymer in the vicinity of the filler is represented in the continuum sense by a material with graded properties whose elasticity is determined based on the local structure. Homogenization theory is the used to obtain the overall composite moduli. The filler size effect on the composite elasticity is evaluated.