Acrylic triblock (AxMyBz) and diblock (MyBz) oligomers containing methyl methacrylate (MMA, M), methacrylic acid (MAA, A) and dimethylaminoethyl methacrylate (DMAEMA, B) groups are intercalated into the layers of montmorillonite. The results indicate that the block oligomer lay flatly between the clay layers. ICP analyses of Na+ content indicate no unexchanged sodium ions are left in the intercalated clay.

Nanocomposites of epoxy and clay modified with block oligomers were synthesized. Glass transition temperature (Tg) of the nanocomposite is 129.6°C (M18B2424+ modified clay) compared to 84.1°C for the physical mixture of epoxy and unmodified clay. Tg increases with decreasing amount of modified clay. When modified clay content are below 2 phr, Tg higher than 131.7 °C can be obtained. Water resistance and light transmittance of the nanocomposite is also improved over composite of epoxy and unmodified clay.

We have investigated the consequences of negative triple junction energy in grain growth. Two and three-dimensional models for total system energy, incorporating varying triple junction energy are developed. These models show that there is a decrease in overall system energy with grain size corresponding to the driving force for grain growth. Although the free energy available to drive grain growth is reduced under some conditions, it is never removed for any reasonable values of the triple junction energy.

Mesoporous silicas were used as hosts for fabrication of nanostructured metals. Due to the confinement effect, densely packed metal nanowire bundles and nano-networks or highly dispersed metal nanoparticles were prepared inside the channels of mesoporous silicas by metal incorporation/reduction processes. The structure of nanostructured metals was analyzed by TEM and PXRD, and the composition was investigated by ICP-AES, EDX and EELS.

(Ni75Fe25)v/(SiO2)1-v nanocomposites with v =0.5, 0.7, and 1.0, where 75 denotes the atomic percent of Ni in the Ni-Fe alloy phase and v denotes the volume fraction of the magnetic constituent in the composite, were synthesized using a wet chemical approach. The x-ray diffraction and TEM experiments show that the synthetic NiFe/SiO2 is a two-phase composite system in that an amorphous insulating SiO2 layer coats each Ni-Fe particle. The Ni-Fe particle is in a fcc Ni-Fe alloy state. Its size can be controlled over a rather large range between 5 nm to 70 nm by adjusting the reaction parameters. Particular attention was paid to reduce the chemical reaction temperature so as to insure the smallness of the particle size. Meanwhile, measurements of the saturation magnetization indicated that the higher the heat treatment temperature, the more complete the chemical reaction to form the Ni-Fe alloys from precursor materials.

We describe a procedure for dispersion bulk Si into a family discretely sized ultrasmall ultrabright nanoparticles. We demonstrate that electrochemically etched, hydrogen capped SinHx clusters with n larger than 20 are obtained within a family of discrete sizes. These sizes are 1.0 (Si29), 1.67 (Si123), 2.15, 2.9, and 3.7 nm diameter. We characterize the particles via direct electron imaging, excitation and emission optical spectroscopy, chromatography, and colloidal crystallization. The band gaps and emission bands are measured. The smallest four are ultrabright blue, green, yellow, and red luminescent particles. The availability of discrete sizes and distinct emission in the red, green and blue range is useful for biomedical tagging, RGB displays, and flash memories.

In order to refine further the material technology for tin-oxide based gas sensing we are exploring the use of precision nanoparticle deposition for the sensing layer. Layers of SnO2 nanoparticles were grown on Quartz Crystal Microbalance (QCM) resonators using the layer-by-layer self-assembly technique. Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and Electron Diffraction Pattern (EDP) analyses were performed on the self-assembled layers of SnO2 nanoparticles. The results showed that SnO2 nanoparticle films are deposited uniformly across the substrate. The size of the nanoparticles is estimated to be about 3-5 nm. Electrical characterization was done using standard current-voltage measurement technique, which revealed that SnO2 nanoparticle films exhibit ohmic behavior. Calcination experiments have also been carried out by baking the substrate (with self-assembled nanoparticles) in air at 350°C. Results show that 50%-70% of the polymer layers (which are deposited as precursor layers and also alternately in-between SnO2 nanoparticle monolayers) are eliminated during the process.

Understanding the role of grain boundaries in controlling heat flow is critical to the success of many envisioned applications of nanocrystalline materials. This study focuses on the effect of grain boundaries on thermal transport behavior in nanocrystalline yttria-stabilized zirconia (YSZ) coatings prepared by metal-organic chemical vapor deposition.

This investigation deals with the production of materials containing a dispersion of magnetic nanoparticles in an insulating matrix. Such a distribution of magnetic centers is expected to absorb electromagnetic radiation in a range of wavelengths. Wüstite-magnetite and magnesiamagnesioferrite nanocrystalline ceramics have been prepared by mechanical milling and spark plasma sintering. As-milled powders have a nanocrystalline structure in both systems. Low energy milling gives rise to an increasingly higher volume fraction of wüstite as a function of milling time in the Fe1-xO-Fe3O4 system. Similar results are obtained in the MgO-MgFe2O4 system with increasingly larger amounts of MgFe2O4 produced by milling. Composites of magnetic particles (Fe3O4 or MgFe2O4) in a nonconductive matrix (FeO or MgO, respectively) are found in the sintered samples. Measurement of magnetic properties can be used to determine conclusively the nature of the developed phases and the effect of grain size.

Sulfur incorporated nanocrystalline carbon (n-C:S) thin films grown on molybdenum substrates by hot-filament chemical vapor deposition (HFCVD) using gas mixtures of methane, hydrogen and a range of hydrogen sulfide (H2S) concentrations are optically examined using Raman spectroscopy (RS) and ex situ spectroscopic phase modulated ellipsometry (SPME) from near IR to near UV (1.5-5.0 eV) obtaining their vibrational frequencies and pseudodielectric function, respectively. The ellipsometry data (<εr(E)>, <εi(E)>) were modeled using Bruggeman effective-medium theory (BEMT) and five parameters Forouhi and Bloomer (FB) dispersion Model. A simplified two-layer model consisting of a top layer comprising an aggregate mixture of sp3C+sp2C+void and a bulk layer (L2), defined as a dense amorphized FB-modeled material was found to simulate the data reasonably well. Through these simulations, it was possible to estimate the dielectric function of our n-C: S material, along with the optical bandgap (Eg), film thickness (d), and roughness layer (σ) as a function of [H2S]. The physical interpretation(s) of the modeling parameters obtained were discussed. The Raman and ellipsometry results indicate that the average size of nanocrystallites in the sulfur-incorporated carbon thin films becomes smaller with increasing H2S concentration, consistent with AFM measurements. The bandgap was found to decrease systematically with increasing H2S concentration, indicating the enhancement of midgap states and sp2 C network, in agreement with RS results. These results are compared to those obtained for the films grown without sulfur (n-C), in order to study the influence of sulfur addition to the CVD process. This analysis led to a correlation between the film microstructure and its electronic properties.

Thin transparent and electrically conductive films of tin doped indium oxide (ITO) were made by sintering of nanoparticle dispersions. The resistivity decreased to 1–10-2 μcm upon treatment at 800°C, while the luminous transmittance remained high. The property evolution was connected with sintering and densification as studied by Scanning Electron Microscopy, X-ray Diffraction, X-ray Fluorescence and Elastic Recoil Detection Analysis.

Transparent polymeric material with enhanced thermal, mechanical and barrier properties are of special interest for advanced structural, optical and photonic applications. The present paper reports a novel solution processing scheme for fabricating optically transparent polymer nanocomposites involving organophilic layered silicates. It is shown that the nanocomposite material prepared with PMMA and an organically modified montmorrilonite maintains the excellent optical transparency of PMMA. Small-angle x-ray scattering of the polymer nanocomposite material does not show any Bragg's reflection of the organophilic layered silicate. The optical transparency of the nanocomposite material is attributed to a high degree of exfoliation of the montmorrilonite in the polymer matrix.

Since their discovery carbon nanotubes have attracted much interest for their peculiar electronic properties which go from metalic to semiconducting behaviour, depending both on diameter and chirality. The exact vaue of their band gap is obviously a crucial point to be addressed because it enters in the nanotube application as microelectronic devices. By making use of an efficient GW scheme, previousy tested on bulk systems, as well as of a model screening function, we obtained for the first time excitation energies and band-gap vaues for carbon nanotubes. Results for (6,0) and (7,0) will be presented and discussed.

Bulk amorphous Zr54.5 Ti7.5Al10Cu20Ni8 is investigated by means of smal-angle neutron scattering (SANS), differential-scanning calorimetry (DSC), high-resolution electron microscopy (HREM) and other methods. The formation of ultrafine nanostructures in the glassy phase is observed and explained by a new model. Structura fluctuations of randomly distributed partialy ordered domains grow during annealing just below the glass transition temperature by local re-ordering. During anneaing the DSC gives evidence for a increasing volume fraction of the localy ordered domains. At high volume fractions of impinging domains a percolation threshold on the interconnected domain boundaries occurs and enhanced diffusion becomes possible. At that stage SANS measurements lead to satistically significant scattering data. The SANS signals are anayzed in terms of a model taking into account spherica particles surrounded by diffusion zones and interparticle interference effects. The mean radius of the nanocrystaline particles is determined to 1 nm and the mean thickness of the depletion zone is 2 nm. The upper limit for the volume fraction after annealing at 653 K for 4hours is about 20 %. Electron microscopy confirms the size and shows that the particle are crystaline.

LiFePO4 was successfully synthesized by high temperature and hydrothermal synthesis. A nanocomposite was formed by carbon coating this material; initial electrochemical results showed that up to 70% capacity could be obtained at 1.0 mA/cm2 current density. In contrast, the hydrothermally prepared LiFePO4 showed a lower capacity even at lower discharge rates due to a partial occupation of lithium sites by iron. This occupation, identified by Rietveld X-ray refinement, decreased both the rate and degree of intercalation and de-intercalation of lithium; chemical reaction with butyl lithium and bromine confirmed the electrochemical behavior. This investigation showed that the cathode could be prepared by high temperature synthesis, followed by a carbon black coating to achieve high capacity at high current density.

Faceting in a polyhedral rutile particle was modeled from transmission electron microscopy images. A double-tilt, rotate transmission electron microscope (TEM) sample holder was used to manipulate the particle. Using this holder, it was possible to align the c axis of the particle along one of the axes of the sample holder. This alignment allowed images to be obtained of the particle in several orientations around its c axis. Comparison of dimensions and angles obtained to those obtained for hypothetical models of the particle gives information about its likely prismatic and pyramidal faceting. This approach to facet modeling is useful for more complete determination of the faceting in individual euhedral particles using transmission electron microscopy.

Nanodispersed lead in metallic and amorphous matrices was synthesized by rapid solidification processing. The optimum microstructure was tailored to avoid percolation of the particles. With these embedded particles it is possible to study quantitatively the effect of size on the superconducting transition temperature by carrying out quantitative microstructural characterization and magnetic measurements. Our results suggest the role of the matrices in enhancement or depression of superconducting transition temperature of lead. The origin of this difference in behavior with respect to different matrices and sizes is discussed.

Three-dimensional superlattices consisting of gold nanoparticles were grown at air/suspension or suspension/solid interfaces. The growth of superlattices was found to be strongly dependent on substrate materials: Micrometer-sized superlattices were grown at air/suspension interfaces and upon silver substrates, whereas no growth was observed on silicon, silicon oxide, or amorphous carbon substrates. To explain the observed substrate dependence, Lifshitz theory was used to calculate the Hamaker constants between gold nanoparticle assemblies and substrates through the suspension. Van der Waals interactions estimated from this calculation fully explain the experimental results.

We have successfully synthesized organic-inorganic and bio-inorganic nanohybrids by applying an intercalation technique systematically to Bi-based cuprate superconductors, Bi2Sr2Cam-1CumOy (m = 1, 2, and 3; BSCCO), and to layered double hydroxides(LDHs), those which are of high importance in terms of basic understanding of intercalation reactions and of their practical applications. The organic-inorganic hybrids were achieved via intercalative complexation of iodine intercalated BSCOO with organic salt of Py-CnH2n+1I (Py = pyridine). The high-Tc superconducting intercalate with its remarkable lattice expansion can be applied as a precursor for superconducting colloids when dispersed in an appropriate solvent. We were also able to demonstrate that the biomolecules stabilized in the interlayer space of LDH retain their chemical and biological integrity. If necessary, LDH, as a reservoir, can be intentionally removed by dissolving it in an acidic media or interlayer biomolecules in LDH can be released via ion-exchange reaction in electrolyte. It is, therefore, concluded that the inorganic LDH can play a role as a good host lattice for gene reservoir or carrier.

Nanocomposites of PMR-15 polyimide and a diamine modified silicate were prepared by addition of the silicate to the PMR-15 resin. The orientation of the ion exchange diamine within the silicate gallery was determined by x-ray diffraction and found to depend on the clay cation exchange capacity. The oligomer melt viscosity exhibited a dependence on the orientation of the diamine in the silicate interlayer, and in some cases, on the length of the diamine. A correlation was observed between the oligomer melt viscosity and the crosslinking enthalpy, where nanocomposites with an increased melt viscosity exhibited a decrease in enthalpy on crosslinking. After crosslinking, those nanocomposites with a high melt viscosity had poorer thermal oxidative stability compared to the less viscous systems. The melt viscosity was tailored by co-exchange of an aromatic diamine and an aliphatic amine into the silicate. Nanocomposites prepared with this silicate exhibited an increase in thermal oxidative stability compared to the neat resin.

Nanosized lithium manganate powders are successfully synthesized via a newly developed reverse-microemulsion (RμE) process. Monophasic LiMn2O4 powders are obtained after calcining the precursor powders at 700°C. The particle size of the spinel compound significantly depends on the concentration of the aqueous phase. Increasing the water-to-oil volume ratio results in an increase in the particle size. While the aqueous phase is equal to 0.5 M, the size of the obtained LiMn2O4 powder is around 60-70 nm. It is found that the specific capacity of nanosized LiMn2O4 particles is greater than that of submicron particles. The large surface area of ultrafine particles is considered to facilitate the intercalation and deintercalation of lithium ions during the cycling test.