Thin films fabricated from a nanoparticle beam

As time advances, man has been able to control technology in finer and finer detail. The microelectronics era is an example of this, with control down to the micrometer. Experts agree that we may be entering a new era, controlling technology down to the nanometer. One aspect of such control is making materials in the nanometer range, i.e. nanoparticles. For this purpose, a new magnetron-sputtering gun, inert gas condensation, nanoparticle source has been designed, built, and tested. ^ Films made from cobalt, nickel, tantalum, molybdenum, chromium, and aluminum have been investigated. Transmission Electron Microscope measurements done at the University of Illinois confirm the thin films are nanostructured. This was also confirmed by Atomic Force Microscope measurements made at the F.I.U. Thin Film Laboratory. ^ Composition, optical and magnetic properties have been measured. In most cases, unique properties have been found that differ significantly from bulk properties. Rutherford Backscattering measurements done at the University of Illinois determined significant percentages of oxygen and carbon in the samples, possibly due to interactions with air. Because of this, optical properties are a composite of oxide, metal, and void properties. Magnetic materials were determined to have spin-glass properties below the irreversibility temperature and superparamagnetic properties above it. Indications of possible future uses for these nanostructured materials are discussed. ^

Characterization of recombinant chloroperoxidase, and F103A and C29H/C79H/C87H mutants

Mechanistically and structurally chloroperoxidase (CPO) occupies a unique niche among heme containing enzymes. Chloroperoxidase catalyzes a broad range of reactions, such as oxidation of organic substrates, dismutation of hydrogen peroxide, and mono-oxygenation of organic molecules. To expand the synthetic utility of CPO and to appreciate the important interactions that lead to CPO’s exceptional properties, a site-directed mutagenesis study was undertaken. ^ Recombinant CPO and CPO mutants were heterologously expressed in Aspergillus niger. The overall protein structure was almost the same as that of wild type CPO, as determined by UV-vis, NMR and CD spectroscopies. Phenylalanine103, which was proposed to regulate substrate access to the active site by restricting the size of substrates and to control CPO’s enantioselectivity, was mutated to Ala. The ligand binding affinity and most importantly the catalytic activity of F103A was dramatically different from wild type CPO. The mutation essentially eliminated the chlorination and dismutation activities but enhanced, 4-10 fold, the epoxidation, peroxidation, and N-demethylation activities. As expected, the F103A mutant displayed dramatically improved epoxidation activity for larger, more branched styrene derivatives. Furthermore, F103A showed a distinctive enantioselectivity profile: losing enantioselectivity to styrene and cis-β-methylstyrene; having a different configuration preference on α-methylstyrene; showing higher enantioselectivites and conversion rates on larger, more branched substrates. Our results show that F103 acts as a switch box that controls the catalytic activity, substrate specificity, and product enantioselectivity of CPO. Given that no other mutant of CPO has displayed distinct properties, the results with F103A are dramatic. ^ The diverse catalytic activity of CPO has long been attributed to the presence of the proximal thiolate ligand. Surprisingly, a recent report on a C29H mutant suggested otherwise. A new CPO triple mutant C29H/C79H/C87H was prepared, in which all the cysteines were replaced by histidine to eliminate the possibility of cysteine coordinating to the heme. No active form protein was isolated, although, successful transformation and transcription was confirmed. The result suggests that Cys79 and Cys87 are critical to maintaining the structural scaffold of CPO. ^ In vitro biodegradation of nanotubes by CPO were examined by scanning electron microscope method, but little oxidation was observed. ^

The Performance and Service Life Prediction of High Performance Concrete in Sulfate and Acidic Environments

Concrete substructures are often subjected to environmental deterioration, such as sulfate and acid attack, which leads to severe damage and causes structure degradation or even failure. In order to improve the durability of concrete, the High Performance Concrete (HPC) has become widely used by partially replacing cement with pozzolanic materials. However, HPC degradation mechanisms in sulfate and acidic environments are not completely understood. It is therefore important to evaluate the performance of the HPC in such conditions and predict concrete service life by establishing degradation models. This study began with a review of available environmental data in the State of Florida. A total of seven bridges have been inspected. Concrete cores were taken from these bridge piles and were subjected for microstructural analysis using Scanning Electron Microscope (SEM). Ettringite is found to be the products of sulfate attack in sulfate and acidic condition. In order to quantitatively analyze concrete deterioration level, an image processing program is designed using Matlab to obtain quantitative data. Crack percentage (Acrack/Asurface) is used to evaluate concrete deterioration. Thereafter, correlation analysis was performed to find the correlation between five related variables and concrete deterioration. Environmental sulfate concentration and bridge age were found to be positively correlated, while environmental pH level was found to be negatively correlated. Besides environmental conditions, concrete property factor was also included in the equation. It was derived from laboratory testing data. Experimental tests were carried out implementing accelerated expansion test under controlled environment. Specimens of eight different mix designs were prepared. The effect of pozzolanic replacement rate was taken into consideration in the empirical equation. And the empirical equation was validated with existing bridges. Results show that the proposed equations compared well with field test results with a maximum deviation of ± 20%. Two examples showing how to use the proposed equations are provided to guide the practical implementation. In conclusion, the proposed approach of relating microcracks to deterioration is a better method than existing diffusion and sorption models since sulfate attack cause cracking in concrete. Imaging technique provided in this study can also be used to quantitatively analyze concrete samples.

Robust and high current cold electron source based on carbon nanotube field emitters and electron multiplier microchannel plate

The aim of this research was to demonstrate a high current and stable field emission (FE) source based on carbon nanotubes (CNTs) and electron multiplier microchannel plate (MCP) and design efficient field emitters. In recent years various CNT based FE devices have been demonstrated including field emission displays, x-ray source and many more. However to use CNTs as source in high powered microwave (HPM) devices higher and stable current in the range of few milli-amperes to amperes is required. To achieve such high current we developed a novel technique of introducing a MCP between CNT cathode and anode. MCP is an array of electron multipliers; it operates by avalanche multiplication of secondary electrons, which are generated when electrons strike channel walls of MCP. FE current from CNTs is enhanced due to avalanche multiplication of secondary electrons and in addition MCP also protects CNTs from irreversible damage during vacuum arcing. Conventional MCP is not suitable for this purpose due to the lower secondary emission properties of their materials. To achieve higher and stable currents we have designed and fabricated a unique ceramic MCP consisting of high SEY materials. The MCP was fabricated utilizing optimum design parameters, which include channel dimensions and material properties obtained from charged particle optics (CPO) simulation. Child Langmuir law, which gives the optimum current density from an electron source, was taken into account during the system design and experiments. Each MCP channel consisted of MgO coated CNTs which was chosen from various material systems due to its very high SEY. With MCP inserted between CNT cathode and anode stable and higher emission current was achieved. It was ∼25 times higher than without MCP. A brighter emission image was also evidenced due to enhanced emission current. The obtained results are a significant technological advance and this research holds promise for electron source in new generation lightweight, efficient and compact microwave devices for telecommunications in satellites or space applications. As part of this work novel emitters consisting of multistage geometry with improved FE properties were was also developed.