The ideal structural steel combines high strength with high fracture toughness. This dissertation discusses the governing principles of strength and toughness, along with the approaches that can be used to improve these properties and the inherent limits to how strong and tough a steel can be.

Solute segregation to ceramic grain boundaries governs material processing and microstructure evolution, and can strongly influence material properties critical to engineering performance. Understanding the evolution and implications of grain boundary chemistry is a vital component in the greater effort to engineer ceramics with controlled microstructures. This study examines solute segregation to engineered grain boundaries in titanium-doped sapphire (Al2O3) bicrystals, and explores relationships between grain boundary structure and chemistry at the nanometer scale using spectroscopic and imaging techniques in the transmission electron microscope (TEM). Results demonstrate dramatic changes in solute segregation stemming from small fluctuations in grain boundary plane and structure. Titanium and silicon solute species exhibit strong tendencies to segregate to non-basal and basal grain boundary planes, respectively. Evidence suggests that grain boundary faceting occurs in low-angle twis t boundaries to accommodate nonequilibrium solute segregation related to slow specimen cooling rates, while faceting of tilt grain boundaries often occurs to expose special planes of the coincidence site lattice (CSL). Moreover, quantitative analysis of grain boundary chemistry indicates preferential segregation of charged defects to grain boundary dislocations. These results offer direct proof that static dislocations in ionic materials can assume a net charge, and emphasize the importance of interactions between charged …

It is well recognized that half the countries in the world will face significant fresh water shortages in the next 20 years, due largely to growing populations and increased agricultural and industrial demands (Gleick, 1997). These shortages will significantly limit economic growth, decrease the quality of life and human health for billions of people, and could potentially lead to violence and conflict over securing scarce supplies of water. In the Middle East, groundwater represents an important part of water supply in most locations, yet it is the least understood and one of the most fragile components of the entire water resource system. The occurrence of water underground contributes to the illusion of an infinite resource that is immune to anthropogenic activities. Nevertheless, as has been learned in the West, it can become highly impaired through the actions of man--through the disposal of human, animal, or industrial wastes, from excessive irrigation and fertilization practices in agriculture, or from simple overproduction and overexploitation--and can remain so for decades or even centuries. Finding solutions to groundwater resource and quality problems can be complex, time consuming, and costly. As is the case in many places in the world, but especially in the Middle East, …

Thomson-scattering based x-ray radiation sources, in which a laser beam is scattered off a relativistic electron beam resulting in a high-energy x-ray beam, are currently being developed by several groups around the world to enable studies of dynamic material properties which require temporal resolution on the order of tens of femtoseconds to tens of picoseconds. These sources offer pulses that are shorter than available from synchrotrons, more tunable than available from so-called Ka sources, and more penetrating and more directly probing than ultrafast lasers. Furthermore, Thomson-scattering sources can scale directly up to x-ray energies in the few MeV range, providing peak brightnesses far exceeding any other sources in this regime. This dissertation presents the development effort of one such source at Lawrence Livermore National Laboratory, the Picosecond Laser-Electron InterAction for the Dynamic Evaluation of Structures (PLEIADES) project, designed to target energies from 30 keV to 200 keV, with a peak brightness on the order of 10{sup 18} photons {center_dot} s{sup -1} {center_dot} mm{sup -2} {center_dot} mrad{sup -2} {center_dot} 0.01% bandwidth{sup -1}. A 10 TW Ti:Sapphire based laser system provides the photons for the interaction, and a 100 MeV accelerator with a 1.6 cell S-Band photoinjector at the front end provides …

This research project was conducted at the National Nuclear Security Administration's Kansas City Plant, operated by Honeywell Federal Manufacturing and Technologies, in conjunction with the Safety Sciences Department of Central Missouri State University, to compare relative removal efficiencies of three wipe sampling techniques currently used at Department of Energy facilities. Efficiencies of removal of beryllium contamination from typical painted surfaces were tested by wipe sampling with dry Whatman 42 filter paper, with water-moistened (Ghost Wipe) materials, and by methanol-moistened wipes. Test plates were prepared using 100 mm X 15 mm Pyrex Petri dishes with interior surfaces spray painted with a bond coat primer. To achieve uniform deposition over the test plate surface, 10 ml aliquots of solution containing 1 beryllium and 0.1 ml of metal working fluid were transferred to the test plates and subsequently evaporated. Metal working fluid was added to simulate the slight oiliness common on surfaces in metal working shops where fugitive oil mist accumulates over time. Sixteen test plates for each wipe method (dry, water, and methanol) were processed and sampled using a modification of wiping patterns recommended by OSHA Method 125G. Laboratory and statistical analysis showed that methanol-moistened wipe sampling removed significantly more (about twice …

Scientific computation is used for the simulation of increasingly complex phenomena, and generates data sets of ever increasing size, often on the order of terabytes. All of this data creates difficulties. Several problems that have been identified are (1) the inability to effectively handle the massive amounts of data created, (2) the inability to get the data off the computer and into storage fast enough, and (3) the inability of a remote user to easily obtain a rendered image of the data resulting from a simulation run. This dissertation presents several techniques that were developed to address these issues. The first is a prototype bin coder based on variable-to-variable length codes. The codes utilized are created through a process of parse tree leaf merging, rather than the common practice of leaf extension. This coder is very fast and its compression efficiency is comparable to other state-of-the-art coders. The second contribution is the Piecewise-Linear Haar (PLHaar) transform, a reversible n-bit to n-bit wavelet-like transform. PLHaar is simple to implement, ideal for environments where transform coefficients must be kept the same size as the original data, and is the only n-bit to n-bit transform suitable for both lossy and lossless coding.

Conventional implementations of collective communications are based on point-to-point communications, and their optimizations have been focused on efficiency of those communication algorithms. However, point-to-point communications are not the optimal choice for modern computing clusters of SMPs due to their two-level communication structure. In recent years, a few research efforts have investigated efficient collective communications for SMP clusters. This dissertation is focused on platform-independent algorithms and implementations in this area. There are two main approaches to implementing efficient collective communications for clusters of SMPs: using shared memory operations for intra-node communications, and overlapping inter-node/intra-node communications. The former fully utilizes the hardware based shared memory of an SMP, and the latter takes advantage of the inherent hierarchy of the communications within a cluster of SMPs. Previous studies focused on clusters of SMP from certain vendors. However, the previously proposed methods are not portable to other systems. Because the performance optimization issue is very complicated and the developing process is very time consuming, it is highly desired to have self-tuning, platform-independent implementations. As proven in this dissertation, such an implementation can significantly out-perform the other point-to-point based portable implementations and some platform-specific implementations. The dissertation describes in detail the architecture of the platform-independent …

In this study, we applied the Nested Partitions method to a U-line balancing problem and conducted experiments to evaluate the application. From the results, it is quite evident that the Nested Partitions method provided near optimal solutions (optimal in some cases). Besides, the execution time is quite short as compared to the Branch and Bound algorithm. However, for larger data sets, the algorithm took significantly longer times for execution. One of the reasons could be the way in which the random samples are generated. In the present study, a random sample is a solution in itself which requires assignment of tasks to various stations. The time taken to assign tasks to stations is directly proportional to the number of tasks. Thus, if the number of tasks increases, the time taken to generate random samples for the different regions also increases. The performance index for the Nested Partitions method in the present study was the number of stations in the random solutions (samples) generated. The total idle time for the samples can be used as another performance index. ULINO method is known to have used a combination of bounds to come up with good solutions. This approach of combining different performance …

This work explores the development and application of chip-scale bioassays based on surface-enhanced Raman scattering (SERS) for high throughput and high sensitivity analysis of biomolecules. The size effect of gold nanoparticles on the intensity of SERS is first presented. A sandwich immunoassay was performed using Raman-labeled immunogold nanoparticles with various sizes. The SERS responses were correlated to particle densities, which were obtained by atomic force microscopy (AFM). The response of individual particles was also investigated using Raman-microscope and an array of gold islands on a silicon substrate. The location and the size of individual particles were mapped using AFM. The next study describes a low-level detection of Escherichia coli 0157:H7 and simulants of biological warfare agents in a sandwich immunoassay format using SERS labels, which have been termed Extrinsic Raman labels (ERLs). A new ERL scheme based on a mixed monolayer is also introduced. The mixed monolayer ERLs were created by covering the gold nanoparticles with a mixture of two thiolates, one thiolate for covalently binding antibody to the particle and the other thiolate for producing a strong Raman signal. An assay platform based on mixed self-assembled monolayers (SAMs) on gold is then presented. The mixed SAMs were prepared from …

Atomic clusters are unique objects, which occupy an intermediate position between atoms and condensed matter systems. For a long time it was thought that physical and chemical properties of atomic dusters monotonically change with increasing size of the cluster from a single atom to a condensed matter system. However, recently it has become clear that many properties of atomic clusters can change drastically with the size of the clusters. Because physical and chemical properties of clusters can be adjusted simply by changing the cluster's size, different applications of atomic clusters were proposed. One example is the catalytic activity of clusters of specific sizes in different chemical reactions. Another example is a potential application of atomic clusters in microelectronics, where their band gaps can be adjusted by simply changing cluster sizes. In recent years significant advances in experimental techniques allow one to synthesize and study atomic clusters of specified sizes. However, the interpretation of the results is often difficult. The theoretical methods are frequently used to help in interpretation of complex experimental data. Most of the theoretical approaches have been based on empirical or semiempirical methods. These methods allow one to study large and small dusters using the same approximations. However, …

Many of the current methods for pathogenic bacterial detection require long sample-preparation and analysis time, as well as complex instrumentation. This dissertation explores simple analytical approaches (e.g., flow cytometry and diffuse reflectance spectroscopy) that may be applied towards ideal requirements of a microbial detection system, through method and instrumentation development, and by the creation and characterization of immunosensing platforms. This dissertation is organized into six sections. In the general Introduction section a literature review on several of the key aspects of this work is presented. First, different approaches for detection of pathogenic bacteria will be reviewed, with a comparison of the relative strengths and weaknesses of each approach, A general overview regarding diffuse reflectance spectroscopy is then presented. Next, the structure and function of self-assembled monolayers (SAMs) formed from organosulfur molecules at gold and micrometer and sub-micrometer patterning of biomolecules using SAMs will be discussed. This section is followed by four research chapters, presented as separate manuscripts. Chapter 1 describes the efforts and challenges towards the creation of imunosensing platforms that exploit the flexibility and structural stability of SAMs of thiols at gold. 1H, 1H, 2H, 2H-perfluorodecyl-1-thiol SAM (PFDT) and dithio-bis(succinimidyl propionate)-(DSP)-derived SAMs were used to construct the platform. Chapter …

The combination of giant magnetoresistive sensors, magnetic labeling strategies, and biomolecule detection is just beginning to be explored. New readout methods and assay formats are necessary for biomolecules detection to flourish. The work presented in this dissertation describes steps toward the creation of a novel detection method for bioassays utilizing giant magnetoresistive sensors as the readout method. The introduction section contains a brief review of some of the current methods of bioassay readout. The theoretical underpinnings of the giant magnetoresistive effect are also discussed. Finally, the more prominent types of giant magnetoresistive sensors are described, as well as their complicated fabrication. Four data chapters follow the introduction; each chapter is presented as a separate manuscript, either already published or soon to be submitted. Chapter 1 presents research efforts toward the production of a bioassay on the surface of a gold-modified GMR sensor. The testing of this methodology involved the capture of goat a-mouse-coated magnetic nanoparticles on the mouse IgG-modified gold surface. The second, third and fourth chapters describe the utilization of a self-referenced sample stick for scanning across the GMR sensor. The sample stick consisted of alternating magnetic reference and bioactive gold addresses. Chapter 2 is concerned with the characterization …

Quantification in liquid chromatography (LC) is becoming very important as more researchers are using LC, not as an analytical tool itself, but as a sample introduction system for other analytical instruments. The ability of LC instrumentation to quickly separate a wide variety of compounds makes it ideal for analysis of complex mixtures. For elemental speciation, LC is joined with inductively coupled plasma mass spectrometry (ICP-MS) to separate and detect metal-containing, organic compounds in complex mixtures, such as biological samples. Often, the solvent gradients required to perform complex separations will cause matrix effects within the plasma. This limits the sensitivity of the ICP-MS and the quantification methods available for use in such analyses. Traditionally, isotope dilution has been the method of choice for LC-ICP-MS quantification. The use of naturally abundant isotopes of a single element in quantification corrects for most of the effects that LC solvent gradients produce within the plasma. However, not all elements of interest in speciation studies have multiple naturally occurring isotopes; and polyatomic interferences for a given isotope can develop within the plasma, depending on the solvent matrix. This is the case for reverse phase LC separations, where increasing amounts of organic solvent are required. For such …

Total internal reflection fluorescence microscopy (TIRFM) was used to study intermolecular interactions of DNAs with unpaired (sticky) ends of different lengths at water/fused silica interface at the single-molecule level. Evanescent field residence time, linear velocity and adsorption/desorption frequency were measured in a microchannel for individual DNA molecules from T7, Lambda, and PSP3 phages at various pH values. The longest residence times and the highest adsorption/desorption frequencies at the constant flow at pH 5.5 were found for PSP3 DNA, followed by lower values for Lambda DNA, and the lowest values for T7 DNA. Since T7, Lambda, and PSP3 DNA molecules contain none, twelve and nineteen unpaired bases, respectively, it was concluded that the affinity of DNAs for the surface increases with the length of the sticky ends. This confirms that hydrophobic and hydrogen-bonding interactions between sticky ends and fused-silica surface are driving forces for DNA adsorption at the fused-silica surface. Described single-molecule methodology and results therein can be valuable for investigation of interactions in liquid chromatography, as well as for design of DNA hybridization sensors and drug delivery systems.

The purposes of our research were: (1) To characterize subunits of highly fluorescent protein R-Phycoerythrin (R-PE) and check their suitability for single-molecule detection (SMD) and cell imaging, (2) To extend the use of R-PE subunits through design of similar proteins that will be used as probes for microscopy and spectral imaging in a single cell, and (3) To demonstrate a high-throughput spectral imaging method that will rival spectral flow cytometry in the analysis of individual cells. We first demonstrated that R-PE subunits have spectroscopic and structural characteristics that make them suitable for SMD. Subunits were isolated from R-PE by high-performance liquid chromatography (HPLC) and detected as single molecules by total internal reflection fluorescence microscopy (TIRFM). In addition, R-PE subunits and their enzymatic digests were characterized by several separation and detection methods including HPLC, capillary electrophoresis, sodium dodecyl sulfate-polyacrilamide gel electrophoresis (SDS-PAGE) and HPLC-electrospray ionization mass spectrometry (ESI-MS). Favorable absorption and fluorescence of the R-PE subunits and digest peptides originate from phycoerythrobilin (PEB) and phycourobilin (PUB) chromophores that are covalently attached to cysteine residues. High absorption coefficients and strong fluorescence (even under denaturing conditions), broad excitation and emission fluorescence spectra in the visible region of electromagnetic spectrum, and relatively low molecular …

The central theme of this thesis work is to develop new block copolymer materials for biomedical applications. While there are many reports of stimuli-responsive amphiphilic [19-21] and crosslinked hydrogel materials [22], the development of an in situ gel forming, pH responsive pentablock copolymer is a novel contribution to the field, Figure 1.1 is a sketch of an ABCBA pentablock copolymer. The A blocks are cationic tertiary amine methacrylates blocked to a central Pluronic F127 triblock copolymer. In addition to the prerequisite synthetic and macromolecular characterization of these new materials, the self-assembled supramolecular structures formed by the pentablock were experimentally evaluated. This synthesis and characterization process serves to elucidate the important structure property relationships of these novel materials, The pH and temperature responsive behavior of the pentablock copolymer were explored especially with consideration towards injectable drug delivery applications. Future synthesis work will focus on enhancing and tuning the cell specific targeting of DNA/pentablock copolymer polyplexes. The specific goals of this research are: (1) Develop a synthetic route for gel forming pentablock block copolymers with pH and temperature sensitive properties. Synthesis of these novel copolymers is accomplished with ATRP, yielding low polydispersity and control of the block copolymer architecture. Well defined macromolecular …

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Metal on semiconductor surfaces has been the topic of intense studies due to its technological applications. As nano-devices shrink in size, the conventional understanding of electronic devices are no longer applicable as quantum effects start to play an important role in the behavior of the devices. At the same time, when structures are approaching atomic scale, the precise fabrication by lithographic techniques, for example, are not even applicable. Very often, the fabrication of regular structures rely on self-assembly which is susceptible to fluctuations. Therefore, a deeper understanding to exploit the quantum behavior of nano-devices and precise control of building nano-structures are highly desired. Si(100) and Si(111) surfaces are the most studied system because they are the Si surfaces with the lowest surface energy. Pb on Si(100) and Si(111) is often chosen as the prototype system for the study of metal/semiconductor interfaces because Pb is not reactive with Si thus forming a clean well-defined hetero-interface. A prominent problem for studying the physics of metal/semiconductor interfaces is that the interface structures are usually not known. While various experimental techniques can be employed to provide clues to the atomic geometries, definite conclusions usually cannot be drawn due to the intrinsic limitations of the …

This work is presented in the following order: A review of the relevant physics and discussion of theoretical predictions for a two gap superconducting compound is given in chapter 2. Chapter 3 provides a review of the basic properties of MgB{sub 2}. Details of sample synthesis and characterization are given in chapter 4. Chapter 5 presents normal state and superconducting properties of Mg(B{sub 1-x}C{sub x}){sub 2} wires. Attempts to increase critical current densities in filaments via titanium additions are discussed in chapter 6. In chapters 7 and 8 alternative methods for synthesizing doped MgB{sub 2} powders are explored. In chapter 7 we synthesize Mg(B{sub 1-x}C{sub x}){sub 2} up to x=0.069 using a mixture of Mg, B, and the binary compound B{sub 4}C. Chapter 8 explores an alternative method, plasma spray synthesis, to produce nanometer sized doped boron powders for powder-in-tube applications. The effects of neutron irradiation on pure MgB{sub 2} wires is discussed in chapter 9. This is followed by a study of the effects of neutron irradiation on Mg(B{sub .962}C{sub .038}){sub 2} wires, presented in chapter 10. I will summarize the results of all of these studies in chapter 11 and discuss future directions for research in understanding the …

Studies of colloidal nanocrystals and their assemblies are presented. Two of these studies concern the atomic-level structural characterization of the surfaces, interfaces, and interiors present in II-VI semiconductor nanorods. The third study investigates the crystallographic arrangement of cobalt nanocrystals in self-assembled aggregates. Crystallographically-aligned assemblies of colloidal CdSe nanorods are examined with linearly-polarized Se-EXAFS spectroscopy, which probes bonding along different directions in the nanorod. This orientation-specific probe is used, because it is expected that the presence of specific surfaces in a nanorod might cause bond relaxations specific to different crystallographic directions. Se-Se distances are found to be contracted along the long axis of the nanorod, while Cd-Se distances display no angular dependence, which is different from the bulk. Ab-initio density functional theory calculations upon CdSe nanowires indicate that relaxations on the rod surfaces cause these changes. ZnS/CdS-CdSe core-shell nanorods are studied with Se, Zn, Cd, and S X-ray absorption spectroscopy (XAS). It is hypothesized that there are two major factors influencing the core and shell structures of the nanorods: the large surface area-to-volume ratio, and epitaxial strain. The presence of the surface may induce bond rearrangements or relaxations to minimize surface energy; epitaxial strain might cause the core and shell lattices …

The objective of this work is to investigate the thick diffusion limit of various spatial discretizations of the one-dimensional, steady-state, monoenergetic, discrete ordinates neutron transport equation. This work specifically addresses the two lowest order nodal methods, AHOT-N0 and AHOT-N1, as well as reconsiders the asymptotic limit of the Diamond Difference method. The asymptotic analyses of the AHOT-N0 and AHOT-N1 nodal methods show that AHOT-N0 does not possess the thick diffusion limit for cell edge or cell average fluxes except under very limiting conditions, which is to be expected considering the AHOT-N0 method limits to the Step method in the thick diffusion limit. The AHOT-N1 method, which uses a linear in-cell representation of the flux, was shown to possess the thick diffusion limit for both cell average and cell edge fluxes. The thick diffusion limit of the DD method, including the boundary conditions, was derived entirely in terms of cell average scalar fluxes. It was shown that, for vacuum boundaries, only when {sigma}{sub t}, h, and Q are constant and {sigma}{sub a} = 0 is the asymptotic limit of the DD method close to the finite-differenced diffusion equation in the system interior, and that the boundary conditions between the systems will …

In the last two decades, the field of nanoscience andnanotechnology has witnessed tremendous advancement in the synthesis andapplication of group II-VI colloidal nanocrystals. The synthesis based onhigh temperature decomposition of organometallic precursors has becomeone of the most successful methods of making group II-VI colloidalnanocrystals. This method is first demonstrated by Bawendi and coworkersin 1993 to prepare cadmium chalcogenide colloidal quantum dots and laterextended by others to prepare other group II-VI quantum dots as well asanisotropic shaped colloidal nanocrystals, such as nanorod and tetrapod.This dissertation focuses on the chemistry of this type of nanocrystalsynthesis. The synthesis of group II-VI nanocrystals was studied bycharacterizing the molecular structures of the precursors and productsand following their time evolution in the synthesis. Based on theseresults, a mechanism was proposed to account for the 2 reaction betweenthe precursors that presumably produces monomer for the growth ofnanocrystals. Theoretical study based on density functional theorycalculations revealed the detailed free energy landscape of the precursordecomposition and monomerformation pathway. Based on the proposedreaction mechanism, a new synthetic method was designed that uses wateras a novel reagent to control the diameter and the aspect ratio of CdSeand CdS nanorods.

In the last two decades, the field of nanoscience andnanotechnology has witnessed tremendous advancement in the synthesis andapplication of group II-VI colloidal nanocrystals. The synthesis based onhigh temperature decomposition of organometallic precursors has becomeone of the most successful methods of making group II-VI colloidalnanocrystals. This methodis first demonstrated by Bawendi and coworkersin 1993 to prepare cadmium chalcogenide colloidal quantum dots and laterextended by others to prepare other group II-VI quantum dots as well asanisotropic shaped colloidal nanocrystals, such as nanorod and tetrapod.This dissertation focuses on the chemistry of this type of nanocrystalsynthesis. The synthesis of group II-VI nanocrystals was studied bycharacterizing the molecular structures of the precursors and productsand following their time evolution in the synthesis. Based on theseresults, a mechanism was proposed to account for the 2 reaction betweenthe precursors that presumably produces monomer for the growth ofnanocrystals. Theoretical study based on density functional theorycalculations revealed the detailed free energy landscape of the precursordecomposition and monomerformation pathway. Based on the proposedreaction mechanism, a new synthetic method was designed that uses wateras a novel reagent to control the diameter and the aspect ratio of CdSeand CdS nanorods.

This thesis reports measurements of the time-dependent CP asymmetries in fully reconstructed B{sup 0} {yields} (D{sup (*){-+}} and B{sup 0} {yields} D{sup {-+}} {rho}{sup {+-}}) decays in approximately 232 million {Upsilon}(4S) {yields} B{bar B} events, collected with the BABAR detector at the PEP-II asymmetric-energy B factory at the Stanford Linear Accelerator Center in California, as published in Ref. [14]. The phenomenon of CP violation allows one to distinguish between matter and antimatter, and, as such, is one of the essential ingredients needed to explain the apparent abundance of matter over antimatter in the universe. The Standard Model describes the observed elementary particles in terms of three generations of quarks and leptons, as well as the weak, electromagnetic, and strong interactions between them. In the Standard Model, CP violation is incorporated in the Cabibbo-Kobayashi-Maskawa (CKM) matrix, which describes the weak interactions between the quarks. The weak interactions between quarks are described by coupling constants that are functions of three real parameters and one irreducible complex phase. The magnitude of all CP violating effects in the Standard Model is related to this complex phase. The measurement of the CP violating phase of the CKM matrix is an important part of the present …