High-Strength Composite Fibers: Realizing True Potential of Carbon Nanotubes in Polymer Matrix through Continuous Reticulate Architecture and Molecular Level Couplings

Carbon nanotubes have unprecedented mechanical properties as defect-free nanoscale building blocks, but their potential has not been fully realized in composite materials due to weakness at the interfaces. Here we demonstrate that through load-transfer-favored three-dimensional architecture and molecular level couplings with polymer chains, true potential of CNTs can be realized in composites as Initially envisioned. Composite fibers with reticulate nanotube architectures show order of magnitude improvement in strength compared to randomly dispersed short CNT reinforced composites reported before. The molecular level couplings between nanotubes and polymer chains results in drastic differences in the properties of thermoset and thermoplastic composite fibers, which indicate that conventional macroscopic composite theory falls to explain the overall hybrid behavior at nanoscale.

Hacia una economía holográfica. Una revisión de la ciencia económica a partir de la ontoepistemología oriental

363 p.

A Mechanical Model For The Quantification Of The Effect Of Laser Quenching On Ctod In Steels

The technology of laser quenching is widely used to improve the surface properties of steels in surface engineering. Generally, laser quenching of steels can lead to two important results. One is the generation of residual stress in the surface layer. In general, the residual stress varies from the surface to the interior along the quenched track depth direction, and the residual stress variation is termed as residual stress gradient effect in this work. The other is the change of mechanical properties of the surface layer, such as the increases of the micro-hardness, resulting from the changes of the microstructure of the surface layer. In this work, a mechanical model of a laser-quenched specimen with a crack in the middle of the quenched layer is developed to quantify the effect of residual stress gradient and the average micro-hardness over the crack length on crack tip opening displacement (CTOD). It is assumed that the crack in the middle of the quenched layer is created after laser quenching, and the crack can be a pre-crack or a defect due to some reasons, such as a void, cavity or a micro-crack. Based on the elastic-plastic fracture mechanics theory and using the relationship between the micro-hardness and yield strength, a concise analytical solution, which can be used to quantify the effect of residual stress gradient and the average micro-hardness over the crack length resulting from laser quenching on CTOD, is obtained. The concise analytical solution obtained in this work, cannot only be used as a means to predict the crack driving force in terms of the CTOD, but also serve as a baseline for further experimental investigation of the effect after laser-quenching treatment on fracture toughness in terms of the critical CTOD of a specimen, accounting for the laser-quenching effect. A numerical example presented in this work shows that the CTOD of the quenched can be significantly decreased in comparison with that of the unquenched. (C) 2008 Elsevier B.V. All rights reserved.

Three-dimensional supercell simulation of novel semiconductor nanostructures

In this thesis we investigate atomic scale imperfections and fluctuations in the quantum transport properties of novel semiconductor nanostructures. For this purpose, we have developed a numerically efficient supercell model of quantum transport capable of representing potential variations in three dimensions. This flexibility allows us to examine new quantum device structures made possible through state-of-the-art semiconductor fabrication techniques such as molecular beam epitaxy and nanolithography. These structures, with characteristic dimensions on the order of a few nanometers, hold promise for much smaller, faster and more efficient devices than those in present operation, yet they are highly sensitive to structural and compositional variations such as defect impurities, interface roughness and alloy disorder. If these quantum structures are to serve as components of reliable, mass-produced devices, these issues must be addressed.

In Chapter 1 we discuss some of the important issues in resonant tunneling devices and mention some of thier applications. In Chapters 2 and 3, we describe our supercell model of quantum transport and an efficient numerical implementation. In the remaining chapters, we present applications.

In Chapter 4, we examine transport in single and double barrier tunneling structures with neutral impurities. We find that an isolated attractive impurity in a single barrier can produce a transmission resonance whose position and strength are sensitive to the location of the impurity within the barrier. Multiple impurities can lead to a complex resonance structure that fluctuates widely with impurity configuration. In addition, impurity resonances can give rise to negative differential resistance. In Chapter 5, we study interface roughness and alloy disorder in double barrier structures. We find that interface roughness and alloy disorder can shift and broaden the n = 1 transmission resonance and give rise to new resonance peaks, especially in the presence of clusters comparable in size to the electron deBroglie wavelength. In Chapter 6 we examine the effects of interface roughness and impurities on transmission in a quantum dot electron waveguide. We find that variation in the configuration and stoichiometry of the interface roughness leads to substantial fluctuations in the transmission properties. These fluctuations are reduced by an attractive impurity placed near the center of the dot.

Mechanistic and kinetic studies of the surface chemistry of iridium and ruthenium

Quantitative investigations of the mechanisms and the kinetics of the surface-catalyzed activation of C-H, N-H, C-C, and C-N bonds on the close-packed surfaces of Ir(111) and Ru(001) have been performed. The interaction of CH_3NH_2 with Ru(001) was investigated in ultrahigh vacuum with the techniques of high-resolution electron energy loss spectroscopy and thermal desorption mass spectrometry. Activation of the central C-N bond is observed, but it is less favored than the competing channel of complete dehydrogenation, by a ratio between 2:1 to 3:1. The decomposition mechanism has been characterized with several surface intermediates and gas-phase products identified. A pronounced preference for the activation of C-H over N-H and C-N bonds has been established. Additionally, the kinetics of the initial dissociation of short chain alkanes on Ir(111) has been examined, and the rate parameters of the activation of C-C bonds and primary, secondary, and tertiary C-H bonds have been determined. The formation of primary alkyl products is favored, over most of the experimental temperature range, despite the thermodynamic preference for the activation of individual secondary and tertiary C-H bonds in comparison to individual primary C-H bonds. At higher surface temperatures, the activation of C-C bonds occurs at competitive rates to the C-H reaction channel. The measured deuterium kinetic isotope effect implicates substantial deformation of the terminal methyl group in the transition state of C-C bond cleavage. Finally, the surface structure sensitivity of C-H bond cleavage has been quantified for smooth (111) and corrugated (110) surfaces of iridium and platinum, as well as for step edge defect sites on Ir(111).

Analysis and optimization of stress wave propagation in two-dimensional granular crystals with defects

Granular crystals are compact periodic assemblies of elastic particles in Hertzian contact whose dynamic response can be tuned from strongly nonlinear to linear by the addition of a static precompression force. This unique feature allows for a wide range of studies that include the investigation of new fundamental nonlinear phenomena in discrete systems such as solitary waves, shock waves, discrete breathers and other defect modes. In the absence of precompression, a particularly interesting property of these systems is their ability to support the formation and propagation of spatially localized soliton-like waves with highly tunable properties. The wealth of parameters one can modify (particle size, geometry and material properties, periodicity of the crystal, presence of a static force, type of excitation, etc.) makes them ideal candidates for the design of new materials for practical applications. This thesis describes several ways to optimally control and tailor the propagation of stress waves in granular crystals through the use of heterogeneities (interstitial defect particles and material heterogeneities) in otherwise perfectly ordered systems. We focus on uncompressed two-dimensional granular crystals with interstitial spherical intruders and composite hexagonal packings and study their dynamic response using a combination of experimental, numerical and analytical techniques. We first investigate the interaction of defect particles with a solitary wave and utilize this fundamental knowledge in the optimal design of novel composite wave guides, shock or vibration absorbers obtained using gradient-based optimization methods.

Negative regulators of a growth factor-mediated signaling pathway in the nematode Caenorhabditis elegans

Vulval differentiation in C. elegans is mediated by an Epidermal growth factor (EGF)- EGF receptor (EGFR) signaling pathway. I have cloned unc-101, a negative regulator of vulval differentiation of the nematode C. elegans. unc-101 encodes a homolog of AP47, the medium chain of the trans-Golgi clathrin-associated protein complex. This identity was confirmed by cloning and comparing sequence of a C. elegans homolog of AP50, the medium chain of the plasma membrane clathrin-associated protein complex. I provided the first genetic evidence that the trans-Golgi clathrin-coated vesicles are involved in regulation of an EGF signaling pathway. Most of the unc-101 alleles are deletions or nonsense mutations, suggesting that these alleles severely reduce the unc-101 activity. A hybrid gene that contains parts of unc-101 and mouse AP4 7 rescued at least two phenotypes of unc-101 mutations, the Unc and the suppression of vulvaless phenotype of let-23(sy1) mutation. Therefore, the functions of AP47 are conserved between nematodes and mammals.

unc-101 mutations can cause a greater than wild-type vulval differentiation in combination with certain mutations in sli-1, another negative regulator of the vulval induction pathway. A mutation in a new gene, rok-1, causes no defect by itself, but causes a greater than wild-type vulval differentiation in the presence of a sli-1 mutation. The unc-101; rok-1; sli-1 triple mutants display a greater extent of vulval differentiation than any double mutant combinations of unc-101, rok-1 and sli-1. Therefore, rok-1 locus defines another negative regulator of the vulval induction pathway.

I analyzed a second gene encoding an AP47 homolog in C. elegans. This gene, CEAP47, encodes a protein 72% identical to both unc-101 and mammalian AP47. A hybrid gene containing parts of unc-101 and CEAP47 sequences can rescue phenotypes of unc-101 mutants, indicating that UNC- 101 and CEAP47 proteins can be redundant if expressed in the same set of cells.

Study of the origins of toughness in amorphous metals

Amorphous metals that form fully glassy parts over a few millimeters in thickness are still relatively new materials. Their glassy structure gives them particularly high strengths, high yield strains, high hardness values, high resilience, and low damping losses, but this can also result in an extremely low tolerance to the presence of flaws in the material. Since this glassy structure lacks the ordered crystal structure, it also lacks the crystalline defect (dislocations) that provides the micromechanism of toughening and flaw insensitivity in conventional metals. Without a sufficient and reliable toughness that results in a large tolerance of damage in the material, metallic glasses will struggle to be adopted commercially. Here, we identify the origin of toughness in metallic glass as the competition between the intrinsic toughening mechanism of shear banding ahead of a crack and crack propagation by the cavitation of the liquid inside the shear bands. We present a detailed study over the first three chapters mainly focusing on the process of shear banding; its crucial role in giving rise to one of the most damage-tolerant materials known, its extreme sensitivity to the configurational state of a glass with moderate toughness, and how the configurational state can be changed with the addition of minor elements. The last chapter is a novel investigation into the cavitation barrier in glass-forming liquids, the competing process to shear banding. The combination of our results represents an increased understanding of the major influences on the fracture toughness of metallic glasses and thus provides a path for the improvement and development of tougher metallic glasses.

Proteomic analysis of the Cdc48/Ubx network identifies a role for Ubx2 in the regulation of lipid biosynthesis

Cdc48/p97 is an essential, highly abundant hexameric member of the AAA (ATPase associated with various cellular activities) family. It has been linked to a variety of processes throughout the cell but it is best known for its role in the ubiquitin proteasome pathway. In this system it is believed that Cdc48 behaves as a segregase, transducing the chemical energy of ATP hydrolysis into mechanical force to separate ubiquitin-conjugated proteins from their tightly-bound partners.

Current models posit that Cdc48 is linked to its substrates through a variety of adaptor proteins, including a family of seven proteins (13 in humans) that contain a Cdc48-binding UBX domain. As such, due to the complexity of the network of adaptor proteins for which it serves as the hub, Cdc48/p97 has the potential to exert a profound influence on the ubiquitin proteasome pathway. However, the number of known substrates of Cdc48/p97 remains relatively small, and smaller still is the number of substrates that have been linked to a specific UBX domain protein. As such, the goal of this dissertation research has been to discover new substrates and better understand the functions of the Cdc48 network. With this objective in mind, we established a proteomic screen to assemble a catalog of candidate substrate/targets of the Ubx adaptor system.

Here we describe the implementation and optimization of a cutting-edge quantitative mass spectrometry method to measure relative changes in the Saccharomyces cerevisiae proteome. Utilizing this technology, and in order to better understand the breadth of function of Cdc48 and its adaptors, we then performed a global screen to identify accumulating ubiquitin conjugates in cdc48-3 and ubxΔ mutants. In this screen different ubx mutants exhibited reproducible patterns of conjugate accumulation that differed greatly from each other, pointing to various unexpected functional specializations of the individual Ubx proteins.

As validation of our mass spectrometry findings, we then examined in detail the endoplasmic-reticulum bound transcription factor Spt23, which we identified as a putative Ubx2 substrate. In these studies ubx2Δ cells were deficient in processing of Spt23 to its active p90 form, and in localizing p90 to the nucleus. Additionally, consistent with reduced processing of Spt23, ubx2Δ cells demonstrated a defect in expression of their target gene OLE1, a fatty acid desaturase. Overall, this work demonstrates the power of proteomics as a tool to identify new targets of various pathways and reveals Ubx2 as a key regulator lipid membrane biosynthesis.

Wire array photovoltaics

Over the past five years, the cost of solar panels has dropped drastically and, in concert, the number of installed modules has risen exponentially. However, solar electricity is still more than twice as expensive as electricity from a natural gas plant. Fortunately, wire array solar cells have emerged as a promising technology for further lowering the cost of solar.

Si wire array solar cells are formed with a unique, low cost growth method and use 100 times less material than conventional Si cells. The wires can be embedded in a transparent, flexible polymer to create a free-standing array that can be rolled up for easy installation in a variety of form factors. Furthermore, by incorporating multijunctions into the wire morphology, higher efficiencies can be achieved while taking advantage of the unique defect relaxation pathways afforded by the 3D wire geometry.

The work in this thesis shepherded Si wires from undoped arrays to flexible, functional large area devices and laid the groundwork for multijunction wire array cells. Fabrication techniques were developed to turn intrinsic Si wires into full p-n junctions and the wires were passivated with a-Si:H and a-SiNx:H. Single wire devices yielded open circuit voltages of 600 mV and efficiencies of 9%. The arrays were then embedded in a polymer and contacted with a transparent, flexible, Ni nanoparticle and Ag nanowire top contact. The contact connected >99% of the wires in parallel and yielded flexible, substrate free solar cells featuring hundreds of thousands of wires.

Building on the success of the Si wire arrays, GaP was epitaxially grown on the material to create heterostructures for photoelectrochemistry. These cells were limited by low absorption in the GaP due to its indirect bandgap, and poor current collection due to a diffusion length of only 80 nm. However, GaAsP on SiGe offers a superior combination of materials, and wire architectures based on these semiconductors were investigated for multijunction arrays. These devices offer potential efficiencies of 34%, as demonstrated through an analytical model and optoelectronic simulations. SiGe and Ge wires were fabricated via chemical-vapor deposition and reactive ion etching. GaAs was then grown on these substrates at the National Renewable Energy Lab and yielded ns lifetime components, as required for achieving high efficiency devices.

Cu2O substrates and epitaxial Cu2O/ZnO thin film hetero-structures for solar energy conversion

Future fossil fuel scarcity and environmental degradation have demonstrated the need for renewable, low-carbon sources of energy to power an increasingly industrialized world. Solar energy with its infinite supply makes it an extraordinary resource that should not go unused. However with current materials, adoption is limited by cost and so a paradigm shift must occur to get everyone on the same page embracing solar technology. Cuprous Oxide (Cu2O) is a promising earth abundant material that can be a great alternative to traditional thin-film photovoltaic materials like CIGS, CdTe, etc. We have prepared Cu2O bulk substrates by the thermal oxidation of copper foils as well Cu2O thin films deposited via plasma-assisted Molecular Beam Epitaxy. From preliminary Hall measurements it was determined that Cu2O would need to be doped extrinsically. This was further confirmed by simulations of ZnO/Cu2O heterojunctions. A cyclic interdependence between, defect concentration, minority carrier lifetime, film thickness, and carrier concentration manifests itself a primary reason for why efficiencies greater than 4% has yet to be realized. Our growth methodology for our thin-film heterostructures allow precise control of the number of defects that incorporate into our film during both equilibrium and nonequilibrium growth. We also report process flow/device design/fabrication techniques in order to create a device. A typical device without any optimizations exhibited open-circuit voltages Voc, values in excess 500mV; nearly 18% greater than previous solid state devices.

Energy transfer between silicon-oxygen-related defects and Yb3+ in transparent glass ceramics containing Ba2TiSi2O 8 nanocrystals

We report on the conversion of near-ultraviolet radiation of 250-350 nm into near-infrared emission of 970-1100 nm in Yb3+-doped transparent glass ceramics containing Ba2TiSi2O8 nanocrystals due to the energy transfer from the silicon-oxygen-related defects to Yb3+ ions. Efficient Yb3+ emission (F-2(5/2)-> F-2(7/2)) was detected under the excitation of defects absorption at 314 nm. The occurrence of energy transfer is proven by both steady state and time-resolved emission spectra, respectively, at 15 K. The Yb2O3 concentration dependent energy transfer efficiency has also been evaluated, and the maximum value is 65% for 8 mol % Yb2O3 doped glass ceramic. These materials are promising for the enhancement of photovoltaic conversion efficiency of silicon solar cells via spectra modification.

Characterization of the human SCF ubiquitin ligases - structure, function, and regulation

The SCF ubiquitin ligase complex of budding yeast triggers DNA replication by cata lyzi ng ubiquitination of the S phase CDK inhibitor SIC1. SCF is composed of several evolutionarily conserved proteins, including ySKP1, CDC53 (Cullin), and the F-box protein CDC4. We isolated hSKP1 in a two-hybrid screen with hCUL1, the human homologue of CDC53. We showed that hCUL1 associates with hSKP1 in vivo and directly interacts with hSKP1 and the human F-box protein SKP2 in vitro, forming an SCF-Iike particle. Moreover, hCUL1 complements the growth defect of yeast CDC53^(ts) mutants, associates with ubiquitination-promoting activity in human cell extracts, and can assemble into functional, chimeric ubiquitin ligase complexes with yeast SCF components. These data demonstrated that hCUL1 functions as part of an SCF ubiquitin ligase complex in human cells. However, purified human SCF complexes consisting of CUL1, SKP1, and SKP2 are inactive in vitro, suggesting that additional factors are required.

Subsequently, mammalian SCF ubiquitin ligases were shown to regulate various physiological processes by targeting important cellular regulators, like lĸBα, β-catenin, and p27, for ubiquitin-dependent proteolysis by the 26S proteasome. Little, however, is known about the regulation of various SCF complexes. By using sequential immunoaffinity purification and mass spectrometry, we identified proteins that interact with human SCF components SKP2 and CUL1 in vivo. Among them we identified two additional SCF subunits: HRT1, present in all SCF complexes, and CKS1, that binds to SKP2 and is likely to be a subunit of SCF5^(SKP2) complexes. Subsequent work by others demonstrated that these proteins are essential for SCF activity. We also discovered that COP9 Signalosome (CSN), previously described in plants as a suppressor of photomorphogenesis, associates with CUL1 and other SCF subunits in vivo. This interaction is evolutionarily conserved and is also observed with other Cullins, suggesting that all Cullin based ubiquitin ligases are regulated by CSN. CSN regulates Cullin Neddylation presumably through CSNS/JAB1, a stochiometric Signalosome subunit and a putative deneddylating enzyme. This work sheds light onto an intricate connection that exists between signal transduction pathways and protein degradation machinery inside the cell and sets stage for gaining further insights into regulation of protein degradation.

Effects of gamma-irradiation on Al2O3 crystals grown under reducing atmosphere

Gamma-ray irradiation-induced color centers in Al2O3 crystals grown by temperature gradient techniques (TGT) under a strongly reducing atmosphere were studied. The transition F+ -> F takes place during the irradiation process. Glow discharge mass spectroscopy (GDMS) and annealing treatments show that Fe3+ impurity ions are present in the crystals. A composite (F+-Fe3+) defect was presented to explain the origin of the 255 nm band absorption in the TGT-Al2O3 crystals. (C) 2006 Elsevier B.V. All rights reserved.

Upconversion luminescence and optical power limiting effect based on two- and three-photon absorption processes of ZnO crystal

Near-infrared to UV and visible upconversion luminescence was observed in single-crystalline ZnO under an 800 nm infrared femtosecond laser irradiation. The optical properties of the crystal reveal that the UV and VIS emission band are due to the exciton transition (D0X) bound to neutral donors and the deep luminescent centers in ZnO, respectively. The relationship between the upconversion luminescence intensity and the pump power of the femtosecond laser reveals that the UV emission belongs to three-photon sequential band-to-band excitation and the VIS emission belongs to two-photon simultaneous defect-absorption induced luminescence. A saturation phenomenon and polarization-dependent effect are also observed in the upconversion process of ZnO. A very good optical power limiting performance at 800 nm has been demonstrated. The two- and three-photon absorption coefficients of ZnO crystal were measured to be 0.2018 cm GW(-1) and 7.102 x 10(-3) cm(3) GW(-2), respectively. The two- and three-photon cross sections were calculated to be 1.189 x 10(-51) cm(4) s and 1.040 x 10(-80) cm(6) s(2), respectively. (c) 2007 Elsevier B.V. All rights reserved.