基于跨尺度模型的界面研究

探索和建立不同尺度理论之间的关联模式是科学研究的重要课题，本文基于跨尺度模型着重探讨了金属陶瓷界面的凝聚能和原子结构问题。本文遵循原始Peierls-Nabarro模型的基本思想，提出了一种处理一维界面失配位错组的新方法。在这个推广的Peierls-Nabarro模型中，本文得到了一个简单而且准确的解析解，此解反映了失配位错的核结构、能量与失配度、剪切模量之间的依赖关系。当界面剪切模量较强而失配度较小时，界面的结构可以用一组奇导师Volterra位错来描述，这与一些原子模拟结果一致。采用这一简单的模型，引入第一原理计算得到的数据，此模型可以估算金属陶瓷界面的凝聚能。一维界面失配位错组的Peierls-Nabarro模型还被解析推广描述一大类较宽的位错。在模型中我们引进了一个参数a，通过控制参数a，我们可以系统地改变失配位错芯的宽度、剪切应力的分布和弹性恢复力。随着a增加，位错宽度增加，同时弹性恢复力和失配位错应力的幅度减少。当界面剪切模量强和失配度小时，失配位错的宽度近似线性反比于弹性恢复力的幅度大小。同时当界面剪切模量和失配度固定时，失配能、弹性能和总的界面能随a的增加而减少。界面能和恢复力律形式密切相关，当界面剪切模量弱和失配度大时，这种依赖关系更强。考虑到界面常常是在晶格两个方向都有失配，本文还引进了描述界面周期失配位错的二维广义Peierls-Nabarro模型，使得我们能够定量地研究界面的结构和能量。文中定量分析了广义堆垛能γ面对界面失配位错的结构和能量的影响，分析了位错网中两种位错组的相互作用。当界面剪切模量τ_0变大和失配度f变小时，随着位错核区占整个界面的比重下降，γ面的形状对界面能量和结构影响减弱，结果两种位错组之间的相互作用也减弱。此外γ面的变化还有可能导致位错网结构的转变，也就是导致界面结构的转变。应用此模型，本文还研究了金属－陶瓷Ag/MgO(100)界面，给出了界面的能量和原子结构。文中得出结论：在Ag/MgO(100)界面将会形成{1/2<110>; <110>}类型的位错网。此外由于界面失配位错的形成，Ag/MgO(100)界面凝聚能的理论值900mJ/m~2将减少214mJ/m~2，最终成为686mJ/m~2。基于第一原理赝势平面波的总能计算，文中给出了金属陶瓷Al/MgO(100)界面弛豫和未弛豫时的广义堆垛能面。然后结合第三章发展的广义二维Peierls-Nabarro模型，详细研究了金属陶瓷Al/MgO(100)界面的原子结构和界面能。文中得出的“在Al/MgO(100)界面将会形成{1/2<110>; <110>}类型位错网”的推论，证实了Vellinga等的猜测；文中还预测了凝聚能的理论是在600mJ/m~2（未弛豫情形）和670mJ/m~2（弛豫情形）之间。这个应用表明此方法能够容易地建立连续介质理论和第一原理计算之间的联系，实现理论上的跨尺度。本文最后提出了一种得到界面原子有效对势的反演方法。通过反演金属－MgO陶瓷界面的第一原理计算的凝聚能曲线，我们得到了一些金属原子和陶瓷离子之间的对势，此对势反映了金属陶瓷键合的特性。本文的反演方法提供了通过第一原理计算数据来拟合界面原子对势的一种可行性途径。这种方法可归结为第一类尺度关联理论，即单向的跨尺度关联模式。

Plastic Deformation Of Nanocrystalline Nickel

A high-resolution electron microscopy study has uncovered the plastic behavior of accommodating large strains in nanocrystalline (NC) Ni subject to cold rolling at liquid nitrogen temperature. The activation of grain-boundary-mediated-plasticity is evidenced in NC-Ni, including twinning and formation of stacking fault via partial dislocation slips from the grain boundary. The formation and storage of 60A degrees full dislocations are observed inside NC-grains. The grain/twin boundaries act as the barriers of dislocation slips, leading to dislocation pile-up, severe lattice distortion, and formation of sub-grain boundary. The vicinity of grain/twin boundary is where defects preferentially accumulate and likely the favorable place for onset of plastic deformation. The present results indicate the heterogeneous and multiple natures of accommodating plastic strains in NC-grains.

An Atomistic-Continuum Hybrid Simulation Of Fluid Flows Over Superhydrophobic Surfaces

Recent experiments have found that slip length could be as large as on the order of 1 mu m for fluid flows over superhydrophobic surfaces. Superhydrophobic surfaces can be achieved by patterning roughness on hydrophobic surfaces. In the present paper, an atomistic-continuum hybrid approach is developed to simulate the Couette flows over superhydrophobic surfaces, in which a molecular dynamics simulation is used in a small region near the superhydrophobic surface where the continuum assumption is not valid and the Navier-Stokes equations are used in a large region for bulk flows where the continuum assumption does hold. These two descriptions are coupled using the dynamic coupling model in the overlap region to ensure momentum continuity. The hybrid simulation predicts a superhydrophobic state with large slip lengths, which cannot be obtained by molecular dynamics simulation alone.

Strong Strain Hardening in Nanocrystalline Nickel

Low strain hardening has hitherto been considered an intrinsic behavior for most nanocrystalline (NC) metals, due to their perceived inability to accumulate dislocations. In this Letter, we show strong strain hardening in NC nickel with a grain size of 20 nm under large plastic strains. Contrary to common belief, we have observed significant dislocation accumulation in the grain interior. This is enabled primarily by Lomer-Cottrell locks, which pin the lock-forming dislocations and obstruct islocation. motion. These observations may help with developing strong and ductile NC metals and alloys.

Twinning partial multiplication at grain boundary in nanocrystalline fcc metals

Most deformation twins in nanocrystalline face-centered cubic fcc metals have been observed to form from grain boundaries. The growth of such twins requires the emission of Shockley partials from the grain boundary on successive slip planes. However, it is statistically improbable for a partial to exist on every slip plane. Here we propose a dislocation reaction and cross-slip mechanism on the grain boundary that would supply a partial on every successive slip plane for twin growth.This mechanism can also produce a twin with macrostrain smaller than that caused by a conventional twin.

Vortex dislocations in wake-type flow induced by spanwise disturbances

Vortex dislocations in wake-type flow induced by three types of spanwise disturbances superimposed on an upstream velocity profile are investigated by direct numerical simulations. Three distinct modes of vortex dislocations and flow transitions have been found. A local spanwise exponential decay disturbance leads to the appearance of a twisted chainlike mode of vortex dislocation. A stepped spanwise disturbance causes a streamwise periodic spotlike mode of vortex dislocation. A spanwise sinusoidal wavy disturbance with a moderate waviness causes a strong unsteadiness of wake behavior. This unsteadiness starts with a systematic periodic mode of vortex dislocation in the spanwise direction followed by the spanwise vortex shedding suppressed completely with increased time and the near wake becoming a steady shear flow. Characteristics of these modes of vortex dislocation and complex vortex linkages over the dislocation, as well as the corresponding dynamic processes related to the appearance of dislocations, are described by examining the variations of vortex lines and vorticity distribution. The nature of the vortex dislocation is demonstrated by the substantial vorticity modification of the spanwise vortex from the original spanwise direction to streamwise and vertical directions, accompanied by the appearance of noticeable vortex branching and complex vortex linking, all of which are produced at the locations with the biggest phase difference or with a frequency discontinuity between shedding cells. The effect of vortex dislocation on flow transition, either to an unsteady irregular vortex flow or suppression of the Kaacutermaacuten vortex shedding making the wake flow steady state, is analyzed. Distinct similarities are found in the mechanism and main flow phenomena between the present numerical results obtained in wake-type flows and the experimental-numerical results of cylinder wakes reported in previous studies.

An atomistic-continuum hybrid simulation of fluid flows over superhydrophobic surfaces

Recent experiments have found that slip length could be as large as on the order of 1 mu m for fluid flows over superhydrophobic surfaces. Superhydrophobic surfaces can be achieved by patterning roughness on hydrophobic surfaces. In the present paper an atomistic-continuum hybrid approach is developed to simulate the Couette flows over superhydrophobic surfaces in which a molecular dynamics simulation is used in a small region near the superhydrophobic surface where the continuum assumption is not valid and the Navier-Stokes equations are used in a large region for bulk flows where the continuum assumption does hold. These two descriptions are coupled using the dynamic coupling model in the overlap region to ensure momentum continuity. The hybrid simulation predicts a superhydrophobic state with large slip lengths which cannot be obtained by molecular dynamics simulation alone.

Molecular genetics of the Drosophila eyes absent gene

The Drosophila compound eye has provided a genetic approach to understanding the specification of cell fates during differentiation. The eye is made up of some 750 repeated units or ommatidia, arranged in a lattice. The cellular composition of each ommatidium is identical. The arrangement of the lattice and the specification of cell fates in each ommatidium are thought to occur in development through cellular interactions with the local environment. Many mutations have been studied that disrupt the proper patterning and cell fating in the eye. The eyes absent (eya) mutation, the subject of this thesis, was chosen because of its eyeless phenotype. In eya mutants, eye progenitor cells undergo programmed cell death before the onset of patterning has occurred. The molecular genetic analysis of the gene is presented.

The eye arises from the larval eye-antennal imaginal disc. During the third larval instar, a wave of differentiation progresses across the disc, marked by a furrow. Anterior to the furrow, proliferating cells are found in apparent disarray. Posterior to the furrow, clusters of differentiating cells can be discerned, that correspond to the ommatidia of the adult eye. Analysis of an allelic series of eya mutants in comparison to wild type revealed the presence of a selection point: a wave of programmed cell death that normally precedes the furrow. In eya mutants, an excessive number of eye progenitor cells die at this selection point, suggesting the eya gene influences the distribution of cells between fates of death and differentiation.

In addition to its role in the eye, the eya gene has an embryonic function. The eye function is autonomous to the eye progenitor cells. Molecular maps of the eye and embryonic phenotypes are different. Therefore, the function of eya in the eye can be treated independently of the embryonic function. Cloning of the gene reveals two cDNA's that are identical except for the use of an alternatively-spliced 5' exon. The predicted protein products differ only at the N-termini. Sequence analysis shows these two proteins to be the first of their kind to be isolated. Trangenic studies using the two cDNA's show that either gene product is able to rescue the eye phenotype of eya mutants.

The eya gene exhibits interallelic complementation. This interaction is an example of an "allelic position effect": an interaction that depends on the relative position in the genome of the two alleles, which is thought to be mediated by chromosomal pairing. The interaction at eya is essentially identical to a phenomenon known as transvection, which is an allelic position effect that is sensitive to certain kinds of chromosomal rearrangements. A current model for the mechanism of transvection is the trans action of gene regulatory regions. The eya locus is particularly well suited for the study of transvection because the mutant phenotypes can be quantified by scoring the size of the eye.

The molecular genetic analysis of eya provides a system for uncovering mechanisms underlying differentiation, developmentally regulated programmed cell death, and gene regulation.

Surface markers of regionalization in the vertebrate nervous system

In order to identify new molecules that might play a role in regional specification of the nervous system, we generated and characterized monoclonal antibodies (mAbs) that have positionally-restricted labeling patterns.

The FORSE-1 mAb was generated using a strategy designed to produce mAbs against neuronal cell surface antigens that might be regulated by regionally-restricted transcription factors in the developing central nervous system (CNS). FORSE-1 staining is enriched in the forebrain as compared to the rest of the CNS until E18. Between E11.5-E13.5, only certain areas of the forebrain are labeled. There is also a dorsoventrally-restricted region of labeling in the hindbrain and spinal cord. The mAb labels a large proteoglycan-like cell-surface antigen (>200 kD). The labeling pattern of FORSE-1 is conserved in various mammals and in chick.

To determine whether the FORSE-1 labeling pattern is similar to that of known transcription factors, the expression of BF-1 and Dlx-2 was compared with FORSE-1. There is a striking overlap between BF-1 and FORSE-1 in the telencephalon. In contrast, FORSE-1 and Dlx-2 have very different patterns of expression in the forebrain, suggesting that regulation by Dlx-2 alone cannot explain the distribution of FORSE-1. They do, however, share some sharp boundaries in the diencephalon. In addition, FORSE-1 identifies some previously unknown boundaries in the developing forebrain. Thus, FORSE-1 is a new cell surface marker that can be used to subdivide the embryonic forebrain into regions smaller than previously described, providing further complexity necessary for developmental patterning.

I also studied the expression of the cell surface protein CD9 in the developing and adult rat nervous system. CD9 is implicated in intercellular signaling and cell adhesion in the hematopoetic system. In the nervous system, CD9 may perform similar functions in early sympathetic ganglia, chromaffin cells, and motor neurons, all of which express the protein. The presence of CD9 on the surfaces of Schwann cells and axons at the appropriate time may allow the protein to participate in the cellular interactions involved in myelination.

Edad de menarquía e indicadores de adiposidad en universitarias del País Vasco

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Molecular neurogenetics of eye development in Drosophila

The compound eye of Drosophila melanogaster begins to differentiate during the late third larval instar in the eye-antennal imaginal disc. A wave of morphogenesis crosses the disc from posterior to anterior, leaving behind precisely patterned clusters of photoreceptor cells and accessory cells that will constitute the adult ommatidia of the retina. By the analysis of genetically mosaic eyes, it appears that any cell in the eye disc can adopt the characteristics of any one of the different cell types found in the mature eye, including photoreceptor cells and non-neuronal accessory cells such as cone cells. Therefore, cells within the prospective retinal epithelium assume different fates presumably via information present in the environment. The sevenless^+ (sev^+) gene appears to play a role in the expression of one of the possible fates, since the mutant phenotype is the lack of one of the pattern elements, namely, photoreceptor cell R7. The sev^+ gene product had been shown to be required during development of the eye, and had also been shown in genetic mosaics to be autonomous to presumptive R7. As a means of better understanding the pathway instructing the differentiation R7, the gene and its protein product were characterized.

The sev+ gene was cloned by P-element transposon tagging, and was found to encode an 8.2 kb transcript expressed in developing eye discs and adult heads. By raising monoclonal antibodies (MAbs) against a sev^+- β-galactosidase fusion protein, the expression of the protein in the eye disc was localized by immuno-electronmicroscopy. The protein localizes to the apical cell membranes and microvilli of cells in the eye disc epithelium. It appears during development at a time coincident with the initial formation of clusters, and in all the developing photoreceptors and accessory cone cells at a time prior to the overt differentiation of R7. This result is consistent with the pluripotency of cells in the eye disc. Its localization in the membranes suggests that it may receive information directing the development of R7. Its localization in the apical membranes and microvilli is away from the bulk of the cell contacts, which have been cited as a likely regions for information presentation and processing. Biochemical characterization of the sev^+ protein will be necessary to describe further its role in development.

Other mutations in Drosophila have eye phenotypes. These were analyzed to find which ones affected the initial patterning of cells in the eye disc, in order to identify other genes, like sev, whose gene products may be involved in generating the pattern. The adult eye phenotypes ranged from severe reduction of the eye, to variable numbers of photoreceptor cells per ommatidium, to sub de defects in the organization of the supporting cells. Developing eye discs from the different strains were screened using a panel of MAbs, which highlight various developmental stages. Two identified matrix elements in and anterior to the furrow, while others identified the developing ommatidia themselves, like the anti-sev MAb. Mutation phenotypes were shown to appear at many stages of development. Some mutations seem to affect the precursor cells, others, the setting up of the pattern, and still others, the maintenance of the pattern. Thus, additional genes have now been identified that may function to support the development of a complex pattern.

飞秒激光微加工：激光精密加工领域的新前沿

飞秒激光微加工技术具有加工精度高、热效应小、损伤阈值低以及能够实现真正的三维微结构加工等优点,这些特性是传统的激光加工技术所无法取代的。首先回顾了激光微加工和超短脉冲激光技术的发展历史,然后介绍超短脉冲激光与金属和介质材料相互作用的机制,接着阐述了飞秒激光直写、干涉和投影制备等各种加工方法的原理,重点讨论飞秒激光在三维光子器件集成、微流体芯片制备及其在生化传感方面的应用等,最后展望了飞秒激光微加工领域所面临的机遇和挑战,指出了未来的研究方向。

Experimental and theoretical studies of Notch signaling-mediated spatial pattern

Notch signaling acts in many diverse developmental spatial patterning processes. To better understand why this particular pathway is employed where it is and how downstream feedbacks interact with the signaling system to drive patterning, we have pursued three aims: (i) to quantitatively measure the Notch system's signal input/output (I/O) relationship in cell culture, (ii) to use the quantitative I/O relationship to computationally predict patterning outcomes of downstream feedbacks, and (iii) to reconstitute a Notch-mediated lateral induction feedback (in which Notch signaling upregulates the expression of Delta) in cell culture. The quantitative Notch I/O relationship revealed that in addition to the trans-activation between Notch and Delta on neighboring cells there is also a strong, mutual cis-inactivation between Notch and Delta on the same cell. This feature tends to amplify small differences between cells. Incorporating our improved understanding of the signaling system into simulations of different types of downstream feedbacks and boundary conditions lent us several insights into their function. The Notch system converts a shallow gradient of Delta expression into a sharp band of Notch signaling without any sort of feedback at all, in a system motivated by the Drosophila wing vein. It also improves the robustness of lateral inhibition patterning, where signal downregulates ligand expression, by removing the requirement for explicit cooperativity in the feedback and permitting an exceptionally simple mechanism for the pattern. When coupled to a downstream lateral induction feedback, the Notch system supports the propagation of a signaling front across a tissue to convert a large area from one state to another with only a local source of initial stimulation. It is also capable of converting a slowly-varying gradient in parameters into a sharp delineation between high- and low-ligand populations of cells, a pattern reminiscent of smooth muscle specification around artery walls. Finally, by implementing a version of the lateral induction feedback architecture modified with the addition of an autoregulatory positive feedback loop, we were able to generate cells that produce enough cis ligand when stimulated by trans ligand to themselves transmit signal to neighboring cells, which is the hallmark of lateral induction.

A multi-scale approach to shaping carbon nanotube structures for hollow microneedles

The concept of a carbon nanotube microneedle array is explored in this thesis from multiple perspectives including microneedle fabrication, physical aspects of transdermal delivery, and in vivo transdermal drug delivery experiments. Starting with standard techniques in carbon nanotube (CNT) fabrication, including catalyst patterning and chemical vapor deposition, vertically-aligned carbon nanotubes are utilized as a scaffold to define the shape of the hollow microneedle. Passive, scalable techniques based on capillary action and unique photolithographic methods are utilized to produce a CNT-polymer composite microneedle. Specific examples of CNT-polyimide and CNT-epoxy microneedles are investigated. Further analysis of the transport properties of polymer resins reveals general requirements for applying arbitrary polymers to the fabrication process.

The bottom-up fabrication approach embodied by vertically-aligned carbon nanotubes allows for more direct construction of complex high-aspect ratio features than standard top-down fabrication approaches, making microneedles an ideal application for CNTs. However, current vertically-aligned CNT fabrication techniques only allow for the production of extruded geometries with a constant cross-sectional area, such as cylinders. To rectify this limitation, isotropic oxygen etching is introduced as a novel fabrication technique to create true 3D CNT geometry. Oxygen etching is utilized to create a conical geometry from a cylindrical CNT structure as well as create complex shape transformations in other CNT geometries.

CNT-polymer composite microneedles are anchored onto a common polymer base less than 50 µm thick, which allows for the microneedles to be incorporated into multiple drug delivery platforms, including modified hypodermic syringes and silicone skin patches. Cylindrical microneedles are fabricated with 100 µm outer diameter and height of 200-250 µm with a central cavity, or lumen, diameter of 30 µm to facilitate liquid drug flow. In vitro delivery experiments in swine skin demonstrate the ability of the microneedles to successfully penetrate the skin and deliver aqueous solutions.

An in vivo study was performed to assess the ability of the CNT-polymer microneedles to deliver drugs transdermally. CNT-polymer microneedles are attached to a hand actuated silicone skin patch that holds a liquid reservoir of drugs. Fentanyl, a potent analgesic, was administered to New Zealand White Rabbits through 3 routes of delivery: topical patch, CNT-polymer microneedles, and subcutaneous hypodermic injection. Results demonstrate that the CNT-polymer microneedles have a similar onset of action as the topical patch. CNT-polymer microneedles were also vetted as a painless delivery approach compared to hypodermic injection. Comparative analysis with contemporary microneedle designs demonstrates that the delivery achieved through CNT-polymer microneedles is akin to current hollow microneedle architectures. The inherent advantage of applying a bottom-up fabrication approach alongside similar delivery performance to contemporary microneedle designs demonstrates that the CNT-polymer composite microneedle is a viable architecture in the emerging field of painless transdermal delivery.

Design strategies for ultra-high efficiency photovoltaics

While concentrator photovoltaic cells have shown significant improvements in efficiency in the past ten years, once these cells are integrated into concentrating optics, connected to a power conditioning system and deployed in the field, the overall module efficiency drops to only 34 to 36%. This efficiency is impressive compared to conventional flat plate modules, but it is far short of the theoretical limits for solar energy conversion. Designing a system capable of achieving ultra high efficiency of 50% or greater cannot be achieved by refinement and iteration of current design approaches.

This thesis takes a systems approach to designing a photovoltaic system capable of 50% efficient performance using conventional diode-based solar cells. The effort began with an exploration of the limiting efficiency of spectrum splitting ensembles with 2 to 20 sub cells in different electrical configurations. Incorporating realistic non-ideal performance with the computationally simple detailed balance approach resulted in practical limits that are useful to identify specific cell performance requirements. This effort quantified the relative benefit of additional cells and concentration for system efficiency, which will help in designing practical optical systems.

Efforts to improve the quality of the solar cells themselves focused on the development of tunable lattice constant epitaxial templates. Initially intended to enable lattice matched multijunction solar cells, these templates would enable increased flexibility in band gap selection for spectrum splitting ensembles and enhanced radiative quality relative to metamorphic growth. The III-V material family is commonly used for multijunction solar cells both for its high radiative quality and for the ease of integrating multiple band gaps into one monolithic growth. The band gap flexibility is limited by the lattice constant of available growth templates. The virtual substrate consists of a thin III-V film with the desired lattice constant. The film is grown strained on an available wafer substrate, but the thickness is below the dislocation nucleation threshold. By removing the film from the growth substrate, allowing the strain to relax elastically, and bonding it to a supportive handle, a template with the desired lattice constant is formed. Experimental efforts towards this structure and initial proof of concept are presented.

Cells with high radiative quality present the opportunity to recover a large amount of their radiative losses if they are incorporated in an ensemble that couples emission from one cell to another. This effect is well known, but has been explored previously in the context of sub cells that independently operate at their maximum power point. This analysis explicitly accounts for the system interaction and identifies ways to enhance overall performance by operating some cells in an ensemble at voltages that reduce the power converted in the individual cell. Series connected multijunctions, which by their nature facilitate strong optical coupling between sub-cells, are reoptimized with substantial performance benefit.

Photovoltaic efficiency is usually measured relative to a standard incident spectrum to allow comparison between systems. Deployed in the field systems may differ in energy production due to sensitivity to changes in the spectrum. The series connection constraint in particular causes system efficiency to decrease as the incident spectrum deviates from the standard spectral composition. This thesis performs a case study comparing performance of systems over a year at a particular location to identify the energy production penalty caused by series connection relative to independent electrical connection.