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At least 163 records · Page 9

Patterned electrode catalyst

Disclosed herein are embodiments of a patterned electrode comprising regions of catalyst and segregating regions that separate the regions of catalyst. The segregating regions may be regions of non-catalytic material. The catalyst regions may correspond to the channels of a flow field. The electrode provides improved fuel cell performance, particularly at high current densities. The electrode may be for all suitable applications, such as in a membrane electrode assembly and/or a fuel cell. Also disclosed is a method for making the patterned electrode. The method may comprise using masks to apply the catalyst and non-catalyst material to a substrate.

Macauley, Natalia↗

Emulation of the calculations of final r -process abundance patterns with a neural network

This work explores the construction of a fast emulator for the calculation of the final pattern of nucleosynthesis in the rapid neutron capture process (the r-process). An emulator is built using a feed-forward artificial neural network (ANN). We train the ANN with nuclear data and relative abundance patterns. We take as input the β-decay half-lives and the one-neutron separation energy of the nuclei in the rare-earth region. The output is the final isotopic abundance pattern. In this work, we focus on the nuclear data and abundance patterns in the rare-earth region to reduce the dimension of the input and output space. We show that the ANN can capture the effect of the changes in the nuclear physics inputs on the final r-process abundance pattern in the adopted astrophysical conditions. We employ the deep ensemble method to quantify the prediction uncertainty of the neural network emulator. The emulator achieves a speed-up by a factor of about 20 000 in obtaining a final abundance pattern in the rare-earth region. The emulator may be utilized in statistical analyses such as uncertainty quantification, inverse problems, and sensitivity analysis.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Diffraction of entangled particles by light gratings

We analyze the diffraction regime of the Kapitza–Dirac effect for particles entangled in momentum. The detection patterns show two-particle interferences. In the single-mode case we identify a discontinuity in the set of joint detection probabilities, associated with the disconnected character of the space of non-separable states. For Gaussian multi-mode states we derive the diffraction patterns, providing an example of the dependence of the light–matter interaction on entanglement. When the particles are identical, we can explore the relation between exchange and entanglement effects. We find a complementary behavior between overlapping and Schmidt’s number. In particular, symmetric entanglement can cancel the exchange effects. - Highlights: • Kapitza–Dirac diffraction of entangled particles shows multiparticle interference. • There is a discontinuity in the set of joint detection patterns of entangled states. • We find a complementary behavior between overlapping and Schmidt’s number. • Symmetric entanglement can cancel the exchange effects.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

A Study of Scientometric Methods to Identify Emerging Technologies via Modeling of Milestones

This work examines a scientometric model that tracks the emergence of an identified technology from initial discovery (via original scientific and conference literature), through critical discoveries (via original scientific, conference literature and patents), transitioning through Technology Readiness Levels (TRLs) and ultimately on to commercial application. During the period of innovation and technology transfer, the impact of scholarly works, patents and on-line web news sources are identified. As trends develop, currency of citations, collaboration indicators, and on-line news patterns are identified. The combinations of four distinct and separate searchable on-line networked sources (i.e., scholarly publications and citation, patents, news archives, and online mapping networks) are assembled to become one collective network (a dataset for analysis of relations). This established network becomes the basis from which to quickly analyze the temporal flow of activity (searchable events) for the example subject domain we investigated.

99 GENERAL AND MISCELLANEOUS↗

Optimal design of chemoepitaxial guideposts for the directed self-assembly of block copolymer systems using an inexact Newton algorithm

Directed self-assembly (DSA) of block copolymers (BCPs) is one of the most promising developments in the cost-effective production of nanoscale devices. The process makes use of the natural tendency for BCP melts to form nanoscale structures upon phase separation. The phase separation can be directed through the use of chemically patterned substrates to promote the formation of morphologies that are essential to the production of semiconductor devices. Moreover, the design of substrate pattern can be formulated as an optimization problem for which we seek optimal substrate designs that effectively produce given target morphologies. In this paper, we adopt a phase field model given by a nonlocal Cahn–Hilliard partial differential equation (PDE) based on the minimization of the Ohta–Kawasaki free energy, and present an efficient PDE-constrained optimization framework for the optimal design problem. The design variables are the locations of circular- or strip-shaped guiding posts that are used to model the substrate chemical pattern. To solve the ensuing optimization problem, we propose a variant of an inexact Newton conjugate gradient algorithm tailored to this problem. Additionally, we demonstrate the effectiveness of our computational strategy on numerical examples that span a range of target morphologies. Owing to our second-order optimizer and fast state solver, the numerical results demonstrate five orders of magnitude reduction in computational cost over previous work. The efficiency of our framework and the fast convergence of our optimization algorithm enable us to rapidly solve the optimal design problem in not only two, but also three spatial dimensions.

97 MATHEMATICS AND COMPUTING↗

Electro-osmo-dialysis through nanoporous layers physically conjugated to micro-perforated ion-exchange membranes: Highly selective accumulation of trace coions

This study explores theoretically and numerically the phenomenon of counter-flow accumulation of trace coions during electro-osmo-dialysis through composite membranes containing nanoporous and perforated ion-exchange layers. The combination of charged nanopores and perforations allows electroosmosis, and ion concentration polarization appears near the ion-exchange layer. Accumulation of trace coions occurs because their advective and electromigration flow velocity components have opposite signs and are locally compensating in depletion regions where electric fields are high. This local compensation of flow components can give rise to high accumulation factors (>1000 in some cases) for trace coions at some distance from the interface between the nanoporous and ion-exchange layers. Moreover, the extent of this accumulation depends on the trace-coion diffusion coefficient. The resulting selectivity between different coions might serve as a basis for environmentally friendly separation of ionic species such as synthetic peptides or rare-earth elements. For example, a periodic process might include accumulation followed by species release into smaller volumes of solution. For both rare-earth ions and peptide-like species, the accumulation selectivity between ions with small differences in mobilities depends on system parameters such as nanoporous-layer thickness, distance between the perforations, and the zeta potential of the nanopore surface. Here, the use of optimal values of these membrane parameters may enable tuning of the electro-osmo-dialysis system for separation of specific ions. Modelling reveals that despite inhomogeneous patterns of fluid and ion flows close to the nanoporous/perforated ion-exchange interface, at relatively short distances from this interface (less than half the distance between the perforations) all the flows become practically one-dimensional (1D). Similarly, the concentration profiles of trace coions also become 1D. The flow one-dimensionality at short distances from the current-polarized interface enables a simple 1D approximation that is useful for an approximate analysis of trends in this multi-parameter system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of diisononyl phthalate on osteopenia in intact mice

Osteopenia is characterized by bone loss and deterioration of trabecular bone, which leads to osteoporotic fractures. This disease is highly prevalent in industrialized areas and is associated with exposure to endocrine disrupting chemicals (EDCs). Diisononyl phthalate (DINP) is one of these EDCs and is mainly used as a plasticizer in flexible polyvinyl chloride (PVC) products. Although it is well known that exposure to DINP is harmful to humans, no studies have been reported concerning its contribution to osteopenia. Therefore, in this study, we injected DINP (2, 20, and 200 mg/kg) into C3H/HeN mice for 6 weeks and found that the uterus weight, bone (femur and tibia) weight, and bone length of the DINP-exposed mice were reduced compared to those of the SHAM group. On the other hand, body weight, the serum alkaline phosphatase (ALP) and inorganic phosphorus (IP) levels in the DINP treated mice were increased compared with those of the SHAM group. The tartrate-resistant acid phosphatase (TRAP) activity (bone resorption marker) was increased and the bone alkaline phosphatase (BALP) activity was lowered by the treatment with DINP as compared with the SHAM group. Furthermore, the microarchitecture of the femur and tibia in the intact mice was destroyed by the DINP injection. The tissue volume (TV), bone volume (BV), BV/TV, bone surface (BS), BS/TV, trabecular thickness (Tb.Th), and trabecular number (Tb.N) were reduced and the trabecular pattern factor (Tb.Pf), structure model index (SMI), and trabecular separation (Tb.Sp) were increased by the DINP injection. The bone mineral density (BMD) of the femur and tibia was lower in the DINP group than in the SHAM group. These results indicate that DINP contributes to an increased risk of osteopenia via destruction of the microarchitecture and enhancement of osteoclast activity. - Highlights: • DINP induces reduction of the uterus weight, bone weight, bone length. • DINP induces enhancement of TRAP activity and suppression of BALP activity. • DINP induces cancellous bone loss in the tibia and femur. • DINP induces reduction of BMD in femur and tibia.

60 APPLIED LIFE SCIENCES↗

Online Ozonolysis Combined with Ion Mobility-Mass Spectrometry Provides a New Platform for Lipid Isomer Analyses

One of the most significant challenges in contemporary lipidomics lies in the separation and identification of lipid isomers that differ only in site(s) of unsaturation or geometric configuration of the carbon-carbon double bonds. While analytical separation techniques including ion mobility spectrometry (IMS) and liquid chromatography (LC) can separate isomeric lipids under appropriate conditions, conventional tandem mass spectrometry cannot provide unequivocal identification. To address this challenge, we have implemented ozone-induced dissociation (OzID) in-line with LC, IMS and high resolution mass spectrometry. Modification of an IMS- capable quadrupole time-of-flight mass spectrometer was undertaken to allow the introduction of ozone into the high-pressure trapping ion funnel region preceding the IMS cell. This enabled the novel LC-OzID-IMS-MS configuration where ozonolysis of ionized lipids occurred rapidly (10 ms) without prior mass-selection. LC-elution time alignment combined with accurate mass and arrival time extraction of ozonolysis products facilitated correlation of precursor and product ions without mass-selection (and associated reductions in duty cycle). Unsaturated lipids across 11 classes were examined using this workflow in both positive and negative ion modalities and in all cases the positions of carbon-carbon double bonds were unequivocally assigned based on predictable OzID transitions. Under these conditions geometric isomers exhibited different IMS arrival time distributions and distinct OzID product ion ratios providing a means for discrimination of cis/trans double bonds in complex lipids. The combination of OzID with multidimensional separations shows significant promise for facile profiling of unsaturation patterns within complex lipidomes.

Environmental Molecular Sciences Laboratory↗

Synthesis, structure, and electrochemical properties of [LNi(R f )(C 4 F 8 )] - and [LNi(R f ) 3 ] - complexes

The new anionic nickelate complexes [(MeCN)Ni(C 4 F 8 )(CF 3 )] -, [(MeCN)Ni(C 4 F 8 )(C 2 F 5 )] - , [(IMes)Ni(C 4 F 8 )(CF 3 )] - , [(IMes)Ni(CF 3 ) 3 ] - (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene), and [(F-NHC)Ni(Rf) 3 ] - (F-NHC = 1,3-bis(2,4-F2Ph), 2,4,6-F 3 Ph- or 3,4,5-F 3 Ph)imidazol-2-ylidene; (R f = CF 3 or C 2 F 5 ) were synthesized and structurally characterized. The electrochemical properties of all new compounds were revealed by cyclic voltammetry studies and compared to the known CF 3 analogue [(MeCN)Ni(CF 3 ) 3 ] -. The IMes-coordinated complexes exhibited initial oxidation events that were well-separated from a second oxidation process in the cyclic voltammograms. The complexes containing F-substituted NHC ligands [(F-NHC)Ni(CF 3 ) 3 ] - are structurally quite similar to the IMes derivative and reveal also two separated oxidation waves in their cyclic voltammograms. The absolute potentials as well as the separation between the two waves vary with the substitution pattern, suggesting that the NHC ligand environment (NHC = N-heterocyclic carbene) is an interesting platform for the development of new redox-triggered reactions that release trifluoromethyl and perfluoroalkyl radicals upon oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scientometric methods for identifying emerging technologies

Provided is a method of generating a scientometric model that tracks the emergence of an identified technology from initial discovery (via original scientific and conference literature), through critical discoveries (via original scientific, conference literature and patents), transitioning through Technology Readiness Levels (TRLs) and ultimately on to commercial application. During the period of innovation and technology transfer, the impact of scholarly works, patents and on-line web news sources are identified. As trends develop, currency of citations, collaboration indicators, and on-line news patterns are identified. The combinations of four distinct and separate searchable on-line networked sources (i.e., scholarly publications and citation, worldwide patents, news archives, and on-line mapping networks) are assembled to become one collective network (a dataset for analysis of relations). This established network becomes the basis from which to quickly analyze the temporal flow of activity (searchable events) for the example subject domain.

42 ENGINEERING↗

AR-CITE: Analysis of Search Results for the Clarification and Identification of Technology Emergence

The Analysis of Search Results for the Clarification and Identification of Technology Emergence (AR-CITE) computer code examines a scientometric model that tracks the emergence of an identified technology from initial discovery (via original scientific and conference literature), through critical discoveries (via original scientific, conference literature and patents), transitioning through Technology Readiness Levels (TRLs) and ultimately on to commercial currency of citations, collaboration indicators, and on-line news patterns are identified. The combinations of four distinct and separate searchable on-line networked sources (i.e. scholarly publications and citation, world patents, news archives, and on-line mapping networks) are assembled to become one collective network (a dataset for analysis of relations). This established network becomes the basis from which to quickly analyze the temporal flow of activity (searchable events) for the subject domain to be clarified and identified.

Source record↗

V‐Groove Si Nanopatterning for the Direct Epitaxy of Orientation‐Patterned III–V Nonlinear Optical Crystals

Orientation‐patterned (OP) III–V semiconductors—used as quasi‐phase‐matched crystals for nonlinear optics applications—are typically epitaxially grown on expensive III–V substrates using a complex process requiring three separate epitaxy steps. In this work, a method is demonstrated for growing orientation‐patterned III–V crystals on Si substrates through V‐groove nanopatterning and a single epitaxial growth. V‐groove Si allows for suppression of random antiphase domain formation that is typical of III–V growth on (001)‐oriented Si through the use of (111)‐faceted trenches patterned on (001)‐oriented Si substrates. By alternating the directions of the V‐groove trenches between [110] and [10], antiphase boundaries can be selectively induced at the boundaries between the two directions of trenches due to the difference in symmetry between the III–V material and Si. This approach allows for a greatly simplified process for growing OP‐III‐Vs and more broadly is a new, robust approach for precisely patterning antiphase boundaries of arbitrary shape and length scales down to 50 nm.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Chains of quantum dot molecules grown on Si surface pre-patterned by ion-assisted nanoimprint lithography

An original approach based on the combination of nanoimprint lithography and ion irradiation through mask has been developed for fabrication of large-area periodical pattern on Si(100). Using the selective etching of regions amorphized by ion irradiation ordered structures with grooves and ridges were obtained. The shape and depth of the relief were governed by ion energy and by the number of etching stages as well. Laterally ordered chains of Ge quantum dots were fabricated by molecular beam epitaxy of Ge on the pre-patterned Si substrates. For small amount of Ge deposited chains contain separate quantum dot molecules. The increase of deposition amount leads to overlapping of quantum dot molecules with formation of dense homogeneous chains of quantum dots. It was shown that the residual irradiation-induced bulk defects underneath the grooves suppress nucleation of Ge islands at the bottom of grooves. On pre-patterned substrates with whole defect regions, etched quantum dots grow at the bottom of grooves. The observed location of Ge quantum dots is interpreted in terms of local strain-mediated surface chemical potential which controls the sites of islands nucleation. The local chemical potential is affected by additional strain formed by the residual defects. It was shown by molecular dynamics calculations that these defects form the compressive strain at the bottom of grooves.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Assessment of serum biomarkers in rats after exposure to pesticides of different chemical classes

There is increasing emphasis on the use of biomarkers of adverse outcomes in safety assessment and translational research. We evaluated serum biomarkers and targeted metabolite profiles after exposure to pesticides (permethrin, deltamethrin, imidacloprid, carbaryl, triadimefon, fipronil) with different neurotoxic actions. Adult male Long–Evans rats were evaluated after single exposure to vehicle or one of two doses of each pesticide at the time of peak effect. The doses were selected to produce similar magnitude of behavioral effects across chemicals. Serum or plasma was analyzed using commercial cytokine/protein panels and targeted metabolomics. Additional studies of fipronil used lower doses (lacking behavioral effects), singly or for 14 days, and included additional markers of exposure and biological activity. Biomarker profiles varied in the number of altered analytes and patterns of change across pesticide classes, and discriminant analysis could separate treatment groups from control. Low doses of fipronil produced greater effects when given for 14 days compared to a single dose. Changes in thyroid hormones and relative amounts of fipronil and its sulfone metabolite also differed between the dosing regimens. Most cytokine changes reflected alterations in inflammatory responses, hormone levels, and products of phospholipid, fatty acid, and amino acid metabolism. These findings demonstrate distinct blood-based analyte profiles across pesticide classes, dose levels, and exposure duration. These results show promise for detailed analyses of these biomarkers and their linkages to biological pathways. - Highlights: • Pesticides typical of different classes produced distinct patterns of change in biomarker panels. • Based on the panels used, alterations suggest impacts on immune, metabolism, and homeostasis functions. • Some changes may reflect actions on neurotransmitter systems involved in immune modulation. • Fipronil effects on thyroid and kinetics differed with acute and repeated administration.

60 APPLIED LIFE SCIENCES↗

Pattern selection and super-patterns in the bounded confidence model

We study pattern formation in the bounded confidence model of opinion dynamics. In this random process, opinion is quantified by a single variable. Two agents may interact and reach a fair compromise, but only if their difference of opinion falls below a fixed threshold. Starting from a uniform distribution of opinions with compact support, a traveling wave forms and it propagates from the domain boundary into the unstable uniform state. Consequently, the system reaches a steady state with isolated clusters that are separated by distance larger than the interaction range. These clusters form a quasi-periodic pattern where the sizes of the clusters and the separations between them are nearly constant. We obtain analytically the average separation between clusters L . Interestingly, there are also very small quasi-periodic modulations in the size of the clusters. Furthermore, the spatial periods of these modulations are a series of integers that follow from the continued-fraction representation of the irrational average separation L .

97 MATHEMATICS AND COMPUTING↗

Grassland Bird Distribution and Raptor Flight Patterns in the Competitive Renewable Energy Zones of the Texas Panhandle [Thesis]

The consistent wind resource in the Great Plains of North America has encouraged the development of wind energy facilities across this region. In the Texas Panhandle, a high quality wind resource is only one factor that has led to the expansion of wind energy development. Other factors include federal tax incentives and the availability of subsidies. Moreover, the State Renewable Portfolio Standards (RPS), mandating production of 10,000 mega-watts of renewable energy in the state by 2025, has contributed to an amicable regulatory and permitting environment (State Energy Conservation Office 2010). Considering the current rate of development, the RPS will be met in coming years (American Wind Energy Association 2011) and the rate of development is likely to continue. To meet increased energy demands in the face of a chronically constrained transmission grid, Texas has developed a comprehensive plan that organizes and prioritizes new transmission systems in high quality wind resource areas called Competitive Renewable Energy Zones (CREZ). The CREZ plan provides developers a solution to transmission constraints and unlocks large areas of undeveloped wind resource areas. In the northern Texas panhandle, there are two CREZs that are classified Class 3 wind (Class 5 is the highest) and range from 862,725 to 1,772,328 ha in size (Public Utility Commission of Texas 2008). Grassland bird populations have declined more than any other bird group in North America (Peterjohn and Sauer 1999, Sauer et al. 2004). Loss of grassland habitat from agricultural development has been the greatest contributor to the decline of grassland bird populations, but development of non-renewable (i.e., oil, coal, and gas) and renewable energy (i.e., wind, solar, biomass, and geothermal) sources have contributed to the decline as well (Pimentel et al. 2002, Maybe and Paul 2007). The effects of wind energy development on declining grassland bird populations has become an area of extensive research, as we attempt to understand and minimize potential impacts of a growing energy sector on declining bird populations. Based on data from post-construction fatality surveys, two grassland bird groups have been the specific focus of research, passerines (songbird guild) and raptors (birds of prey). The effects of wind energy development on these two groups of birds, both of conservation concern, have been examined over the last decade. The primary focus of this research has been on mortality resulting from collision with wind turbines (Kuvlesky et al. 2007). Most studies just quantify post-construction fatality levels (e.g., Erickson et al. 2002) while very few studies provide a comparison of bird populations prior to development through a Before-After-Control-Impact (BACI) study design. Before-After-Control-Impact studies provide powerful evidence of avian/wind energy relationships (Anderson et al. 1999). Despite repeated urgency on conducting these types of studies (Anderson et al. 1999, Madders and Whitfield 2006, Kuvelsky et al. 2007), few have been conducted in North America. Although several European researchers (Larsson 1994, de Lucas et al. 2007) have used BACI designs to examine whether wind facilities modified raptor behavior, there is a scarcity of BACI data relating to North America grassland ecosystems that examine avian-wind energy relationships. There are less than a handful of studies in the entire United States, let alone the southern short grass prairie ecosystem, that incorporate preconstruction data to form the baseline for post-construction impact estimates (Johnson et al. 2000, Erickson et al. 2002). Although declines in grassland bird populations are well-documented (Peterjohn and Sauer 1999, Sauer et al. 2004), the causal mechanisms affecting the decline of grassland birds with increasing wind energy development in the southern short grass prairie are not well-understood (Kuvlesky et al. 2007, Maybe and Paul 2007). Several factors may potentially affect the bird population when wind turbines are constructed in areas with high bird densities (de Lucas et al. 2007). Habitat fragmentation, noise from turbines, physical movement of turbine blades, and increased vehicle traffic have been suggested as causes of decreased density of nesting grassland birds in Minnesota (Leddy et al. 1999), Oklahoma (O’Connell and Piorkowski 2006), and South Dakota (Shaffer and Johnson 2008). Similarly, constructing turbines in areas where bird flight patterns place them at similar heights of turbine blades increases the potential for bird collisions (Johnson et al. 2000, Hoover 2002). Raptor fatalities have been associated with topographic features such as ridges, saddles and rims where birds use updrafts from prevailing winds (Erickson et al. 2000, Johnson et al. 2000, Barrios and Rodriquez 2004, Hoover and Morrison 2005). Thus, wind energy development can result in indirect (e.g., habitat avoidance, decreased nest success) and direct (e.g., collision fatalities) impacts to bird populations (Anderson et al. 1999). Directly quantifying the level of potential impacts (e.g., estimated fatalities/mega-watthour) from wind energy development is beyond the scope of this study. Instead, I aim to quantify density, occupancy and flight behavior for the two bird groups mentioned earlier: obligate grassland songbirds and raptors, respectively, predict where impacts may occur, and provide management recommendations to minimize potential impacts. The United States Department of Energy (DOE), through the Office of Energy Efficiency and Renewable Energy Allocation, contracted Texas Tech University to investigate grassland bird patterns of occurrence in the anticipated CREZ in support of DOE’s 20% Wind Energy by 2030 initiative. In cooperation with Iberdrola Renewables, Inc., studies initiated by Wulff (2010) at Texas Tech University were continued at an area proposed for wind energy development and a separate reference site unassociated with wind energy development. I focused on four primary objectives and this thesis is accordingly organized in four separate chapters that address grassland bird density, grassland bird occupancy, raptor flight patterns, and finally I summarize species diversity and composition. The following chapters use formatting from the Journal of Wildlife Management guidelines (Block et al. 2011) with modifications as required by the Texas Tech University Graduate School. 1) I estimate pre-construction bird density patterns using methods that adjust for imperfect detection. I used a distance sampling protocol that effectively accounts for incomplete detection in the field where birds are present but not detected (Buckland et al. 2001). I improved density estimates with hierarchical distance sampling models, a modeling technique that effectively incorporates the detection process with environmental covariates that further influence bird density (Royle et al. 2004, Royle and Dorazio 2008). Covariates included road density and current oil and gas infrastructure to determine the relationship between existing energy development and bird density patterns. Further, I used remote sensing techniques and vegetation field data to investigate how landcover characteristics influenced bird density patterns. I focused species-specific analyses on obligate grassland birds with >70 detections per season namely grasshopper sparrow (Ammodramus savannarum) and horned lark (Eremophila alpestris). Chapter II focuses on hierarchical models that model and describe relationships between grassland bird density and anthropogenic and landscape features. 2) A large number of bird detections (>70) are needed to estimate density using distance sampling and collection of such quantity are often not feasible, particularly for cryptic species or species that naturally occur at low densities (Buckland et al. 2001). Occupancy models operate with far fewer data and are often used as a surrogate for bird abundance when there are fewer detections (MacKenzie and Nichols 2004). I used occupancy models that allow for the possibility of imperfect detection and species abundance to improve estimates of occurrence probability (Royal 2004). I focused species-specific analyses on grassland birds with few detections: Cassin’s sparrow (Peucaea cassinii), eastern meadowlark (Sturnella magna), and upland sandpiper (Bartramia longicauda). Chapter III uses a multi-season dynamic site occupancy model that incorporates bird abundance to better estimate occurrence probability. 3) When I considered the topographic relief of the study sites, the proposed design of the wind facility and its location within the central U.S. migratory corridor, I expanded the study to investigate raptor abundance and flight behavior (Hoover 2002, Miller 2008). I developed a new survey technique that improved the accuracy of raptor flight height estimates and compared seasonal counts and flight heights at the plateau rim and areas further inland. I used counts and flight behaviors to calculate species-specific collision risk indices for raptors based on topographic features. I focused species-specific analyses on raptors with the highest counts: American kestrel (Falco sparverius), northern harrier (Circus cyaneus), red-tailed hawk (Buteo jamaicensis), Swainson’s hawk (Buteo swainsoni), and turkey vulture (Cathartes aura). Chapter IV describes patterns of seasonal raptor abundance and flight behavior and how topography modulates collision risk with proposed wind energy turbines. 4) Finally, for completeness, in Chapter V I summarize morning point count data for all species and provide estimates of relative composition and species diversity with the Shannon-Wiener Diversity Index (Shannon and Weaver 1949).

17 WIND ENERGY↗

Direct Writing of X-ray Gratings Using Zone-Plate-Array Lithography (ZPAL)

With the objective of providing the synchrotron and free-electron-laser communities with rapid turnaround and low prices for the highest quality and most advanced gratings and diffractive-focusing optics, LumArray has made specific improvements to its ZP-150 maskless photolithography system, which is based on Zone-Plate-Array Lithography (ZPAL), a technology unique to Lumarray. ZPAL’s advantages include an ability to correct in software for systematic patterning errors. Emphasis was placed on interferometric measurements of various contributors to patterning errors using Fizeau interferometry and a Mireau technique that was developed specifically for measuring errors within a micron-scale area. Average line-placement error was reduced below 20 nm using both pattern-file distortion and address-grid modification. The preferred implementation, address-grid modification, is hardware-based and requires no user intervention while also correcting more types of error. With continued iteration and refinement of the error measurements, we anticipate achieving global line-placement error below10nm. In order to investigate line-edge smoothness and high-frequency line-placement errors, a scheme for inspecting micron-sized areas was invented and implemented based on Mireau interferometry. This enabled the various contributions to be separately evaluated and measured. These included: exposure-dose variation, pattern-writing strategy and errors in the positioning of the microlenses. Deleterious crosstalk between microlenses was minimized via a pattern-dependent software modification. The impact of exposure threshold was revealed and adjustment made. The impact of address-grid fineness on line-edge roughness was likewise shown. Lastly, techniques were developed to measure and correct errors in the positioning of microlenses within the array. We expect final calibration of microlens positions to within 5nm.

42 ENGINEERING↗

3D Printed, Low Tortuosity Garnet Framework For Beyond 500 Wh/kg Batteries

In this project, we developed LLZO garnet ink recipes and processes for 3D-printing highly ordered ionically conductive garnet porous structures on dense garnet separators. Using this technique, we are able to fabricate controlled architecture LLZO garnet solid-state electrolyte (SSE) trilayers for application in solid-state lithium batteries. The trilayer comprises a thin dense center layer sandwiched between a 3D-printed patterned porous layer and a random porous layer. The dense layer functions as the ionic separator between the anode and cathode. The random porous layer hosts the lithium-metal anode and provides the structural support. The 3D-printed SSE patterned porous layer hosts the cathode, providing continuous, low tortuosity pathways for fast 3D Li+ transport through the cell while increasing the electrode/electrolyte interface area to decrease the interfacial resistance. Compared to the random porous structure, this ordered patterned structure possesses more vacant space for higher cathode loading without sacrificing ionically conducting capability, thus potentially greatly increasing the cell energy density. For demonstration purposes, we developed two patterns for the 3D-printed porous layer: grids and columns, for hosting sulfur and NMC cathode, respectively. The corresponding two types of cells were fabricated and tested, and have demonstrated achievement of theoretical discharge capacity without cathode calendaring. In addition, we developed a fundamental solid-state ionic and electronic transport model to optimize the 3D-printed structures for maximum energy and power density. The model was validated by experiment and provides the critical design criteria for achieving the >500 Wh/kg energy goal as function of C-rate.

25 ENERGY STORAGE↗