This final report summarizes work accomplished in the Program from January 1, 2001 through December 31, 2004. Most of the key technical objectives for this program were achieved. A breakthrough material system has lead to the development of an OTM (oxygen transport membrane) compact planar reactor design capable of producing either syngas or hydrogen. The planar reactor shows significant advantages in thermal efficiency and a step change reduction in costs compared to either autothermal reforming or steam methane reforming with CO{sub 2} recovery. Syngas derived ultra-clean transportation fuels were tested in the Nuvera fuel cell modular pressurized reactor and in International Truck and Engine single cylinder test engines. The studies compared emission and engine performance of conventional base fuels to various formulations of ultra-clean gasoline or diesel fuels. A proprietary BP oxygenate showed significant advantage in both applications for reducing emissions with minimal impact on performance. In addition, a study to evaluate new fuel formulations for an HCCI engine was completed.

An investigation of the crystal structure and the phase relationships in the Ce{sub 5}Si{sub 4-x}Ge{sub x} system has been carried out. The crystal structures of the single phase intermetallics were characterized using X-ray powder diffraction and subsequent refinement employing the Rietveld analysis technique was performed. The intermetallic system was found to crystallize in three distinct crystal structures. The Ce{sub 5}Si{sub 4}-based solid solution extends from x = 0 to x = 2.15 and it was found to crystallize in the well-known Zr{sub 5}Si{sub 4}-type tetragonal structure. The germanium rich alloys, where 3.1 {le} x {le} 4, crystallized in the Sm{sub 5}Ge{sub 4}-type orthorhombic structure. The crystal structure of the intermediate phase, when 2.35 {le} x {le} 2.8, was found out to be of the Gd{sub 5}Si{sub 2}Ge{sub 2}-type monoclinic structure. Microhardness tests were conducted on the samples in order to probe the trend in mechanical properties in this alloy system as a function of Ge concentration. The magnetic, thermal and magnetocaloric properties of the Ce{sub 5}Si{sub 4-x}Ge{sub x} alloy system have been investigated for x = 0, 1.0, 1.8, 2.5, 2.8, 3.5, 3.8 and 4.0. The phases with x = 0, 1.0 and 1.8 crystallize in the tetragonal Zr{sub 5}Si{sub …

The goal of this work, which is a collaborative effort between Indiana University, NIST, and Hamilton College, is to extend the technique of polarized neutron scattering into new domains by the development and application of polarized 3He-based neutron spin filters. After the IPNS experiment which measured Zeeman sp[litting in surface scattered neutrons using a polarized 3He cell as a polarization analyzer transporterd by car from Bloomington to Chicago, the Indiana work focused on technical developments to improve the 3He polarization of the Indiana compression system. The compression system was rebuilt with a new valve system which allows gas trapped in the dead volume of the compressors at the end of the piston stroke to be exhausted and conducted back to the optical pumping cell where it can be repolarized. We also incorporated a new intermediate storage volume made at NIST from 1720 glass which will reduce polarization losses between the compressors. Furthermore, we improved the stability of the 1083 nm laser by cooling the LMA rod. We achieved 60% 3he polarization in the optical pumping cell and 87% preservation of the polarization during compression. In parallel we built a magnetically-shielded transport solenoid for use on neutron scattering instruments such as …

This quarterly report covers the period from January 1, 2005 through March 31, 2005. It covers: technical development, permitting status, engineering status, construction status, operations summary and marketing support activities for this period. Plant startup is still continuing. Testing of admixtures to enhance extrusion and SDA wetting is continuing. Efforts are underway to improve plant availability.

Ground excavation constitutes a significant component of production costs in any surface mining operation. The excavation process entails material digging and removal in which the equipment motion is constrained by the workspace geometry. A major excavation problem is the variability of material properties, resulting in varying mechanical energy input and stress loading of shovel dipper-and-tooth assembly across the working bench. This variability has a huge impact on the shovel dipper and tooth assembly in hard formations. With this in mind, the primary objectives of the project were to (i) provide the theoretical basis to develop the Intelligent Shovel Excavation (ISE) technology to solve the problems associated with excavation in material formations; (ii) advance knowledge and frontiers in shovel excavation through intelligent navigation; and (iii) submit proposal for the design, development and implementation of the ISE technology for shovel excavation at experimental surface mining sites. The mathematical methods were used to (i) develop shovel's kinematics and dynamics, and (ii) establish the relationship between shovel parameters and the resistive forces from the material formation during excavation process. The ADAMS simulation environment was used to develop the hydraulic and cable shovel virtual prototypes. Two numerical examples are included to test the theoretical hypotheses …

The Bi(111) surface was studied by scanning tunneling microscopy (STM), transmission electron microscopy (TEM) and angle-resolved photoemission (ARPES) in order to verify the existence of a recently proposed surface charge density wave (CDW) [Ch. R. Ast and H. Hoechst Phys. Rev. Lett. 90, 016403 (2003)]. The STM and TEM results to not support a CDW scenario at low temperatures. Furthermore, the quasiparticle interference pattern observed in STM confirms the spin-orbit split character of the surface states which prevents the formation of a CDW, even in the case of good nesting. The dispersion of the electronic states observed with ARPES agrees well with earlier findings. In particular, the Fermi contour of the electron pocket at the centre of the surface Brillouin zone is found to have a hexagonal shape. However, no gap opening or other signatures of a CDW phase transition can be found in the temperature-dependent data.

The main purpose of this work is to investigate the glassy behavior of microemulsions and block copolymers. The origin of glassy behavior in microemulsions and block copolymers is frustration due to a competition between short-range interaction and long range interaction. According to the charge frustrated Ising model, the competition between ferromagnetic interaction and antiferromagnetic interaction is the origin of frustration in microemulsions. The competition between entropic effects and stoichiometric constraints responsible for the formation of micelles in microemulsions can lead to the emergence of a self generated glassy behavior in these systems. In the block copolymer, the competition between the repulsive short range interaction between monomers in polymer chains and the long range interaction by chemical bonds can lead to the emergence of a self generated glassy behavior. The criteria for the fluctuation induced first order transition and our microemulsion and block copolymer glasses are essentially the same. Both are a consequence of the large phase space of low energy excitations (14) (62) (all states with momenta q which fulfill |q| = q{sub m}) and are of at the most a moderate supercooling of the liquid state is required. This is strongly supported by the observation in Ref. (14) that …

The purpose of the ''Next Generation'' project was to develop technology that will provide a quantitative description of natural fracture properties and locations in low-permeability reservoirs. The development of this technology has consistently been ranked as one of the highest priority needs by industry. Numerous researchers and resource assessment groups have stated that the ability to identify area where intense clusters of natural fractures co-exist with gas-charged sands, the so called ''sweet spots'', will be the key to unlocking the vast quantities of gas in-place contained in these low-permeability gas basins. To meet this technology need, the ''Next Generation'' project was undertaken with three performance criteria in mind: (1) provide an integrated assessment of the burial and tectonic stresses in a basin responsible for natural fracture genesis (using seismic data, a significantly modified application of geomechanics, and a discrete natural fracture generation model); (2) link the assessment of natural fracture properties and locations to the reservoir's fluid, storage and flow properties; and, (3) provide a reservoir simulation-based calculation of the gas (and water) production capacity of a naturally fractured reservoir system. Phase III of the ''Next Generation'' project entailed the performance of a field demonstration of the software in an …

The case-hardening process modifies the near-surface permeability and conductivity of steel, as can be observed through changes in alternating current potential drop (ACPD) along a rod. In order to evaluate case depth of case hardened steel rods, analytical expressions are derived for the alternating current potential drop on the surface of a homogeneous rod, a two-layered and a three-layered rod. The case-hardened rod is first modeled by a two-layer rod that has a homogeneous substrate with a single, uniformly thick, homogeneous surface layer, in which the conductivity and permeability values differ from those in the substrate. By fitting model results to multi-frequency ACPD experimental data, estimates of conductivity, permeability and case depth are found. Although the estimated case depth by the two-layer model is in reasonable agreement with the effective case depth from the hardness profile, it is consistently higher than the effective case depth. This led to the development of the three-layer model. It is anticipated that the new three-layered model will improve the results and thus makes the ACPD method a novel technique in nondestructive measurement of case depth. Another way to evaluate case depth of a case hardened steel rod is to use induction coils. Integral form …

Capillary channels of cm-length and at plasma density low compared to gas jets are promising setups for low noise laser wakefield acceleration. Computationally, however, the large discrepancy of the length scales of the plasma and the laser are a big challenge. Methods are therefore sought that relax the need to concurrently resolve both length scales. Average methods, which split the electromagnetic field into a fast and a slowly varying part, allow to relax the constraint to resolve the laser wavelength. Such an envelope model is currently being incorporated into the VORPAL plasma simulation code. Simulation results for benchmark cases and for laser pulse propagation in a cm-scale channel are presented.

The work presented in this dissertation combines highly sensitive and selective fluorescence line-narrowing spectroscopy (FLNS) detection with various modes of immunoanalytical techniques. It has been shown that FLNS is capable of directly probing molecules immunocomplexed with antibodies, eliminating analytical ambiguities that may arise from interferences that accompany traditional immunochemical techniques. Moreover, the utilization of highly cross-reactive antibodies for highly specific analyte determination has been demonstrated. Finally, they demonstrate the first example of the spectral resolution of diastereomeric analytes based on their interaction with a cross-reactive antibody.

Two novel intermetallic compounds containing lanthanum and tin have been obtained for the first time. Single crystal structures of these two phases, La{sub 30}Sn{sub 30} and La{sub 32}Ni{sub 2}Sn{sub 35} have been studied by X-ray crystallography. La{sub 30}Sn{sub 30} is a new 1:1 binary containing La and Sn and has been refined in the Cmmm space group. This phase was made at high temperatures (<1200 C) from a loaded composition of La{sub 68}Sn{sub 70}. Unlike the reported 1:1 binary, LaSn which crystallizes in the Cmcm space group (only powder X-ray diffraction studies reported), La{sub 30}Sn{sub 30} forms good crystals for structural determination. The crystal structure of La{sub 30}Sn{sub 30} show Sn-Sn dimers and Sn-centered, face-sharing biaugmented triangular prisms composed of La atoms. La{sub 30}Sn{sub 30} does not belong to any known structure-type. La{sub 32}Ni{sub 2}Sn{sub 35} was obtained in high yields at high temperatures (> 1200 C) and refined in the 14/mmm space group. It belongs to the USi structure type in which the Ni/Sn atoms occupy the Si sites, and La/Sn atoms occupy the U sites. The crystal structure of La{sub 32}Ni{sub 2}Sn{sub 35} consists of buckled sheets made from La-centered, corner-shared octahedra of Sn. These sheets are intraconnected …

Surface undulations known as rumpling have been shown to develop at the surface of bond coats used in advanced thermal barrier coating systems. Rumpling can result in cracking and eventual spallation of the top coat. Many mechanisms to explain rumpling have been proposed, and among them is a martensitic transformation. High-temperature x-ray diffraction, differential scanning calorimetry and potentiometry were used to investigate the nature of the martensitic transformation in bulk platinum-modified nickel aluminides. It was found that the martensitic transformation has strong time dependence and can form over a range of temperatures. Cyclic oxidation experiments were performed on the bulk alloys to investigate the effect of the martensitic transformation on surface rumpling. It was found that the occurrence of rumpling was associated with the martensitic transformation. The degree of rumpling was found to increase with an increasing number of cycles and was independent of the heating and cooling rates used. The thickness of the oxide layer at the surface of the samples had a significant impact on the amplitude of the resulting undulations, with amplitude increasing with increasing oxide-layer thickness. Rumpling was also observed in an alloy based on the {gamma}-{gamma}' region of the nickel-aluminum-platinum phase diagram. Rumpling in this …

Many particle-laden flows in engineering applications involve turbulent gas flows. Modeling multiphase turbulent flows is an important research topic with applications in fluidized beds and particle conveying. A predictive multiphase turbulence model can help CFD codes to be more useful for engineering applications, such as the scale-up in the design of circulating fluidized combustor and coal gasifications. In engineering applications, the particle volume fraction can vary from dilute (<10{sup -4}) to dense ({approx} 50%). It is reasonable to expect that multiphase turbulence models should at least satisfy some basic modeling and performance criteria and give reasonable predictions for the canonical problems in dilute particle-laden turbulent flows. In this research, a comparative assessment of predictions from Simonin and Ahmadi's turbulence models is performed with direct numerical simulation (DNS) for two canonical problems in particle-laden turbulent flows. Based on the comparative assessment, some criteria and the areas for model improvement are identified: (1) model for interphase TKE transfer, especially the time scale of interphase TKE transfer, and (2) correct prediction of TKE evolution with variation of particle Stokes number. Some deficiencies that are identified in the Simonin and Ahmadi models, limit the applicability. A new multiphase turbulence model, the Equilibration of Energy …

This report documents a 3-year research program conducted by the Engines & Energy Conversion Laboratory (EECL) at Colorado State University (CSU) to develop micropilot ignition systems for existing pipeline compressor engines. Research activities for the overall program were conducted with the understanding that the efforts are to result in a commercial product to capture and disseminate the efficiency and environmental benefits of this new technology. An extensive state-of-art review was conducted to leverage the existing body of knowledge of micropilot ignition with respect to retrofit applications. Additionally, commercially-available fuel injection products were identified and applied to the program where appropriate. This approach will minimize the overall time-to-market requirements, while meeting performance and cost criteria. The objective for Phase I was to demonstrate the feasibility of micropilot ignition for large bore, slow speed engines operating at low compression ratios under laboratory conditions at the EECL. The primary elements of Micropilot Phase I were to develop a single-cylinder test chamber to study the injection of pilot fuel into a combustion cylinder and to develop, install and test a multi-cylinder micropilot ignition system for a 4-cylinder, natural gas test engine. In all, there were twelve (12) tasks defined and executed to support these …

Electrochemically modulated liquid chromatography (EMLC) employs a conductive material as both a stationary phase for chromatographic separations and as a working electrode for performing electrochemistry experiments. This dual functionality gives EMLC the capacity to manipulate chromatographic separations by changing the potential applied (E{sub app}) to the stationary phase with respect to an external reference. The ability to monitor retention as a function of E{sub app} provides a means to chromatographically monitor electrosorption processes at solid-liquid interfaces. In this dissertation, the retention mechanism for EMLC is examined from the perspective of electrical double layer theory and interfacial thermodynamics. From the chromatographic data, it is possible to determine the interfacial excess ({Lambda}) of a solute and changes in interfacial tension (d{gamma}) as a function of both E{sub app} and the supporting electrolyte concentration. Taken together, these two experimentally manipulated parameters can be examined within the context of the Gibbs adsorption equation to delineate the contribution of a variety of interfacial properties, including the charge of solute on the stationary phase and the potential of zero charge (PZC), to the mechanism behind EMLC-based retention. The chromatographic probing of interfacial phenomena is complemented by electroanalytical experiments that exploit the ability to monitor the electronic …

The objectives of this project are to evaluate the feasibility of carbon dioxide (CO{sub 2}) sequestration in Texas low-rank coals and to determine the potential for enhanced coalbed methane (CBM) recovery as an added benefit of sequestration. The main objective for this reporting period was to perform pressure transient testing to determine permeability of deep Wilcox coal to use as additional, necessary data for modeling performance of CO{sub 2} sequestration and enhanced coalbed methane recovery. To perform permeability testing of the Wilcox coal, we worked with Anadarko Petroleum Corporation in selecting the well and intervals to test and in designing the pressure transient test. Anadarko agreed to allow us to perform permeability tests in coal beds in an existing shut-in well (Well APCT2). This well is located in the region of the Sam K. Seymour power station, a site that we earlier identified as a major point source of CO{sub 2} emissions. A service company, Pinnacle Technologies Inc. (Pinnacle) was contracted to conduct the tests in the field. Intervals tested were 2 coal beds with thicknesses of 3 and 7 feet, respectively, at approximately 4,100 ft depth in the Lower Calvert Bluff Formation of the Wilcox Group in east-central Texas. …

New thermoelectric materials using Quantum Well (QW) technology are expected to increase the energy conversion efficiency to more than 25% from the present 5%, which will allow for the low cost conversion of waste heat into electricity. Hi-Z Technology, Inc. has been developing QW technology over the past six years. It will use Caterpillar, Inc., a leader in the manufacture of large scale industrial equipment, for verification and life testing of the QW films and modules. Other members of the team are Pacific Northwest National Laboratory, who will sputter large area QW films. The Scope of Work is to develop QW materials from their present proof-of-principle technology status to a pre-production level over a proposed three year period. This work will entail fabricating the QW films through a sputtering process of 50 {micro}m thick multi layered films and depositing them on 12 inch diameter, 5 {micro}m thick Si substrates. The goal in this project is to produce the technology for fabricating a basic 10-20 watt module that can be used to build up any size generator such as: a 5-10 kW Auxiliary Power Unit (APU), a multi kW Waste Heat Recovery Generator (WHRG) for a class 8 truck or as …

A detailed study of exchange-biased Fe/MnF{sub 2} bilayers using magneto-optical Kerr Effect shows that the magnetization reversal occurs almost fully through domain wall nucleation and propagation for external fields parallel to the exchange bias direction. For finite angles {phi} between bias and external field the magnetization is aligned perpendicular to the field cooling direction for a limited field range for decreasing fields. For external fields perpendicular to the bias direction the magnetization aligns with the field cooling direction for descending and ascending fields before fully reversing. The field range for which the magnetization is close to perpendicular to the external field can be estimated using a simple effective field model.

This report summarizes work performed by Physical Sciences Inc. (PSI) to advance the state-of-the-art of surveying for leaks of natural gas from transmission and distribution pipelines. The principal project goal was to develop means of deploying on an automotive platform an improved version of the handheld laser-based standoff natural gas leak detector previously developed by PSI and known as the Remote Methane Leak Detector or RMLD. A laser beam which interrogates the air for methane is projected from a spinning turret mounted upon a van. As the van travels forward, the laser beam scans an arc to the front and sides of the van so as to survey across streets and to building walls from a moving vehicle. When excess methane is detected within the arc, an alarm is activated. In this project, we built and tested a prototype Mobile RMLD (MRMLD) intended to provide lateral coverage of 10 m and one lateral scan for every meter of forward motion at forward speeds up to 10 m/s. Using advanced detection algorithms developed as part of this project, the early prototype MRMLD, installed on the back of a truck, readily detected simulated gas leaks of 50 liters per hour. As a …

Global structural optimizations with a genetic algorithm were performed for atomic cluster and surface systems including aluminum atomic clusters, Si magic clusters on the Si(111) 7 x 7 surface, silicon high-index surfaces, and Ag-induced Si(111) reconstructions. First, the global structural optimizations of neutral aluminum clusters Al{sub n} (n up to 23) were performed using a genetic algorithm coupled with a tight-binding potential. Second, a genetic algorithm in combination with tight-binding and first-principles calculations were performed to study the structures of magic clusters on the Si(111) 7 x 7 surface. Extensive calculations show that the magic cluster observed in scanning tunneling microscopy (STM) experiments consist of eight Si atoms. Simulated STM images of the Si magic cluster exhibit a ring-like feature similar to STM experiments. Third, a genetic algorithm coupled with a highly optimized empirical potential were used to determine the lowest energy structure of high-index semiconductor surfaces. The lowest energy structures of Si(105) and Si(114) were determined successfully. The results of Si(105) and Si(114) are reported within the framework of highly optimized empirical potential and first-principles calculations. Finally, a genetic algorithm coupled with Si and Ag tight-binding potentials were used to search for Ag-induced Si(111) reconstructions at various Ag and …

This project was awarded under U.S. Department of Energy (DOE) National Energy Technology Laboratory (NETL) Program Solicitation DE-PS26-00NT40769 and specifically addressed Technical Topical Area 4-Testing Novel and Less Mature Control Technologies on Actual Flue Gas at the Pilot Scale. The project team included the Energy & Environmental Research Center (EERC) as the main contractor; W.L. Gore & Associates, Inc., as a technical and financial partner; and the Big Stone Power Plant operated by Otter Tail Power Company, host for the field-testing portion of the research. Since 1995, DOE has supported development of a new concept in particulate control called the advanced hybrid particulate collector (AHPC). The AHPC has been licensed to W.L. Gore & Associates, Inc., and has been marketed as the Advanced Hybrid{trademark} filter by Gore. The Advanced Hybrid{trademark} filter combines the best features of electrostatic precipitators (ESPs) and baghouses in a unique configuration, providing major synergism between the two collection methods, both in the particulate collection step and in the transfer of dust to the hopper. The Advanced Hybrid{trademark} filter provides ultrahigh collection efficiency, overcoming the problem of excessive fine-particle emissions with conventional ESPs, and it solves the problem of reentrainment and re-collection of dust in conventional baghouses. …

This dissertation contains five papers in the format required for journal publication which describe (in part) my research accomplishments as a graduate student at Iowa State University. This work can be broadly categorized as the binding of weakly-coordinating ligands to cationic organometallic ruthenium fragments, and consists of two main areas of study. Chapters 2-4 are investigations into factors that influence the binding of dibenzothiophenes to {l_brace}Cp'Ru(CO){sub 2}{r_brace}{sup +} fragments, where Cp' = {eta}{sup 5}-C{sub 5}H{sub 5} (Cp) and {eta}{sup 5}-C{sub 5}Me{sub 5} (Cp*). Chapters 5 and 6 present the synthesis and structural characterization of complexes containing corannulene buckybowls that are {eta}{sup 6}-coordinated to {l_brace}Cp*Ru{r_brace}{sup +} fragments. The first chapter contains a brief description of the difficulty in lowering sulfur levels in diesel fuel along with a review of corannulene derivatives and their metal complexes. After the final paper is a short summary of the work herein (Chapter 7). Each chapter is independent, and all equations, schemes, figures, tables, references, and appendices in this dissertation pertain only to the chapter in which they appear.

The Neel temperatures, T{sub N}, of Tb{sub x}Er{sub 1-x}Ni{sub 2}B{sub 2}C samples have been determined from the temperature dependence of magnetization measurements. A breakdown of the de Gennes scaling of T{sub N} with a clear turning point around x = 0.45 has been observed. The T{sub N} values of Tb{sub x}Er{sub 1-x}Ni{sub 2}B{sub 2}C do not change much within the range of O < x < 0.45 and then, for larger x they increase almost linearly with concentration until T{sub N} = 14.9K is reached for x = 1, TbNi{sub 2}B{sub 2}C. The clear change in the x-dependence of T{sub N} around x = 0.45 can be linked to a change in the local moment ordering direction from transverse to longitudinal, a change which is consistent with recent resonant X-ray scattering data. These features in T{sub N}(x) can be explained using a mean field model.