Publications

A microkinetic chemical reaction mechanism capable of describing both the storage and regeneration processes in a fully formulated lean NOx trap (LNT) is presented. The mechanism includes steps occurring on the precious metal, barium oxide (NOx storage), and cerium oxide (oxygen storage) sites of the catalyst. The complete reaction set is used in conjunction with a transient plug flow reactor code (including boundary layer mass transfer) to simulate not only a set of long storage/regeneration cycles with a CO/H2 reductant, but also a series of steady flow temperature sweep experiments that were previously analyzed with just a precious metal mechanism and a steady state code neglecting mass transfer. The results show that, while mass transfer effects are generally minor, NOx storage is not negligible during some of the temperature ramps, necessitating a re-evaluation of the precious metal kinetic parameters. The parameters for the entire mechanism are inferred by finding the best overall fit to the complete set of experiments. Rigorous thermodynamic consistency is enforced for parallel reaction pathways and with respect to known data for all of the gas phase species involved. It is found that, with a few minor exceptions, all of the basic experimental observations can be reproduced with the transient simulations. In addition to accounting for normal cycling behavior, the final mechanism should provide a starting point for the description of further LNT phenomena such as desulfation and the role of alternative reductants.

A microkinetic chemical reaction mechanism capable of describing both the storage and regeneration processes in a fully formulated lean NO{sub x} trap (LNT) is presented. The mechanism includes steps occurring on the precious metal, barium oxide (NO{sub x} storage), and cerium oxide (oxygen storage) sites of the catalyst. The complete reaction set is used in conjunction with a transient plug flow reactor code to simulate not only conventional storage/regeneration cycles with a CO/H{sub 2} reductant, but also steady flow temperature sweep experiments that were previously analyzed with just a precious metal mechanism and a steady state code. The results show that NO{sub x} storage is not negligible during some of the temperature ramps, necessitating a re-evaluation of the precious metal kinetic parameters. The parameters for the entire mechanism are inferred by finding the best overall fit to the complete set of experiments. Rigorous thermodynamic consistency is enforced for parallel reaction pathways and with respect to known data for all of the gas phase species involved. It is found that, with a few minor exceptions, all of the basic experimental observations can be reproduced with these purely kinetic simulations, i.e., without including mass-transfer limitations. In addition to accounting for normal cycling behavior, the final mechanism should provide a starting point for the description of further LNT phenomena such as desulfation and the role of alternative reductants.

A microkinetic reaction sub-mechanism designed to account for the sulfation and desulfation of a commercial lean NO_x trap (LNT) is presented. This set of reactions is appended to a previously developed mechanism for the normal storage and regeneration processes in an LNT in order to provide a comprehensive modeling tool. The reactions describing the storage, release, and reduction of sulfur oxides are patterned after those involving NO_x, but the number of reactions is kept to the minimum necessary to give an adequate simulation of the experimental observations. Values for the kinetic constants are estimated by fitting semi-quantitatively the somewhat limited experimental data, using a transient plug flow reactor code to model the processes occurring in a single monolith channel. Rigorous thermodynamic constraints are imposed in order to ensure that the overall mechanism is consistent both internally and with the known properties of all gas-phase species. The final mechanism is shown to be capable of reproducing the principal aspects of sulfation/desulfation behavior, most notably (a) the essentially complete trapping of SO₂ during normal cycling; (b) the preferential sulfation of NO_x storage sites over oxygen storage sites and the consequent plug-like and diffuse sulfation profiles; (c) the degradation of NO_x storage and reduction (NSR) capability with increasing sulfation level; and (d) the mix of H₂S and SO₂ evolved during desulfation by temperature-programmed reduction.

A one-dimensional isobaric reactor model is used to simulate hydrogen isotope exchange processes taking place during flow through a powdered palladium bed. This simple model is designed to serve primarily as a platform for the initial development of detailed chemical mechanisms that can then be refined with the aid of more complex reactor descriptions. The one-dimensional model is based on the Sandia in-house code TPLUG, which solves a transient set of governing equations including an overall mass balance for the gas phase, material balances for all of the gas-phase and surface species, and an ideal gas equation of state. An energy equation can also be solved if thermodynamic properties for all of the species involved are known. The code is coupled with the Chemkin package to facilitate the incorporation of arbitrary multistep reaction mechanisms into the simulations. This capability is used here to test and optimize a basic mechanism describing the surface chemistry at or near the interface between the gas phase and a palladium particle. The mechanism includes reversible dissociative adsorptions of the three gas-phase species on the particle surface as well as atomic migrations between the surface and the bulk. The migration steps are more general than those used previously in that they do not require simultaneous movement of two atoms in opposite directions; this makes possible the creation and destruction of bulk vacancies and thus allows the model to account for variations in the bulk stoichiometry with isotopic composition. The optimization code APPSPACK is used to adjust the mass-action rate constants so as to achieve the best possible fit to a given set of experimental data, subject to a set of rigorous thermodynamic constraints. When data for nearly isothermal and isobaric deuterium-to-hydrogen (D {yields} H) and hydrogen-to-deuterium (H {yields} D) exchanges are fitted simultaneously, results for the former are excellent, while those for the latter show pronounced deviations at long times. These discrepancies can be overcome by postulating the presence of a surface poison such as carbon monoxide, but this explanation is highly speculative. When the method is applied to D {yields} H exchanges intentionally poisoned by known amounts of CO, the fitting results are noticeably degraded from those for the nominally CO-free system but are still tolerable. When TPLUG is used to simulate a blowdown-type experiment, which is characterized by large and rapid changes in both pressure and temperature, discrepancies are even more apparent. Thus, it can be concluded that the best use of TPLUG is not in simulating realistic exchange scenarios, but in extracting preliminary estimates for the kinetic parameters from experiments in which variations in temperature and pressure are intentionally minimized.

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Overall project goal: Obtain the fundamental surface chemistry knowledge needed for the design and optimal utilization of NOx trap catalysts, thereby helping to speed the widespread adoption of this technology. Relevance to VT Program goals: Effective, durable advanced aftertreatment systems for lean-burn engines must be available if the fuel economy advantages of these engines are to be realized. Specific current year objective: Identify and correct any deficiencies in the previously developed reaction mechanism describing normal storage/regeneration cycles, and complete development of a supplementary mechanism accounting for the effects of sulfation. A fundamental understanding of LNT chemistry is needed to realize the full potential of this aftertreatment technology, which could lead to greater use of fuel-efficient lean-burn engines. We have used a multi-tiered approach to developing an elementary chemical mechanism benchmarked against experimental data: (1) Simulate a set of steady flow experiments, with storage effects minimized, to infer a tentative mechanism for chemistry on precious metal sites (completed). (2) Simulate a set of long cycle experiments to infer a mechanism for NOx and oxygen storage sites while simultaneously finalizing precious metal chemistry (completed). (3) Simulate a simplified sulfation/desulfation protocol to obtain a supplementary set of reactions involving sulfur on all three kinds of sites (nearly completed). (4) Investigate the potential role of reductants other than CO and H{sub 2}. While simulation of isothermal experiments is the preferred way to extract kinetic parameters, simulation of realistic storage/regeneration cycles requires that exotherms be considered. Our ultimate goal is to facilitate improved designs for LNT-based aftertreatment systems and to assist in the development of improved catalysts.

Our previously developed microkinetic model for lean NOx trap (LNT) storage and regeneration has been updated to address some longstanding issues, in particular the formation of N2O during the regeneration phase at low temperatures. To this finalized mechanism has been added a relatively simple (12-step) scheme that accounts semi-quantitatively for the main features observed during sulfation and desulfation experiments, namely (a) the essentially complete trapping of SO2 at normal LNT operating temperatures, (b) the plug-like sulfation of both barium oxide (NOx storage) and cerium oxide (oxygen storage) sites, (c) the degradation of NOx storage behavior arising from sulfation, (d) the evolution of H2S and SO2 during high temperature desulfation (temperature programmed reduction) under H2, and (e) the complete restoration of NOx storage capacity achievable through the chosen desulfation procedure.

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A new chemically-oriented mathematical model for the development step of the LIGA process is presented. The key assumption is that the developer can react with the polymeric resist material in order to increase the solubility of the latter, thereby partially overcoming the need to reduce the polymer size. The ease with which this reaction takes place is assumed to be determined by the number of side chain scissions that occur during the x-ray exposure phase of the process. The dynamics of the dissolution process are simulated by solving the reaction-diffusion equations for this three-component, two-phase system, the three species being the unreacted and reacted polymers and the solvent. The mass fluxes are described by the multicomponent diffusion (Stefan-Maxwell) equations, and the chemical potentials are assumed to be given by the Flory-Huggins theory. Sample calculations are used to determine the dependence of the dissolution rate on key system parameters such as the reaction rate constant, polymer size, solid-phase diffusivity, and Flory-Huggins interaction parameters. A simple photochemistry model is used to relate the reaction rate constant and the polymer size to the absorbed x-ray dose. The resulting formula for the dissolution rate as a function of dose and temperature is ?t to an extensive experimental data base in order to evaluate a set of unknown global parameters. The results suggest that reaction-assisted dissolution is very important at low doses and low temperatures, the solubility of the unreacted polymer being too small for it to be dissolved at an appreciable rate. However, at high doses or at higher temperatures, the solubility is such that the reaction is no longer needed, and dissolution can take place via the conventional route. These results provide an explanation for the observed dependences of both the dissolution rate and its activation energy on the absorbed dose.

We present a methodology for solving the inverse-quantitative structure-activity relationship (QSAR) problem using the molecular descriptor called signature. This methodology is detailed in four parts. First, we create a QSAR equation that correlates the occurrence of a signature to the activity values using a stepwise multilinear regression technique. Second, we construct constraint equations, specifically the graphicality and consistency equations, which facilitate the reconstruction of the solution compounds directly from the signatures. Third, we solve the set of constraint equations, which are both linear and Diophantine in nature. Last, we reconstruct and enumerate the solution molecules and calculate their activity values from the QSAR equation. We apply this inverse-QSAR method to a small set of LFA-1/ICAM-1 peptide inhibitors to assist in the search and design of more-potent inhibitory compounds. Many novel inhibitors were predicted, a number of which are predicted to be more potent than the strongest inhibitor in the training set. Two of the more potent inhibitors were synthesized and tested in-vivo, confirming them to be the strongest inhibiting peptides to date. Some of these compounds can be recycled to train a new QSAR and develop a more focused library of lead compounds. © 2003 Elsevier Inc. All rights reserved.

A phenomenological model was developed for multicomponent transport of charged species with simultaneous electrochemical reactions in concentrated solutions, and was applied to model processes in a thermal battery cell. A new general framework was formulated and implemented in GOMA (a multidimensional, multiphysics, finite-element computer code developed and being enhanced at Sandia) for modeling multidimensional, multicomponent transport of neutral and charged species in concentrated solutions. The new framework utilizes the Stefan-Maxwell equations that describe multicomponent diffusion of interacting species using composition-insensitive binary diffusion coefficients. The new GOMA capability for modeling multicomponent transport of neutral species was verified and validated using the model problem of ternary gaseous diffusion in a Stefan tube. The new GOMA-based thermal battery computer model was verified using an idealized battery cell in which concentration gradients are absent; the full model was verified by comparing with that of Bernardi and Newman (1987) and validated using limited thermal battery discharge-performance data from the open literature (Dunning 1981) and from Sandia (Guidotti 1996). Moreover, a new Liquid Chemkin Software Package was developed, which allows the user to handle manly aspects of liquid-phase kinetics, thermodynamics, and transport (particularly in terms of computing properties). Lastly, a Lattice-Boltzmann-based capability was developed for modeling pore- or micro-scale phenomena involving convection, diffusion, and simplified chemistry; this capability was demonstrated by modeling phenomena in the cathode region of a thermal battery cell.