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Immiscibility in the Fe3O4-FeCr2O4 Spinel Binary

Description: A recent thermodynamic model of mixing in spinel binaries, based on changes in cation disordering (x) between tetrahedral and octahedral sites, is investigated for applicability to the Fe{sub 3}O{sub 4}-FeCr{sub 2}O{sub 4} system under conditions where incomplete mixing occurs. Poor agreement with measured consolute solution temperature and solvus is attributed to neglect of: (1) ordering of magnetic moments of cations in the tetrahedral sublattice antiparallel to the moments of those in the octahedral sublattice and (2) pair-wise electron hopping between octahedral site Fe{sup 3+} and Fe{sup 2+} ions. Disordering free energies ({Delta}G{sub D}), from which free energies of mixing are calculated, are modeled by {Delta}G{sub D} = {alpha}{chi} + {beta}{chi}{sup 2} - T(S{sub c} + {chi}{sigma}{sub el} + {gamma}{chi}{sigma}{sup mag}) where the previously-neglected effects are accommodated by: (1) adding a non-configurational entropy term to provide coupling between cation disordering and magnetic ordering and (2) revising the configurational entropy (S{sub c}) analysis. Applying the constraint {alpha} = -(2/3){beta} and regressing the existing database for Fe{sup 2+} ion disorder in Fe{sub 3}O{sub 4} gives: {beta} = -31,020 {+-} 1050 J mol{sup -1}, {sigma}{sub el}/R = -0.730 {+-} 0.081 and {gamma}, the coupling parameter between cation disordering and magnetic ordering, = -0.664 {+-} 0.075. The revised mixing model predicts a consolute solution temperature (T{sub cs}) = 600 C and a solvus at 500 C of n = 0.05 and 0.70 for the Fe(Fe{sub 1-n}Cr{sub n}){sub 2}O{sub 4} spinel binary.
Date: March 20, 2003
Creator: Ziemniak, S.E. & Castelli, R.A.
Partner: UNT Libraries Government Documents Department

Structure Map for Embedded Binary Alloy Nanocrystals

Description: The equilibrium structure of embedded nanocrystals formed from strongly segregating binary-alloys is considered within a simple thermodynamic model. The model identifies two dimensionlessinterface energies that dictate the structure, and allows prediction of the stable structure for anychoice of these parameters. The resulting structure map includes three distinct nanocrystal mor-phologies: core/shell, lobe/lobe, and completely separated spheres.
Date: September 20, 2008
Creator: Yuan, C.W.; Shin, S.J.; Liao, C.Y.; Guzman, J.; Stone, P.R.; Watanabe, M. et al.
Partner: UNT Libraries Government Documents Department

HIGH TEMPERATURE HIGH PRESSURE THERMODYNAMIC MEASUREMENTS FOR COAL MODEL COMPOUNDS

Description: The enthalpy of a fluid measured with respect to some reference temperature and pressure (enthalpy increment or Cp) is required for many engineering designs. Different techniques for determining enthalpy increments include direct measurement, integration of heat capacity as a function of temperature at constant pressure, and calculation from accurate density measurements as a function of temperature and pressure with ideal-gas enthalpies. Techniques have been developed for measurement of heat capacities using differential scanning calorimeters, but routine measurements with a precision better than 3% are rare. For thermodynamic model development, excess enthalpies or enthalpies of mixing of binary and ternary systems are generally required. Although these data can be calculated from measured values of incremental enthalpies of mixtures and corresponding pure components, the method of calculation involves subtraction of large numbers, and it is impossible to obtain accurate results from relatively accurate incremental enthalpy data. Directly measured heats of mixing provide better data for model development. In what follows, we give a brief literature survey of experimental methods available for measurement of incremental enthalpies as well as heats of mixing.
Date: February 24, 1999
Creator: Kabadi, Vinayak N.
Partner: UNT Libraries Government Documents Department

Dynamic Simulation and Optimization of Nuclear Hydrogen Production Systems

Description: This project is part of a research effort to design a hydrogen plant and its interface with a nuclear reactor. This project developed a dynamic modeling, simulation and optimization environment for nuclear hydrogen production systems. A hybrid discrete/continuous model captures both the continuous dynamics of the nuclear plant, the hydrogen plant, and their interface, along with discrete events such as major upsets. This hybrid model makes us of accurate thermodynamic sub-models for the description of phase and reaction equilibria in the thermochemical reactor. Use of the detailed thermodynamic models will allow researchers to examine the process in detail and have confidence in the accurary of the property package they use.
Date: July 31, 2009
Creator: Barton, Paul I.; Kaximi, Mujid S.; Bollas, Georgios & Munoz, Patricio Ramirez
Partner: UNT Libraries Government Documents Department

Condensation analysis for plate-frame heat exchangers

Description: A theoretical analysis is presented to predict single component and binary-mixture condensation in plate-frame heat exchangers. A thermodynamic property model based on the Peng-Robinson equation of state was developed for the binary-mixture equilibrium and formulated into a performance prediction program. A set of equations was formulated and a calculation algorithm was developed to predict the local rate of heat and mass transfer for binary mixtures. Friction-factor and heat-transfer-coefficient correlations were developed using experimental data obtained with ammonia condensation. The role of the mass-transfer resistance associated with the condensation process were analyzed for a propane/butane mixture using two limiting cases: (1) no liquid-phase mass-transfer resistance, and (2) infinite liquid-phase mass-transfer resistance. The results show that the vapor-phase mass-transfer resistance is the controlling mechanism for binary-mixture condensation.
Date: July 1, 1995
Creator: Arman, B. & Rabas, T.J.
Partner: UNT Libraries Government Documents Department

Low-density ionization behavior

Description: As part of a continuing study of the physics of matter under extreme conditions, I give some results on matter at extremely low density. In particular I compare a quantum mechanical calculation of the pressure for atomic hydrogen with the corresponding pressure given by Thomas-Fermi theory. (This calculation differs from the ``confined atom`` approximation in a physically significant way.) Since Thomas-Fermi theory in some sense, represents the case of infinite nuclear charge, these cases should represent extremes. Comparison is also made with Saha theory, which considers ionization from a chemical point of view, but is weak on excited-state effects. In this theory, the pressure undergoes rapid variation as electron ionization levels are passed. This effect is in contrast to the smooth behavior of the Thomas-Fermi fixed temperature, complete ionization occurs in the low density limit, I study the case where the temperature goes appropriately to zero with the density. Although considerable modification is required, Saha theory is closer to the actual results for this case than is Thomas-Fermi theory.
Date: April 1, 1995
Creator: Baker, G.A. Jr.
Partner: UNT Libraries Government Documents Department

An analytical method of predicting Lee-Kesler-Ploecker binary interaction coefficients: Part 1, For non-polar hydrocarbon mixtures

Description: An analytical method is proposed for finding numerical values of binary interaction coefficients for non-polar hydrocarbon mixtures when the Lee-Kesler (LK) equation of state is applied. The method is based on solving simultaneous equations, which are Ploecker`s mixing rules for pseudocritical parameters of a mixture, and the Lee-Kesler equation for the saturation line. For a hydrocarbon mixture, the method allows prediction of {kappa}{sub ij} interaction coefficients (ICs) which are close to values obtained by processing experimental p-v-t data on the saturation line and subsequent averaging. For mixtures of hydrocarbon molecules containing from 2 to 9 carbon atoms, the divergence between calculated and experimentally based ICs is no more than {plus_minus}0.4%. The possibility of extending application of this method to other non-polar substances is discussed.
Date: December 31, 1994
Creator: Sand, J.R.
Partner: UNT Libraries Government Documents Department

Thermodynamic Cycle Analysis Program (TCAP)

Description: This report describes the Thermodynamic Cycle Analysis Program (TCAP) software developed in support of the Collaborative Advanced Gas Turbine (CAGT) research project. The goal of the CAGT project was to evaluate different configurations of gas turbine-based power generation cycles. TCAP software enables the user to graphically construct power cycles that incorporate a variety of components such as compressors, turbines, heat exchangers, and reactors. The user also specifies the input condition of the working fluid and the parameters associated with each component. TCAP then calculates the composition and thermodynamic properties of the working fluid at every point in the cycle. From this data, TCAP calculates the overall thermodynamic efficiency of the cycle and emission levels of specific chemicals. Thermodynamic and chemical kinetic data are based on the Chemkin family of application codes and libraries.
Date: January 1, 1997
Creator: Yoshimura, A.S.
Partner: UNT Libraries Government Documents Department

Exploratory Research on Simulation of CO2-Brine-Mineral Interactions

Description: Application of many carbon sequestration strategies requires knowledge of thermodynamic properties for the extremely complex chemical system of CO{sub 2}-SO{sub 2}-H{sub 2}O-NaCl-CaCl{sub 2}-MgCl{sub 2}. This University Coal Research Phase I program has been successful and highly productive in exploring an approach to develop an equation of state (EOS) to describe thermodynamic properties in the above chemical system. We have compiled available laboratory experimental data and thermodynamic models, and evaluated their appropriateness for the carbon sequestration process. Based on this literature review, we provided an improved CO{sub 2} solubility model for the CO{sub 2}-H{sub 2}O-NaCl system, which incorporates newly available experimental measurements funded by DOE, and is valid in temperature range from 273 to 533 K, pressure from 0 to 2000 bar, and salinity from 0 to 4.5 molality of NaCl equivalent. The improved model also greatly improves the computational efficiency of CO{sub 2} solubility calculations and thus is better suited to be incorporated into large computer simulation models (e.g., reservoir simulation models). The literature review and model development provided insights of the data needs and directions for future work. Synergetic collaboration with DOE scientists has resulted in simulations of injected CO{sub 2} fate in sandstone aquifer with a one-dimensional numerical coupled reactive transport model. We evaluated over 100 references on CO{sub 2} solubility and submitted two manuscripts to peer-reviewed journals. One paper has been accepted for publication in ''Environmental Geosciences''.
Date: November 1, 2005
Creator: Zhu, Chen & Chiang, Shiao hung
Partner: UNT Libraries Government Documents Department

The Melting Curve and High-Pressure Chemistry of Formic Acid to 8 GPa and 600 K

Description: We have determined the melting temperature of formic acid (HCOOH) to 8.5 GPa using infrared absorption spectroscopy, Raman spectroscopy and visual observation of samples in a resistively heated diamond-anvil cell. The experimentally determined melting curve compares favorably with a two-phase thermodynamic model. Decomposition reactions were observed above the melting temperature up to a pressure of 6.5 GPa, where principal products were CO{sub 2}, H{sub 2}O and CO. At pressures above 6.5 GPa, decomposition led to solid-like reaction products. Infrared and Raman spectra of these recovered products indicate that pressure affects the nature of carbon-carbon bonding.
Date: April 13, 2005
Creator: Montgomery, W; Zaug, J M; Howard, W M; Goncharov, A F; Crowhurst, J C & Jeanloz, R
Partner: UNT Libraries Government Documents Department

TRANSPORT AND REDUCTION POSSIBILITIES DURING TPBAR EXTRACTION

Description: In light of the discovery of the activated zinc 65 in the TEF process piping, a discussion of potential sources and mechanisms for the production of this species has been initiated. A suspected source is the presence of Cu as a contaminant in many of the alloy components that comprise the TPBARs and the presence of Zn as a contaminant in the aluminide coating. These two sources are expected to produce metallic transmutation products that could be mobile and be extracted from the metallic components of the TPBARs. Another potential source is the presence of ZnO that is present as part of the crud on the external surfaces of the TPBARs. In addition, it is conceivable to have ZnO within the TPBARs from transmutation products and subsequent oxidation reactions with water. This memo does not attempt to address all of the possible sources, nor does it derive the most likely scenarios as to how Zn or ZnO may be present in the TPBARs it merely posits that it is present as a transmutation product and if present, elementally, it may be mobile under high vacuum conditions at high temperatures as indicated by the pressure temperature curve shown in Fig. 1. Further, this document shows that it is thermodynamically feasible to reduce ZnO to Zn by solid state reactions of the ZnO with other metallic components in the TPBARs. However, for these reactions to occur, the ZnO must be in contact with the more active metal so that the chemical reactions can occur. The proposed reactions are based on equilibrium thermodynamics. For simplicity, they do not take into account the quantities of the various materials, the compositions, the effect of alloying, or other technical issues, they are intended only to provide feasibility for the reduction reactions. A more complete thermodynamic model ...
Date: May 19, 2008
Creator: Korinko, P
Partner: UNT Libraries Government Documents Department

CO2 CAPTURE BY ABSORPTION WITH POTASSIUM CARBONATE

Description: The objective of this work is to improve the process for CO{sub 2} capture by alkanolamine absorption/stripping by developing an alternative solvent, aqueous K{sub 2}CO{sub 3} promoted by piperazine. A rigorous thermodynamic model has been developed with a stand-alone FORTRAN code to represent the CO{sub 2} vapor pressure and speciation of the new solvent. Parameters have been developed for use of the electrolyte NRTL model in AspenPlus. Analytical methods have been developed using gas chromatography and ion chromatography. The heat exchangers for the pilot plant have been ordered.
Date: April 1, 2003
Creator: Rochelle, Gary T.; Chen, Eric; Cullinane, J. Tim; Hilliard, Marcus & Jones, Terraun
Partner: UNT Libraries Government Documents Department

Analytical and numerical models of uranium ignition assisted by hydride formation

Description: Analytical and numerical models of uranium ignition assisted by the oxidation of uranium hydride are described. The models were developed to demonstrate that ignition of large uranium ingots could not occur as a result of possible hydride formation during storage. The thermodynamics-based analytical model predicted an overall 17 C temperature rise of the ingot due to hydride oxidation upon opening of the storage can in air. The numerical model predicted locally higher temperature increases at the surface; the transient temperature increase quickly dissipated. The numerical model was further used to determine conditions for which hydride oxidation does lead to ignition of uranium metal. Room temperature ignition only occurs for high hydride fractions in the nominally oxide reaction product and high specific surface areas of the uranium metal.
Date: May 1, 1996
Creator: Totemeier, T.C. & Hayes, S.L.
Partner: UNT Libraries Government Documents Department

Hydrogen fueling station development and demonstration

Description: This is the final report of a one-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). This project sought to develop and demonstrate a hydrogen fueling station for vehicles. Such stations are an essential infrastructural element in the practical application of hydrogen as vehicle fuel, and a number of issues such as safety, efficiency, design, and operating procedures can only be accurately addressed by a practical demonstration. Regardless of whether the vehicle is powered by an internal combustion engine or fuel cell, or whether the vehicle has a liquid or gaseous fuel tank, the fueling station is a critical technology that is the link between the local storage facility and the vehicle.
Date: September 1, 1996
Creator: Edeskuty, F.J.; Daney, D.; Daugherty, M.; Hill, D. & Prenger, F.C.
Partner: UNT Libraries Government Documents Department

EFFECT OF HEATING RATE ON THE THERMODYNAMIC PROPERTIES OF PULVERIZED COAL

Description: This semi-annual technical progress report describes work performed under DOE Grant No. DE-FG22-96PC96224 during the period March 24, 1999 to September 23, 1999 which covers the last (sixth) six months of the project. During this reporting period, extraction of devolatilization time-scales and temperature data at these time-scales analyzing the high-speed films taken during the experiments was complete. Also a new thermodynamic model was developed to predict the heat transfer behavior for coal particles subjected to a range of heating rates using one approach based on the analogy of polymers. Sensitivity analyses of this model suggest that bituminous coal particles behave like polymers during rapid heating on the order of 10{sup 4}-10{sup 7} K/s. At these heating rates during the early stages within the first few milliseconds of heating time, the vibrational part of the heat capacity of the coal molecules appears to be still frozen but during the transition from heat-up to devolatization, the heat capacity appears to attain a sudden jump in its value as in the case of polymers. There are few data available in the coal literature for 10{sup 2}-10{sup 3} K/s obtained by UTRC in their previous studies. These data were obtained for a longer heating duration on the order of several seconds as opposed to the 10 milliseconds heating time in the single particle experiments discussed above. The polymer analogy model is being modified to include longer heating time on the order of several seconds to test these data. It is expected that the model might still do a good job in the case of these larger heating time but very low heating rate experiments. Completion of the numerical analysis of the experimental data and preparation of the final report are in progress.
Date: November 2, 1999
Creator: Sampath, Ramanathan
Partner: UNT Libraries Government Documents Department

EFFECT OF HEATING RATE ON THE THERMODYNAMIC PROPERTIES OF PULVERIZED COAL

Description: This final technical report describes work performed under DOE Grant No. DE-FG22-96PC96224 during the period September 24, 1996 to September 23, 1999 which covers the entire performance period of the project. During this period, modification, alignment, and calibration of the measurement system, measurement of devolatilization time-scales for single coal particles subjected to a range of heating rates and temperature data at these time-scales, and analysis of the temperature data to understand the effect of heating rates on coal thermal properties were carried out. A new thermodynamic model was developed to predict the heat transfer behavior for single coal particles using one approach based on the analogy for thermal property of polymers. Results of this model suggest that bituminous coal particles behave like polymers during rapid heating on the order of 10{sup 4}-10{sup 5} K/s. At these heating rates during the early stages of heating, the vibrational part of the heat capacity of the coal molecules appears to be still frozen but during the transition from heat-up to devolatilization, the heat capacity appears to attain a sudden jump in its value as in the case of polymers. There are a few data available in the coal literature for low heating rate experiments (10{sup 2}-10{sup 3} K/s) conducted by UTRC, our industrial partner, in this project. These data were obtained for a longer heating duration on the order of several seconds as opposed to the 10 milliseconds heating time of the single particle experiments discussed above. The polymer analogy model was modified to include longer heating time on the order of several seconds to test these data. However, the model failed to predict these low heating rate data. It should be noted that UTRC's work showed reasonably good agreement with Merrick model heat capacity predictions at these low heating rates, but at ...
Date: January 1, 2000
Creator: Sampath, Ramanathan
Partner: UNT Libraries Government Documents Department

Thermodynamic Modeling of Savannah River Evaporators

Description: A thermodynamic model based on the code SOLGASMIX is developed to calculate phase equilibrium in evaporators and related tank wastes at the Savannah River Site (SRS). This model uses the Pitzer method to calculate activity coefficients, and many of the required Pitzer parameters have been determined in the course of this work. Principal chemical species in standard SRS simulant solutions are included, and the temperature range for most parameters has been extended above 100 C. The SOLGASMIX model and calculations using the code Geochemists Workbench are compared to actual solubility data including silicate, aluminate, and aluminosilicate solutions. In addition, SOLGASMIX model calculations are also compared to transient solubility data involving SRS simulant solutions. These comparisons indicate that the SOLGASMIX predictions closely match reliable data over the range of temperature and solution composition expected in the SRS evaporator and related tanks. Predictions using the Geochemists Workbench may be unreliable, due primarily to the use of an inaccurate activity coefficient model.
Date: August 2, 2001
Creator: Weber, C.F.
Partner: UNT Libraries Government Documents Department

Superheating and supercooling of Ge nanocrystals embedded inSiO2

Description: Free-standing nanocrystals exhibit a size-dependant thermodynamic melting point reduction relative to the bulk melting point that is governed by the surface free energy. The presence of an encapsulating matrix, however, alters the interface free energy of nanocrystals and their thermodynamic melting point can either increase or decrease relative to bulk. Furthermore, kinetic contributions can significantly alter the melting behaviors of embedded nanoscale materials. To study the effect of an encapsulating matrix on the melting behavior of nanocrystals, we performed in situ electron diffraction measurements on Ge nanocrystals embedded in a silicon dioxide matrix. Ge nanocrystals were formed by multi-energy ion implantation into a 500 nm thick silica thin film on a silicon substrate followed by thermal annealing at 900 C for 1 h. We present results demonstrating that Ge nanocrystals embedded in SiO{sub 2} exhibit a 470 K melting/solidification hysteresis that is approximately symmetric about the bulk melting point. This unique behavior, which is thought to be impossible for bulk materials, is well described using a classical thermodynamic model that predicts both kinetic supercooling and kinetic superheating. The presence of the silica matrix suppresses surface pre-melting of nanocrystals. Therefore, heterogeneous nucleation of both the liquid phase and the solid phase are required during the heating and cooling cycle. The magnitude of melting hysteresis is governed primarily by the value of the liquid Ge/solid Ge interface free energy, whereas the relative values of the solid Ge/matrix and liquid Ge/matrix interface free energies govern the position of the hysteresis loop in absolute temperature.
Date: August 21, 2006
Creator: Xu, Q.; Sharp, I.D.; Yuan, C.W.; Yi, D.O.; Liao, C.Y.; Glaeser,A.M. et al.
Partner: UNT Libraries Government Documents Department

Comprehensive Approaches to Multiphase Flows in Geophysics - Application to nonisothermal, nonhomogenous, unsteady, large-scale, turbulent dusty clouds I. Hydrodynamic and Thermodynamic RANS and LES Models

Description: The objective of this manuscript is to fully derive a geophysical multiphase model able to ''accommodate'' different multiphase turbulence approaches; viz., the Reynolds Averaged Navier-Stokes (RANS), the Large Eddy Simulation (LES), or hybrid RANSLES. This manuscript is the first part of a larger geophysical multiphase project--lead by LANL--that aims to develop comprehensive modeling tools for large-scale, atmospheric, transient-buoyancy dusty jets and plume (e.g., plinian clouds, nuclear ''mushrooms'', ''supercell'' forest fire plumes) and for boundary-dominated geophysical multiphase gravity currents (e.g., dusty surges, diluted pyroclastic flows, dusty gravity currents in street canyons). LES is a partially deterministic approach constructed on either a spatial- or a temporal-separation between the large and small scales of the flow, whereas RANS is an entirely probabilistic approach constructed on a statistical separation between an ensemble-averaged mean and higher-order statistical moments (the so-called ''fluctuating parts''). Within this specific multiphase context, both turbulence approaches are built up upon the same phasic binary-valued ''function of presence''. This function of presence formally describes the occurrence--or not--of any phase at a given position and time and, therefore, allows to derive the same basic multiphase Navier-Stokes model for either the RANS or the LES frameworks. The only differences between these turbulence frameworks are the closures for the various ''turbulence'' terms involving the unknown variables from the fluctuating (RANS) or from the subgrid (LES) parts. Even though the hydrodynamic and thermodynamic models for RANS and LES have the same set of Partial Differential Equations, the physical interpretations of these PDEs cannot be the same, i.e., RANS models an averaged field, while LES simulates a filtered field. In this manuscript, we also demonstrate that this multiphase model fully fulfills the second law of thermodynamics and fulfills the necessary requirements for a well-posed initial-value problem. In the next manuscripts, we will further develop specific closures for ...
Date: September 5, 2005
Creator: Dartevelle, S.
Partner: UNT Libraries Government Documents Department

Chemistry of Actinides in Molten Glasses and Its Correlation to Structural Performance of Solid Glasses: Filling the Knowledge Gap

Description: This proposal focuses on the following basic objectives to generate critical information for the following research Needs: (a) to conduct spectroscopic speciation of uranium compounds in glass-forming melts as a function of the acid-base composition of the glasses and melt temperatures, and to use these data to develop a general thermodynamic model for the dissolution of actinide species in oxidic glass matrices, (b ) to build a scientific basis for a new methodology to measure the basicity of glasses via optical spectra of in-situ immobilized actinides and to use this optical basicity as a primary actinide structure indicator for solid glass matrices, (c) to define the local environment of actinides in solid glasses via fluorescence lifetime distribution methods, (d) to correlate the above spectral ''fingerprints'' of actinides in solid and molten glasses with glass stability and the leaching rates of individual actinide species from a glass matrix.
Date: June 1, 2002
Creator: Dai, Sheng; Boatner, Lynn; Schumacher, Ray F. & Barnes, C. E.
Partner: UNT Libraries Government Documents Department

Chemistry of Actinides in Molten Glasses and Its Correlation to Structural Performance of Solid Glasses: Filling the Knowledge Gap

Description: This proposal focuses on the following basic objectives to generate critical information for the following research Needs: (a) to conduct spectroscopic speciation of uranium compounds in glassforming melts as a function of the acid-base composition of the glasses and melt temperatures, and to use these data to develop a general thermodynamic model for the dissolution of actinide species in oxidic glass matrices, (b ) to build a scientific basis for a new methodology to measure the basicity of glasses via optical spectra of in-situ immobilized actinides and to use this optical basicity as a primary actinide structure indicator for solid glass matrices, (c) to define the local environment of actinides in solid glasses via fluorescence lifetime distribution methods, (d) to correlate the above spectral ''fingerprints'' of actinides in solid and molten glasses with glass stability and the leaching rates of individual actinide species from a glass matrix.
Date: June 15, 2003
Creator: Dai, Sheng; Boatner, Lynn; Schumacher, Ray F. & Barnes, C. E.
Partner: UNT Libraries Government Documents Department

Chemistry of Actinides in Molten Glasses and Its Correlation to Structural Performance of Solid Glasses: Filling the Knowledge Gap (Project 81926)

Description: This proposal focuses on the following basic objectives to generate critical information for the following research Needs: (a) to conduct spectroscopic speciation of uranium compounds in glass forming melts as a function of the acid-base composition of the glasses and melt temperatures, and to use these data to develop a general thermodynamic model for the dissolution of actinide species in oxidic glass matrices, (b) to build a scientific basis for a new methodology to measure the basicity of glasses via optical spectra of in-situ immobilized actinides and to use this optical basicity as a primary actinide structure indicator for solid glass matrices, (c) to define the local environment of actinides in solid glasses via fluorescence lifetime distribution methods, (d) to correlate the above spectral ''fingerprints'' of actinides in solid and molten glasses with glass stability and the leaching rates of individual actinide species from a glass matrix.
Date: June 25, 2005
Creator: Dai, Sheng; Boatner, Lynn & Schumacher, Ray F.
Partner: UNT Libraries Government Documents Department

Thermodynamic Modeling of the SRS Evaporators: Part V. Validation

Description: A thermodynamic model has been proposed to predict solids formation in the SRS evaporators from measured feed compositions using a commercially available software package, the Geochemist's Workbench (GWB). In support of this work, researchers at Pacific Northwest National Laboratory (PNNL) and Oak Ridge National Laboratory (ORNL) have performed experiments to evaluate solids formation under evaporator-like conditions in the laboratory. The purpose of this report is to compare these experimental results to the calculated results from GWB. Researchers at PNNL conducted experiments to evaluate the thermodynamic boundary between the precipitation of the deleterious sodium aluminosilicate gel (NASgel) and the field of benign potential precipitation of aluminum hydroxide formation. Several solutions were prepared and held at several temperatures to evaluate solids formation over various periods of time. Observed solids compared well to GWB calculations. Researchers at ORNL prepared several mixtures of simulated SRS Tank 43 (high aluminum) and DWPF recycle (high silicon) solutions. These solutions were then evaporated, and precipitated solids were examined by XRD. Again, there was good agreement between observations and GWB calculations. No NASgel was identified, and none was predicted to form. Researchers at ORNL also prepared several high caustic solutions, additional mixtures of simulated SRS Tank 43 and DWPF solutions, and simulated 3H evaporator feed. Solids deposition on stainless steel coupons with and without evaporation was examined. Because these solids were not rigorously characterized, direct comparison to GWB calculations is not appropriate. However, it should be noted that NASgel was not predicted by GWB to form, and no NASgel was identified in these experiments. Overall, the experimental observations validate the GWB calculational results, showing that GWB is an appropriate tool for use in SRS evaporator modeling and control.
Date: July 21, 2003
Creator: Pareizs, J.M.
Partner: UNT Libraries Government Documents Department