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At least 289 records · Page 16

Sub-Grid Model Improving Shrinking Core Simulations of Redox-Sensitive Technetium Release From Slag Cement Waste Forms - 17295

Numerical simulation of Tc transport in reducing cementitious materials undergoing oxidation is challenging because the effective solid-solute partition coefficient (K{sub d}) varies greatly between the reduced and oxidized states, assuming the Tc mass loading far exceeds that required to reach solubility in the aqueous phase, as is typical in waste disposal. In a conventional finite-volume formulation, the local aqueous concentration increases orders of magnitude when a computational cell switches from a reducing to oxidizing condition, which is an artifact of numerical discretization. In principal such artifacts can be reduced to an insignificant level by refining the computational grid. However, this approach is not feasible in typical facility scale applications due to computer runtime and storage limitations. In this paper an alternative sub-grid Tc release model is derived to approximately capture redox processes occurring at scales smaller than the computational mesh. This alternative approach introduces minimal additional computational expense, while significantly reducing numerical artifacts in the form of Tc concentration / flux spikes. The method is illustrated for two simple geometries and the Savannah River Site Saltstone waste Disposal Facility. The sub-grid model is shown to significantly reduce artificial spikes in Tc-99 release, resulting in more physically realistic numerical simulations. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Technetium oxidation in slag-based sodium salt waste forms exposed to water and moist Hanford soil - 15514

Several U.S. DOE sites use or plan to use waste forms and/or concrete containment structures for radioactive waste disposal that are designed to have a chemically reducing environment to immobilize selected contaminants such as Tc(VII)O{sub 4}{sup -} and Cr(VI)O{sub 4}{sup 2-}. These waste forms and containment structures are typically deployed in near surface unsaturated oxidizing environments. Consequently, the effect of exposure to air (oxygen) and water containing dissolved oxygen during production, during the period of institutional control, and over the long term period of performance is important for predicting the speciation and mobility of the redox sensitive radioactive and stable contaminants. Both the SRS and Hanford waste streams contain soluble technetium which may require stabilization to meet disposal requirements. Technetium stabilization is a difficult problem because: 1) Tc is soluble and very mobile in the oxidized form typical of near surface environments, and 2) Tc-99 is a long-lived isotope with a half-life of 2.1 E+05 years which places demanding requirements on the engineered barriers and environment to meet current regulatory disposal requirements. A depth-discrete sampling and leaching method approach for measuring contaminant oxidation rate (effective contaminant specific oxidation rate) was used in this study. The method was modified by coating all sides of a cylindrical sample with an impermeable epoxy and cutting a fresh surface 2 to 2.5 cm from the original top surface eliminates sample inhomogeneity as the result of settling as a reason from observed results and provides 1-D soluble ion transport and gas transport information. Soluble Tc was leached from all of the depth-discrete sub-samples from both Tc2-9 and Tc2-10 which strongly suggests that oxygen was present in the entire length of both samples. About 24 mass percent of the Tc in the original sample, was leached (soluble) from sub-samples between 0.8 and 46 mm below the exposed surface of Tc2-9 (exposed to Hanford sediment). The same percent (24%) was leached from the sub-samples between 0.8 and 11 mm below the exposed surface of Tc2-10 (exposed to DI water). This suggests that the rate of oxygen migration into the sample exposed to soil was faster than the rate of migration into the sample exposed to water which is consistent with the more rapid transport of ions through a gas phase as compared to a liquid phase. It is assumed that moisture in the Hanford sediment was not sufficient to completely block the surface pores with respect to gas transport across the soil-waste form boundary. Based on nitrate leaching results for the depth- discrete sub-samples, regions depleted in nitrates were identified from the top surfaces to 9.5 and 3 mm into samples Tc2-9 (exposed to moist Hanford sediment) and Tc2-10 (DI water). Low mass fractions of nitrate were leached from these depth-discrete samples compared to samples further from the exposed surface presumably because a significant portion of the nitrate had already migrated into the soil or water, respectively. Depth-discrete sub-sample leaching results for Na can be interpreted in the same way over the same regions in the two samples tested. In conclusion, leaching monolithic porous cementitious waste forms in water appears to be conservative for non-redox sensitive contaminants. However, leaching data obtained under saturated exposure conditions do not appear to be conservative for redox sensitive contaminants which are easily oxidized. Leaching crushed samples in water still seems to be a conservative approach to estimating the concentrations of soluble contaminants in a waste form. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Radiation–Conduction Heat-Transfer Study for Mold Flux by Thermoviewer-Enhanced Infrared Emitter Technique

A thermoviewer-enhanced infrared emitter technique was developed in this article to study the heat-transfer behavior of mold flux in the continuous casting mold. Then, a radiation–conduction heat-transfer model was built to determine the radiative/conductive heat flux, thermal conductivity, and optical properties of slag. The results showed that the mold/slag interfacial thermal resistance decreases with the increasing temperature of slag surface at the mold side, and then reaches the minimum when the slag surface is the hottest, and finally increases slightly with further increase in slag crystallization. In addition, the radiative heat flux decreases with the increasing depth of radiation propagating into the slag. While the amount of heat of radiation lost is being converted to produce an additional radiative heat source to heat the slag, the increase in the conductive heat flux in the slag is realized. Furthermore, the apparent transmittivity is obtained as 0.63 for the glassy slag disk and as 0.41 for the partially crystallized slag disk. Besides, when mold heat flux decreases from the maximum to a saturation value due to the further slag crystallization, the corresponding apparent transmittivity of slag disk decreases from 0.58 to 0.41, and the ratio of the heat across the slag disk by radiation decreases from 67.3 to 50.0 pct.

36 MATERIALS SCIENCE↗

Reactions in the Tuyere Zone of Ironmaking Blast Furnace

A series of slags can be formed in the lower part of the ironmaking blast furnace that play important roles in smooth furnace operation, and in determining iron quality and productivity. The final slag tapped from the BF has been investigated extensively as it can be collected directly. Unfortunately, difficulties in accessing the interiors of the blast furnace limit the full understanding of other slags such as primary and bosh slags. In this study, different types of samples directly obtained from the tuyere zone of the blast furnace have been systematically analyzed and characterized using scanning electron microscopy (SEM), electron probe X-ray microanalysis (EPMA), and X-ray fluorescence (XRF), with focus on the characteristics of slags formed in the tuyere level. The samples were identified into three groups according to their morphological, mineralogical, and chemical properties: (1) tuyere slags originating from the reactions between ash and dripping slags; (2) bosh slags in the CaO-SiO{sub 2}-Al{sub 2}O{sub 3}-MgO-FeO system, with a CaO/SiO{sub 2} weight ratio of around 1.50, and Al{sub 2}O{sub 3} and MgO concentrations close to those of final slags; and (3) coke ash that did not react with bosh slags. These findings will provide useful information on the evaluation of slags inside the blast furnace and the reactions in the tuyere zone.

36 MATERIALS SCIENCE↗

Indirect measurement of molten steel level in tundish based on laser triangulation

For real-time and precise measurement of molten steel level in tundish during continuous casting, slag level and slag thickness are needed. Among which, the problem of slag thickness measurement has been solved in our previous work. In this paper, a systematic solution for slag level measurement based on laser triangulation is proposed. Being different from traditional laser triangulation, several aspects for measuring precision and robustness have been done. First, laser line is adopted for multi-position measurement to overcome the deficiency of single point laser range finder caused by the uneven surface of the slag. Second, the key parameters, such as installing angle and minimum requirement of the laser power, are analyzed and determined based on the gray-body radiation theory to fulfill the rigorous requirement of measurement accuracy. Third, two kinds of severe noises in the acquired images, which are, respectively, caused by heat radiation and Electro-Magnetic Interference (EMI), are cleaned via morphological characteristic of the liquid slag and color difference between EMI and the laser signals, respectively. Fourth, as false target created by stationary slag usually disorders the measurement, valid signals of the slag are distinguished from the false ones to calculate the slag level. Then, molten steel level is obtained by the slag level minus the slag thickness. The measuring error of this solution is verified by the applications in steel plants, which is ±2.5 mm during steady casting and ±3.2 mm at the end of casting.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Microscopic and Metallurgical Aspects of the Space Shuttle Columbia Accident Investigation and Reconstruction

The Space Shuttle Columbia was descending for a landing at the Kennedy Space Center (KSC) on February 1, 2003. Approximately 20 minutes prior to touchdown, the Columbia began disintegrating over the western United States; the majority of debris eventually impacted in eastern Texas and western Louisiana. A monumental effort eventually recovered approximately 84,000 pieces of debris, approximately 38% of the Orbiter's original dry weight. The debris was transported to KSC, where the items were catalogued and evaluated. Critical areas of interest, such as the left and right leading edge surfaces and the underside of the ship, were placed upon a grid to aid in the reconstruction. Items of interest included metallic structures, reinforced carbon-carbon composites, and ceramic heat insulation tiles. Many of the leading edge elements had re-solidified metallic deposits spattered on them. These deposits became known as slag and were one of the main focuses of the investigation. In order to help determine the sequence of events inside the left wing during the accident, the slag's composition, layering order, and directionality of deposition were studied. A myriad of analytical tests were performed in an attempt to ascertain the compositional and depositional characteristics of selected slag deposits, including the ordering of deposited layers within each individual slag deposit harvested. Initially, Scanning Electron Microscopy and Energy Dispersive X-Ray Spectroscopy (SEM/EDX) were performed to quickly characterize the overall composition of individual slag deposits: SEM utilizes a narrowlyfocused high-energy electron beam impinging upon a specimen. The incident beam excites and liberates lower energy secondary electrons, which are detected and analyzed, providing a visual representation of the sample's surface topography. EDX also relies on an incident electron beam, except an EDX unit measures X-ray energies generated by the impinging beam. Each element generates a unique X-ray signature; the EDX detector measures these discreet energies. EDX actually penetrates approximately 2 microns into the bulk of the sample. However, random examination of various portions of slag, coupled with the semiquantitative nature of the SEM/EDX analysis, did not yield convincingly pertinent data. Therefore, X-ray dot mapping was conducted, which provided more understandable data, both in terms of slag layering and composition. An X-ray dot map is generated by performing numerous EDX scans for individual elements, then compiling the scans in a visual representation. Eventually, specimens consisting of not only the slag, but of the adjacent RCC substrate as well were cross-sectioned. X-Ray dot mapping of the materialographicallymounted and -polished cross- sections provided a visual representation of both the layering sequence and compositional characteristics of the slag. Contemporaneously, Electron Spectroscopy for Chemical Analysis/X-Ray Photoelectron Spectroscopy (ESCA/XPS) and powdered X-Ray Diffraction (XRD) were performed to further characterize the deposits and to attempt to identify what, if any, compounds were present. The ESCA/XPS analysis allowed the analyst to "sputter" into the sample with an electron gun, aiding in the identification of the layering sequence. XPS uses photons, rather than electrons, which impinge upon the surface of the sample. XPS measures the electrons emitted from within the first 5 nm of the sample's surface. The XRD measures the scatter angles of incident X-rays; the angle and intensity of scatter depend upon the crystalline structure of the pulverized sample. XRD is considered a qualitative rather than quantitative technique. ESCA/XPS revealed that the final layer to deposit was predominantly carbonaceous. XRD was successful in identifying specific compounds, such as Al 2O3, Al and/or Al3 21SiO47, mullite (3(Al2)O3 -SiO2), and nickel-aluminides. Eventually, Electron MicroProbe Analysis (EMPA) was conducted on the marialographically-prepared cross- sections of selected slag deposits. Microprobe combines SEM and Wavelength Dispersive X-Ray Spectroscopy (WDS), and, like EDX, uses a narrowly-focused high-energy electron beam impinging upon a specimen to elicit, in the case of EPMA, characteristic X-rays with specific wavelengths. This quantitative, analytical tool proved the most useful in determining depositional layering and composition of the slag deposits. This information was utilized in verifying the location of the breach in the left leading edge of the wing of the Columbia.

McDaniels, Steven J.↗

Kinetic Study on Alloying Element Transfer During an Electroslag Remelting Process

Experimental and theoretical studies have been carried out to investigate the effects of slag on the alloying elements in ingots during the electroslag remelting (ESR) process with a focus on developing a mass-transfer model to understand the mechanism of slag-metal reaction. Stainless steel 1Cr21Ni5Ti was used as the electrode and remelted with two different kinds of slags using a 50-kg ESR furnace. The contents of sulfur, aluminum, titanium and silicon along the axial direction of the produced ingots were analyzed. On the basis of the penetration and film theories, the theoretical model developed in this work elucidates the kinetics of the slag-metal reaction revealing the mechanism of alloying element transfer during the ESR process. The calculation results obtained from the model agree well with the experimental results. The model indicates that the resultant [O] coming from the desulfurization reaction of (O{sup 2−}) + [S] = (S{sup 2−}) + [O] causes the oxidation of alloying elements in steel by [M] + [O] = (MO). The distribution ratio of sulfur L{sub S} decreases with the increase of slag temperature in the first slag-temperature-rising period, and the concentration of sulfur in the ingot at the beginning of the ESR process is lower than in the rest of the process because of the combination of the large distribution ratio of sulfur L{sub S} and excellent kinetic conditions. The concentration of aluminum along the height of the ingot has an increasing trend in the first slag-temperature-rising period, while it has a decreasing trend in the rest of the process. Two methods can solve this problem: one is starting up the ESR furnace by high temperature molten slag technology and the other is continually adding extra titania into the molten slag in the first slag-temperature-rising period.

36 MATERIALS SCIENCE↗

Study on Formation Mechanism of CaO-SiO{sub 2}-Based Inclusions in Saw Wire Steel

Attempts were made to elucidate the formation mechanism of CaO-SiO{sub 2}-based inclusions in saw wires by both laboratory experiments and industrial trials. The key point was to make clear the origin of CaO in such oxide inclusions. Probable origins of [Ca] in steel were first discussed, which can be taken into steel from the steel-slag reaction or ferrous alloy. As a result, slag-steel chemical reaction equilibrium was carefully evaluated at 1873 K (1600 °C) to classify the changes of dissolved aluminum ([Al]), total magnesium (Mg), and total calcium (Ca) in steel and the caused composition variations of inclusions. With the rise of slag basicity from 0.5 to 1.8, [Al] was remarkably increased from 0.00045 to 0.00139 mass pct, whereas Mg varied in the range of 0.00038 to 0.00048 mass pct. By contrast, Ca was constantly kept below 0.00003 mass pct. Accordingly, Al{sub 2}O{sub 3} and MgO in inclusions witnessed obvious rises from 5 to 23 mass pct and from 2 to 8 mass pct, respectively. By contrast, inclusions were free of CaO when slag basicity was below 1.5. With slag basicity further increased to 1.8, CaO witnessed a negligible rise to only 1.0 mass pct on average. This phenomenon agreed well with thermodynamic calculations, which revealed that chemical reaction between steel and CaO in slag (for example, between [Si] and CaO) was weak to hardly supplying sufficient [Ca] to steel to increase CaO in inclusions. Ca contained in ferrous alloys as contaminations was not the cause of CaO-SiO{sub 2}-based inclusions, either. The industrial trial results indicated that CaO-SiO{sub 2}-based inclusions have been readily produced in short time just after BOF tapping. Also, a percentage of them changed slightly with the proceeding of refining. Based on the good agreement of laboratory, industrial, and thermodynamics calculations results, it can be reasonably concluded that CaO-SiO{sub 2}-based inclusions in saw wire were exogenous particles from entrapped/emulsified top slag, but not products of slag-steel-inclusion chemical reactions.

36 MATERIALS SCIENCE↗

Dynamic Model of Basic Oxygen Steelmaking Process Based on Multi-zone Reaction Kinetics: Model Derivation and Validation

A multi-zone kinetic model coupled with a dynamic slag generation model was developed for the simulation of hot metal and slag composition during the basic oxygen furnace (BOF) operation. The three reaction zones (i) jet impact zone, (ii) slag–bulk metal zone, (iii) slag–metal–gas emulsion zone were considered for the calculation of overall refining kinetics. In the rate equations, the transient rate parameters were mathematically described as a function of process variables. A micro and macroscopic rate calculation methodology (micro-kinetics and macro-kinetics) were developed to estimate the total refining contributed by the recirculating metal droplets through the slag–metal emulsion zone. The micro-kinetics involves developing the rate equation for individual droplets in the emulsion. The mathematical models for the size distribution of initial droplets, kinetics of simultaneous refining of elements, the residence time in the emulsion, and dynamic interfacial area change were established in the micro-kinetic model. In the macro-kinetics calculation, a droplet generation model was employed and the total amount of refining by emulsion was calculated by summing the refining from the entire population of returning droplets. A dynamic Fe{sub t}O generation model based on oxygen mass balance was developed and coupled with the multi-zone kinetic model. The effect of post-combustion on the evolution of slag and metal composition was investigated. The model was applied to a 200-ton top blowing converter and the simulated value of metal and slag was found to be in good agreement with the measured data. The post-combustion ratio was found to be an important factor in controlling Fe{sub t}O content in the slag and the kinetics of Mn and P in a BOF process.

36 MATERIALS SCIENCE↗

Correlation between the critical viscosity and ash fusion temperatures of coal gasifier ashes

Coal gasification yields synthesis gas, an important intermediate in chemical manufacturing. It is also vital to the production of liquid fuels through the Fischer-Tropsch process and electricity in Integrated Gasification Combined Cycle power generation. Minerals naturally present in coal become molten in entrained-flow slagging gasifiers. Molten coal ash slag penetrates and dissolves refractory bricks, leading to costly plant shutdowns. The extent of coal ash slag penetration and refractory brick dissolution depends on the slag viscosity, the gasification temperature, and the composition of slag and bricks. We measured the viscosity of several synthetic coal ash slags with a high-temperature rotary viscometer and their ash fusion temperatures through optical image analysis. All measurements were made in a carbon monoxide-carbon dioxide reducing atmosphere that approximates coal gasification conditions. Empirical correlation models based on ash fusion temperatures were used to calculate critical viscosity temperatures based on the coal ash compositions. These values were then compared with those obtained from thermodynamic phase-transition models. An understanding of slag viscosity as a function of ash composition is important to reducing refractory wear in slagging coal gasifiers, which would help to reduce the cost and environmental impact of coal for chemical and electricity production.

01 COAL, LIGNITE, AND PEAT↗

SRM Internal Flow Tests and Computational Fluid Dynamic Analysis: RSRM Full Scale Motor Analyses - Volume 2

The purpose of the RSRM Nozzle Slag Ejection Precursor Test is to investigate the effect that slag ejection from the RSRM nozzle has on the chamber pressure and trust of the SRB's. In past firings of the Reusable Solid Rocket Motor (RSRM) both static test and flight motors have shown small pressure perturbations occurring primarily between 65 and 80 seconds. A joint NASA/Thiokol team investigation concluded that the cause of the pressure perturbations was the periodic ingestion and ejection of molten aluminum oxide slag from the cavity around the submerged nozzle nose which tends to trap and collect individual aluminum oxide droplets from the approach flow. The conclusions of the team were supported by numerous data and observations from special tests including high speed photographic films, real time radiography, plume calorimeters, accelerometers, strain gauges, nozzle TVC system force gauges, and motor pressure and thrust data. A simplistic slag ballistics model was formulated to relate a given pressure perturbation to a required slag quantity. Also, a cold flow model using air and water was developed to provide data on the relationship between the slag flow rate and the chamber pressure increase. Both the motor and the cold flow model exhibited low frequency oscillations in conjunction with periods of slag ejection. Motor and model frequencies were related to scaling parameters. The data indicate that there is a periodicity to the slag entrainment and ejection phenomena which is possibly related to organized oscillations from instabilities in the dividing streamline shear layer which impinges on the underneath surface of the nozzle.

Source record↗