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27 records · Page 2

Carbon sequestration of steel slag and carbonation for activating RO phase

Carbonation of Ca/Mg minerals in industrial alkaline residues is a technology to sequester CO{sub 2} and reduce its emissions to the atmosphere. In this work, BSE-EDS were used to determine the mineral phase in steel slag; compositions of RO phase were identified and simulated. The carbon sequestration of steel slag was studied, and RO phase was activated by carbonation. Result shows that the amount of CO{sub 2} sequestered in steel slag and RO phase increases as carbonation time increases. Under autoclaving condition, the hydration ratio of MgO in RO phase was 20.10%. Through carbonation, up to 58.83% of MgO in RO phase can be converted into MgCO{sub 3}, and the activation of RO phase by carbonation was manifested. The mechanical properties and volume stability of carbonated steel slag were improved, proving that the positive effect of carbonation on steel slag when applied in cement and cementitious materials.

36 MATERIALS SCIENCE↗

The Impact of Ethylenediaminetetraacetic Acid (EDTA) on the Sorption of Nd(III), Th{sup (IV)}, and U(VI) onto Dolomite in WIPP-Relevant Brines, GWB and ERDA-6 - 20356

Storage of legacy, transuranic waste at the Waste Isolation Pilot Plant (WIPP) requires accurate risk models for performance assessments. These models must predict the long-term fate and transport of contaminants in the WIPP and surrounding environment. Laboratory support is necessary for the development of an accurate model through better understanding of contaminant behavior in the WIPP. The WIPP is a deep geologic repository that is characterized by high ionic strength due to evaporite deposits in the Salado formation (porewaters up to 7.4 M). High concentrations of sodium chloride (NaCl), calcium chloride (CaCl{sub 2}), and magnesium chloride (MgCl{sub 2}) are particularly of concern due to their potential impact on solubility and ultimately transport of contaminants of concern. Additionally, ligands capable of forming strong complexes with metals are found in significant concentrations in the WIPP environment due to their disposal from waste processing and formation during degradation of repository components (e.g. cellulose degradation by calcium hydroxide in cement). Consequently, there is a need to investigate the fate and transport of contaminants in the WIPP environment with a focus on the effects of high ionic strength and strongly coordinating ligands. Contaminants of high concern include the actinides (U(VI), Pu(IV), and Am(III)). Laboratory support of the WIPP modeling efforts was provided by this research. A series of batch experiments were utilized to study the impact of ionic strength, contaminant concentration, and the presence of ethylenediaminetetraacetic acid (EDTA) on the sorption of Nd(III), Th(IV), and U(VI) onto dolomite, a carbonate mineral found within the Culebra formation. The Culebra formation is the most transmissive layer above the WIPP, making transport of contaminants the most likely route in previous risk assessments. Two brines specifically designed to imitate conditions within the WIPP environment were used in these experiments. The U.S. Energy Research and Development Administration Well 6 (ERDA-6, 95%) brine simulates a low Mg environment, while the generic weep brine (GWB, 95%) simulates the WIPP environment with a high Mg concentration. Mg is added to the repository in the form of MgO as an engineered barrier and is naturally present in some formations. It is expected to scavenge carbonate from solutions decreasing formation of the highly soluble and competitive uranium-carbonate complexes. EDTA is used during manipulations of nuclear materials due to its ability to form strong, stable complexes with the actinides and may be found in high concentrations (up to 0.08 mM) within the WIPP as waste canisters degrade. Further, it may provide additional avenues for unwanted transport of contaminants. Nd(III) and Th(IV) were used as stable analogues of Am(III) and Pu(IV), respectively, to represent the most common oxidation states of actinides in the WIPP environment in addition to U(VI). The potential for colloid formation was also investigated with low and high concentrations of contaminants (10 and 1000 μg/L) using three size-dependent particle separation steps. The results of this research provide a better understanding of potential behavior of actinides in the presence of EDTA and within WIPP-relevant brines. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Alkali Vapor Corrosion of Spinel (MgAl 2 O 4 ) and Gahnite (ZnAl 2 O 4 ) Refractories—A Comparative Study

Alkali vapor corrosion is critical for refractories used in the kilns and furnaces of diverse high-temperature processing and manufacturing sectors such as gasifiers, cement production, and glass making. Gahnite (ZnAl 2 O 4 ) is being investigated as a potential chrome-free refractory because of its similarity with the structure and properties of magnesium aluminate (MgAl 2 O 4 ) spinel. The alkali vapor corrosion of ZnAl 2 O 4 , MgAl 2 O 4 , and Mg 0.5 Zn 0.5 Al 2 O 4 was studied, according to ASTM C987-10, at 1371°C for 24 h using sodium carbonate (Na 2 CO 3 ). The surface and the polished cross-sections of the corroded ZnAl 2 O 4 , MgAl 2 O 4 , and Mg 0.5 Zn 0.5 Al 2 O 4 specimens were analyzed using x-ray diffraction (XRD), microscopy, and energy-dispersive spectroscopy (EDS) techniques. MgO in MgAl 2 O 4 , ZnO in ZnAl 2 O 4 , Mg 0.77 Zn 0.23 O, and NaAlO 2 were detected as the corrosion products for these specimens. The extent of corrosion substantially varied among the specimens despite the similarity in the corrosion products. The corrosion resistance increased in the following order: Mg 0.5 Zn 0.5 Al 2 O 4 > MgAl 2 O 4 > ZnAl 2 O 4 . The formation of a dense MgO and Mg 0.77 Zn 0.23 O layer for MgAl 2 O 4 and Mg 0.5 Zn 0.5 Al 2 O 4 , respectively, contributed to their superior resistance to alkali vapor corrosion. The underlying corrosion mechanisms are discussed based on experimental observations supported by thermodynamic analysis. Additionally, the results suggest that a partial Zn 2+ substitution for Mg 2+ in MgAl 2 O 4 can enhance the resistance to alkali vapor corrosion.

alkali corrosion↗

Phase formation in the CaO–Al 2 O 3 –ZnO system as an analogue to CaO–Al 2 O 3 –MgO in spinel containing refractories

Recently, gahnite (ZnAl 2 O 4 ) is gaining attraction as a potential refractory ceramic because of the similarity of its structure and properties with those of magnesium aluminate (MgAl 2 O 4 ) spinel refractories. Formation of MgO and hibonite solid solution (CaMg x Al 12−x O 19−0.5x ; 0 ≤ x ≤ 0.18), CAM-I (Ca 2 Mg 2−3x Al 28+2x O 46 (0 ≤ x ≤ 0.3), and CAM-II (CaMg 2−3x Al 16+2x O 27 , 0 ≤ x ≤ 0.2) phases with platelet and interlocking microstructure in the CaO–Al 2 O 3 –MgO ternary system significantly enhances the high temperature mechanical properties of refractory castables. The CaO–Al 2 O 3 –ZnO ternary system has been studied, for the first time to our knowledge, in a selected compositional range with reference to the CaO–Al 2 O 3 –MgO system from 1650°C to 1700°C. The formation of ZnO and hibonite solid solution (CaZn x Al 12−x O 19−0.5x ; 0 < x < 0.18), CAZ-I (Ca 2 Zn 2−3x Al 28+2x O 46 ; 0 ≤ x ≤ 0.3), and CAZ-II (CaZn 2−3x Al 16+2x O 27 ; 0 ≤ x ≤ 0.2) phases with platelet and interlocking morphology have been found. The crystal structures and lattice parameters of ZnO and hibonite solid solution, CAZ-I, and CAZ-II are comparable, respectively, with MgO and hibonite solid solution, CAM-I, and CAM-II. Furthermore, CAZ-I and CAZ-II phases also form due to reaction between hibonite (CaO·6Al 2 O 3 ) and ZnAl 2 O 4 .

calcium aluminate cement↗

Distribution of rare earth elements in the pilot-scale processing of fly ashes derived from eastern Kentucky coals: Comparisons of the feed and processed ashes

Beneficiated fly ash from the combustion of Central Appalachian high volatile bituminous coals was extracted with HNO 3 in a pilot-scale processing plant. Several major oxides (notably CaO and SO 3 , but also including Fe 2 O 3 , MgO, K 2 O, and P 2 O 5 ) and minor elements (Mn, As, Sr, Ba, and Pb) are depleted in the post-HNO 3 -extraction spent ash. The total lanthanides, Y, and Sc concentration is reduced by about 20% in the spent ash, with Gd showing the greatest decrease. Along with Gd, Nd and Dy are also well differentiated between the feed and spent ashes, with La and Sm showing minimal partitioning. The Gd decrease is correlated with the depletion of Fe 2 O 3 . The heavy rare earth elements (REE heavier than Eu) and Y are disproportionately concentrated in the HNO 3 -leachate compared to the light REE. For the ashes studied, Sc did not partition between the feed and spent ashes. Pozzolanicity tests show that the compressive strength and strength activity indices of the spent ash + ordinary Portland cement (OPC) mixes are comparable to 100% OPC, indicating that the spent ashes produced in the pilot-scale runs have the potential to be sold as a Class F fly ash. Finally, the beneficiated ash chemistry influences the chemistry of the post-HNO 3 -extraction spent ash and the HNO 3 -leachate. A 500-ppm-REE fly ash will presumably be a more economically favorable feedstock than an ash with a significantly lesser concentration.

01 COAL, LIGNITE, AND PEAT↗

Diode end pumped laser and harmonic generator using same

A second harmonic, optical generator is disclosed in which a laser diode produces an output pumping beam which is focused by means of a graded, refractive index rod lens into a rod of lasant material, such as Nd:YAG, disposed within an optical resonator to pump the lasant material and to excite the optical resonator at a fundamental wavelength. A non-linear electro-optic material such as MgO:LiNbO.sub.3 is coupled to the excited, fundamental mode of the optical resonator to produce a non-linear interaction with the fundamental wavelength producing a harmonic. In one embodiment, the gain medium and the non-linear material are disposed within an optical resonator defined by a pair of reflectors, one of which is formed on a face of the gain medium and the second of which is formed on a face of the non-linear medium. In another embodiment, the non-linear, electro-optic material is doped with the lasant ion such that the gain medium and the non-linear doubling material are co-extensive in volume. In another embodiment, a non-linear, doubling material is disposed in an optical resonator external of the laser gai medium for improved stability of the second harmonic generation process. In another embodiment, the laser gain medium andthe non-linear material are bonded together by means of an optically transparent cement to form a mechanically stable, monolithic structure. In another embodiment, the non-linear material has reflective faces formed thereon to define a ring resonator to decouple reflections from the non-linear medium back to the gain medium for improved stability.

Byer, Robert L.↗

Foam and Unreacted Material Reduction in Magnesium Oxysulfate for SRPPF Waste Solidification

A magnesium oxysulfate (MOS) grout formulation has been proposed to solidify the liquid effluent from the Savannah River Plutonium Processing Facility (SRPPF) Aqueous Recovery System (ARS). This formulation uses a combination of light-burnt MgO, anhydrous MgSO 4 , and dead-burnt MgO resulting in a grout with good mixability and acceptable density. The setting time for the grout is within the operational limits of the SRPPF facility and the leachate pH is ~9.4, which is within the assumed pH range of the brine from the Waste Isolation Pilot Plant (WIPP). When first tested at the 1-gallon small-scale and 55-gallon full-scale, there was a significant foam layer that raised concerns of a nonhomogeneous final form. A nonhomogeneous mixture could have variable density throughout the waste form and therefore allow for unequal shielding. To reduce the potential for unequal shielding in the final form, a series of foam reduction tests were carried out and a final formulation of 28 wt% light burnt MgO, 10 wt% MgSO 4 , and 62 wt% dead burnt MgO was used to remove the foam in under two hours while still maintaining a mix that has an acceptable density, mix time, peak temperature, and set time.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Impactites from Popigai Crater

Impactites (tagamites and suevites) from Popigai impact crater, whose diameter is about 100 km, are distributed over an area of 5000 sq km. The continuous sheet of suevite overlies the allogenic polymict breccia and partly authogenic breccia, and may also be observed in lenses or irregular bodies. The thickness of suevites in the central part of the crater is more than 100 m. Suevites may be distinguished by content of vitroclasts, lithoclasts, and crystalloclasts, by their dimensions, and by type of cementation, which reflects the facial settings of ejection of crushed and molten material, its sedimentation and lithification. Tagamites (impact melt rocks) are distributed on the surface predominantly in the western sector of the crater. The most characteristic are thick sheetlike bodies overlying the allogenic breccia and occurring in suevites where minor irregular bodies are widespread. The maximal thickness of separate tagamite sheets is up to 600 m. Tagamites, whose matrix is crystallized to a different degree, include fragments of minerals and gneiss blocks, among them shocked and thermally metamorphosed ones. Tagamite sheets have a complex inner structure; separate horizontal zones distinguish in crystallinity and fragment saturation. Differentiation in the impact melt in situ was not observed. The average chemical compositions of tagamites and suevites are similar, and correspond to the composition of biotite-garnet gneisses of the basement. According to the content of supplied Ir, Ni, and other siderophiles, impact melt was contaminated by 5 percent cosmic matter of collided body, probably ordinary chondrite. The total volume of remaining products of chilled impact melt is about 1750 cu km. Half this amount is represented by tagamite bodies. Though impact melt was in general well homogenized, the trend analysis showed that the concentric zonation is distribution of SiO2, MgO, and Na2O and the bandlike distribution of FeO and Al2O3 content testifies to a certain inheritance and heterogeneity in country rock composition laterally and vertically in the melting zone.

Masaitis, V. L.↗

Effects of SRPPF ARS Effluent Variations on Magnesium Oxysulfate Solidification

A magnesium oxysulfate (MOS) grout formulation has been identified to solidify the liquid effluent from the Savannah River Plutonium Processing Facility (SRPPF) Aqueous Recovery System (ARS). The formulation uses reactive, light burnt MgO (28 wt%), anhydrous MgSO 4 (10 wt%), and dead burnt MgO (62 wt%), resulting in a grout with good mixability, acceptable density, acceptable setting times, and a leachate pH around 9.4, within the assumed Waste Isolation Pilot Plant (WIPP) brine pH range. A series of tests were then designed to observe how this formula reacted to variations in the liquid effluent. Liquid effluent temperature, the caustic pH level, concentration of NaNO 3 , and the presence of neutralization products, trace metals, and/or sodium sulfate (all potential residuals found in the effluent from upstream processing), were evaluated to see how each impacts the grout mixing time, peak temperature, setting time, presence of bleed water, leachate pH, and density. The standard mix has an average mixing time of 18 minutes, peak temperature of 100.5 °C, and set time of 60 minutes. Increasing the temperature of the liquid effluent increased the reaction rate of the mix and reduced mixing and setting times. Between 30 and 40°C the change was relatively small, raising no more than 6 °C compared to the standard mix maximum temperature. Increasing the pH of the liquid effluent had no significant impact on the mix. The addition of neutralization products and trace metals had an overall impact of decreasing the reactivity of the mix. The addition of more ions in the liquid effluent, such as an increase in the concentration of NaNO 3 and the addition of Na 2 SO 4 , generally decreased the reactivity of the mix. None of the variations to the liquid effluent hindered solidification as indicated by the lack of bleed water found on all the samples. The leachate pH values for all mixes tested did not significantly vary from the expected pH of 9.4 and none of the density values fell below 1.8 g/cm 3 . Overall, changes to the liquid effluent were found to have a minimal impact on the formulation suggesting the grout's ability to properly form despite increased temperatures and the presence of residuals typically found in the liquid effluent from the ARS.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗