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At least 37 records · Page 2

Combined Technologies for In Situ Remediation of Tc-99 and U in Subsurface Sediments

In this study, combinations of chemical remedies were tested in bench-scale batch experiments to evaluate a two-step reduction-sequestration approach to effectively stabilize high concentrations of inorganic contaminant mixtures. Bench tests simulated contaminant and geochemical conditions of a perched aquifer located within the Central Plateau at the Hanford Site, located in southeastern Washington State (USA). Pairwise combinations of a reductant [e.g., zero valent iron, sulfur modified iron (SMI), or calcium polysulfide] and a sequestering agent [e.g., calcite, apatite, or dilute alkaline solution (e.g., NaOH)] were evaluated for immobilization and stabilization of technetium (Tc) (50,000 pCi/L), uranium (U) (150 mg/L), and nitrate (NO 3 ) (200 mg/L) in high ionic strength groundwater. The results of these batch studies demonstrated that reduction by SMI and sequestration in apatite or calcite are the most effective combination for these contaminant mixtures and conditions. Aqueous concentrations of Tc and U decreased by 95.6% ± 2.5% and 101.1% ± 5.2%, respectively, with SMI-apatite and 98.3% ± 0.0% and 101.2% ± 5.2%, respectively, with SMI-calcite. Sequential extractions showed that sequestered contaminants had limited capacity for re-oxidation; in fact, less than 10% of immobilized Tc and U was recovered by selective extraction of mineral phases most susceptible to oxidation. In addition, X-ray absorption near edge structure analysis of the sediment samples treated with SMI-calcite showed the presence of only U(IV), while both U(IV) and U(VI) were present in the SMI apatite combination [ratio of 0.43 U(IV):0.59 U(VI)].This study describes preliminary results that a two-step approach for stabilizing contaminant mixtures of long-lived radionuclides can be effective at reducing contaminant fluxes to groundwater from vadose and perched water zones.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Synthesis and characterization of high-Tc superconductors in the Tl-Ca-Ba-Cu-O system

Both Tl2Ca2Ba2Cu3O10 and TlCa3BaCu3O8.5 are investigated for superconductivity as a function of the sintering temperature, time, atmosphere, and quench rate in an effort to synthesize the high-Tc superconducting phase in the thallium system. The samples are characterized by electrical resistivity measurements, X-ray diffraction, and scanning electron microscopy. Samples of starting composition Tl2Ca2Ba2Cu3O10 fired in air at 860-900 C and rapidly quenched show a Tc of 96-107 K. In contrast, specimens of starting composition TlCa3BaCu3O8.5 when baked at 900 C and slowly cooled in oxygen superconduct at 116 K and above and consist of Tl2Ca2Ba2Cu3O(10+x) as the dominant phase. The results also show that, in contrast to the case of YBa2Cu3O(7-x), doping with a small concentration of fluorine sharpens the resistive transition and produces a large Tc increase in thallium-based superconductors.

Bansal, Narottam P.↗

High Tc superconducting materials and devices

The high Tc Y1Ba2Cu3O(7-x) ceramic materials, initially developed in 1987, are now being extensively investigated for a variety of engineering applications. The superconductor applications which are presently identified as of most interest to NASA-LaRC are low-noise, low thermal conductivity grounding links; large-area linear Meissner-effect bearings; and sensitive, low-noise sensors and leads. Devices designed for these applications require the development of a number of processing and fabrication technologies. Included among the technologies most specific to the present needs are tapecasting, melt texturing, magnetic field grain alignment, superconductor/polymer composite fabrication, thin film MOD (metal-organic decomposition) processing, screen printing of thick films, and photolithography of thin films. The overall objective of the program was to establish a high Tc superconductivity laboratory capability at NASA-LaRC and demonstrate this capability by fabricating superconducting 123 material via bulk and thin film processes. Specific objectives include: order equipment and set up laboratory; prepare 1 kg batches of 123 material via oxide raw material; construct tapecaster and tapecaster 123 material; fabricate 123 grounding link; fabricate 123 composite for Meissner linear bearing; develop 123 thin film processes (nitrates, acetates); establish Tc and Jc measurement capability; and set up a commercial use of space program in superconductivity at LaRC. In general, most of the objectives of the program were met. Finally, efforts to implement a commercial use of space program in superconductivity at LaRC were completed and at least two industrial companies have indicated their interest in participating.

Haertling, Gene H.↗

Development of high Tc (greater than 100 K) Bi, Tl and Y-based materials as superconducting circuit elements

Results on this project over the past three years have shown that the Bi and Tl-based superconducting materials in bulk form are noticeably different from the Y-based 123 material in that superconductivity is considerably harder to achieve, maintain and reproduce. This is due primarily to the difficulty in obtaining the higher Tc phase in pure form since it commonly co-exists with other undesirable, lower Tc phases. In particular, it has been found that long processing times for calcining and firing (20 - 200 hrs.) and close control of temperatures which are very near the melting point are required in order to obtain higher proportions of the desirable, high Tc (2223) phase.

Haertling, Gene↗

Proximity-Coupled High-Tc Josephson Junctions: Do They Exist?

A significant portion of the worldwide effort to develop high-Tc Josephson junctions for electronic applications has been dedicated to superconductor-normal-superconductor (SNS) junctions. Numerous groups have reported nominally-SNS junctions with a variety of geometries and normal interlayers. Until recently, the electrical properties of these junctions have been interpreted almost exclusively in terms of conventional proximity effect theory, which describes very well the behavior of low-Tc SNS devices. It is now clear, however, that it is only recently that proximity effect theory was successfully applied to any high-Tc SNS junctions are far better understood by assuming that transport occurs through unintended pinholes in the normal interlayers [1], an idea that is rapidly gaining in acceptance.

Josephson↗

Partitioning of Fe(II) in reduced nontronite (NAu-2) to reactive sites: Reactivity in terms of Tc(VII) reduction

Abstract Clay minerals impart important chemical properties to soils, in part, by virtue of changes in the redox state of Fe in their crystal structures. Therefore, measurement of Fe(III)/Fe(II) and partitioning of Fe(II) in different reactive sites in clay minerals (during biological and chemical Fe(III) reduction) is essential to understand their role and their relative reactivity in terms of reduction and immobilization of heavy metal contaminants such as technetium. This study had three objectives: (1) to understand the degree of dissolution of nontronite (Fe-rich smectite) as a result of chemical and biological reduction of Fe(III) in the structure; (2) to quantify partitioning of chemically and biologically produced Fe(II) into different reactive sites in reduced nontronite, including aqueous Fe 2+ , ammonium chloride-extractable Fe(II) (mainly from the ion-exchangeable sites, denoted as Fe ( II ) NH 4 Cl ${\rm{Fe}}{\left( {{\rm{II}}} \right)_{{\rm{N}}{{\rm{H}}_4}{\rm{Cl}}}}$ ), sodium acetate-extractable Fe(II) (mainly from the surface complexation sites, denoted as Fe(II) acetate ), and structural Fe(II) (denoted as Fe(II) str ); and (3) to evaluate the reactivity of these Fe(II) species in terms of Tc(VII) reduction. Chemical and biological reduction of Fe(III) in nontronite (NAu-2) was performed, and reduced nontronite samples with different extents of Fe(III) reduction (1.2–71%) were prepared. The extent of reductive dissolution was measured as a function of the extent of Fe(III) reduction. Our results demonstrated that chemically and biologically produced Fe(II) in NAu-2 may be accommodated in the NAu-2 structure if the extent of Fe(III) reduction is small (< ∼30%). When the extent of reduction was >∼30%, dissolution of nontronite occurred with a corresponding decrease in crystallinity of residual nontronite. The Fe(II) produced was available for partitioning into four species: Fe ( ab ) 2 + ${\rm{Fe}}_{\left( {{\rm{ab}}} \right)}^{2 + }$ , Fe(II) acetate , Fe ( II ) NH 4 Cl ${\rm{Fe}}{\left( {{\rm{II}}} \right)_{{\rm{N}}{{\rm{H}}_4}{\rm{Cl}}}}$ , and Fe(II) str . The increase in Fe(II) acetate during the early stages of Fe(III) reduction indicated that the Fe(II) released had the greatest affinity for the surface-complexation sites, but this site had a limited capacity (∼60 µmol of Fe(II)/g of NAu-2). The subsequent increase in Fe ( II ) NH 4 Cl ${\rm{Fe}}{\left( {{\rm{II}}} \right)_{{\rm{N}}{{\rm{H}}_4}{\rm{Cl}}}}$ indicated that the released Fe(II) partitioned into the exchangeable sites once the amount of Fe at the surface-complexation sites reached half of its maximum site capacity. The fraction of Fe(II) str decreased concomitantly, as a result of Fe(II) release from the NAu-2 structure, from 100% when the extent of Fe(III) reduction was <30% to nearly 65% when the extent of Fe(III) reduction reached 71%. The Fe(II) acetate and Fe(II) str exhibited greater reactivity in terms of Tc(VII) reduction than the Fe ( II ) NH 4 Cl ${\rm{Fe}}{\left( {{\rm{II}}} \right)_{{\rm{N}}{{\rm{H}}_4}{\rm{Cl}}}}$ . Clearly, the surface-complexed and structural Fe(II) are the desirable species when reduced clay minerals are used to reduce and immobilize soluble heavy metals in contaminated groundwater and soils. These results have important implications for understanding microbe—clay mineral interactions and heavy metal immobilization in clay-rich natural environments.

54 ENVIRONMENTAL SCIENCES↗

Uranyl-Tc( vii )/Tc( v ) hybrid clusters

Pertechnetate ( 99 Tc VII O 4 − ) and autoreduced 99 Tc(v), species coordinate to UO 2 2+ to form hybrid clusters. These clusters have important implications to understanding technetium chemistry in spent nuclear fuel and legacy wastes.

Chemistry↗

Synthesis of Mg2IrH5: A potential pathway to high-Tc hydride superconductivity at ambient pressure

Following long-standing predictions associated with hydrogen, high-temperature superconductivity has recently been observed in several hydride-based materials. Nevertheless, these high-Tc phases only exist at extremely high pressures, and achieving high transition temperatures at ambient pressure remains a major challenge. Recent predictions of the complex hydride Mg2IrH6 may help overcome this challenge with calculations of high-Tc superconductivity (65K

High-temperature superconductors↗

Total absorption spectroscopy of the β decay of 101,102 Zr and 109 Tc

The β decay of 101,102 Zr and 109 Tc was studied using the technique of total absorption spectroscopy. The experiment was performed at the National Superconducting Cyclotron Laboratory using the Summing NaI(Tl) (SuN) detector in the first-ever application of total absorption spectroscopy with a fast beam produced via projectile fragmentation. The β -decay feeding intensity and Gamow-Teller transition strength distributions were extracted for these three decays. The extracted distributions were compared to three different quasiparticle random-phase approximation (QRPA) models based on different mean-field potentials. A comparison with calculations from one of the QRPA models was performed to learn about the ground-state shape of the parent nucleus. For 101 Zr and 102 Zr, calculations assuming a pure shape configuration (oblate or prolate) were not able to reproduce the extracted distributions. These results may indicate that some type of mixture between oblate and prolate shapes is necessary to reproduce the extracted distributions. For 109 Tc, a comparison of the extracted distributions with QRPA calculations suggests a dominant oblate configuration. The other two QRPA models are commonly used to provide β-decay properties in r-process network calculations. This work shows the importance of making comparisons between the experimental and theoretical β-decay distributions, rather than just half-lives and β-delayed neutron emission probabilities, as close to the r-process path as possible.

79 ASTRONOMY AND ASTROPHYSICS↗

Demonstrating PyCalphad, ESPEI, and MSTDB-TC for MSR Applications

The utility of thermochemical modeling tools PyCalphad, ESPEI, and MSTDB-TC are demonstrated for applications relevant to molten salt reactor design, safety, and licensing. Given the availability of experimental data, the demonstration is predominantly focused on the use of MSTDB-TC v3.0 to model Li- and Be-bearing fluoride salt mixtures. Nonetheless, the methodology reported in using these tools for such applications can be applied to any salt system given requisite data availability.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

A search for technetium (Tc II) in barium stars

The authors searched without success for the lines of Tc II at 2647.02, 2610.00 and 2543.24 A in IUE spectra of the barium stars HR 5058, Omicron Vir, and Zeta Cap. The lack of Tc II implies that the observed s-process enhancements were produced more than half a million years ago and supports the suggestion that the spectral peculiarities of barium stars are probably related to the binary nature of the stars.

Little-Marenin, Irene R.↗

An experimental study of high Tc superconducting microstrip transmission lines at 35 GHz and the effect of film morphology

Microstrip transmission lines in the form of ring resonators were fabricated from a number of in-situ grown laser ablated films and post-annealed co-sputtered YBa2Cu3O(7-x) films. The properties of these resonators were measured at 35 GHz and the observed performance is examined in light of the critical temperature (Tc) and film thickness and also the film morphology which is different for the two deposition techniques. It is found that Tc is a major indicator of the film performance for each growth type with film thickness becoming important as it decreases towards 100 A. It is also found that the films with a mixed grain orientation (both a axis and c axis oriented grains) have poorer microwave properties as compared with the primarily c axis oriented material. This is probably due to the significant number of grain boundaries between the different crystallites, which may act as superconducting weak links and contribute to the surface resistance.

Chorey, C. M.↗

An experimental study of high Tc superconducting microstrip transmission lines at 35 GHz and the effect of film morphology

Microstrip transmission lines in the form of ring resonators were fabricated from a number of in-situ grown laser ablated films and post-annealed co-sputtered YBa2Cu3O(7-x) films. The properties of these resonators were measured at 35 GHz and the observed performance is examined in light of the critical temperature (Tc) and film thickness, and also the film morphology, which is different for the two deposition techniques. It is found that Tc is a major indicator of the film performance for each growth type, with film thickness becoming important as it decreases towards 1000 A. It is also found that the films with a mixed grain orientation (both a-axis and c-axis oriented grains) have poorer microwave properties as compared with the primarily c-axis oriented material. This is probably due to the significant number of grain boundaries between the different crystallites, which may act as superconducting weak links and contribute to the surface resistance.

Chorey, C. M.↗

Rugged Low-Resistance Contacts To High-Tc Superconductors

Newly developed technique involving use of gold makes possible to fabricate low-resistance contacts with rugged connections to high-Tc superconductors. Gold diffused into specimen of superconducting material by melting gold beads onto surface of specimen, making strong mechanical contacts. Shear strength of gold bead contacts greater than epoxy or silver paste. Practical use in high-current-carrying applications of new high-Tc materials, including superconducting magnets, long-wavelength sensors, electrical ground planes at low temperatures, and efficient transmission of power.

Caton, Randall↗

Fabrication Of High-Tc Superconducting Integrated Circuits

Microwave ring resonator fabricated to demonstrate process for fabrication of passive integrated circuits containing high-transition-temperature superconductors. Superconductors increase efficiencies of communication systems, particularly microwave communication systems, by reducing ohmic losses and dispersion of signals. Used to reduce sizes and masses and increase aiming accuracies and tracking speeds of millimeter-wavelength, electronically steerable antennas. High-Tc superconductors preferable for such applications because they operate at higher temperatures than low-Tc superconductors do, therefore, refrigeration systems needed to maintain superconductivity designed smaller and lighter and to consume less power.

Bhasin, Kul B.↗

High Tc superconducting bolometric and nonbolometric infrared (IR) detectors

The original workplan for the first year of the project includes the following: establishment of a pilot superconductivity application laboratory at UDC to support the research component of the project; research on the source of electrical noise in High Tc superconducting films in order to optimize the film microstructure and lower the NEP; and lay the foundation of an academic support for exposing UDC students to the theory and application of High Tc superconductivity. Attached to this status report are abstracts and the course description for Introduction to Applications of Superconductivity.

Lakeou, Samuel↗

Electromagnetic Thermocouple (TC) Anomaly Mechanisms During Atmospheric Entry

Thermocouples (TCs) are a critical diagnostic sensor for high enthalpy environments including Thermal Protection Systems (TPS) for atmospheric entry, hypersonic wind tunnels, and arc jet test facilities. They are used for both evaluating facility environmental conditions (enthalpy, and heat flux) as well as for measuring in-situ material thermal response under test conditions (thermal conductivity, heat capacity, etc.). Consequently, accurate TC measurements are fundamental for both material and facility Verification and Validation (V&V). However, a number of electromagnetic TC anomalies have been observed in both ground tests and flight instrumentations. These anomalies are caused via various coupling mechanisms: surface voltage coupling, Hall effect currents, and RF rectification. All of these mechanisms can, if unaddressed, result in obviously compromised results or worse, non-physical measurements which appear reasonable. This talk will provide an overview of each of these anomaly mechanisms and discuss ongoing efforts to quantify and mitigate them.

Magnus Haw↗