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Alternative High-Performance Ceramic Waste Forms

This final report (M5NU-12-NY-AU # 0202-0410) summarizes the results of the project titled “Alternative High-Performance Ceramic Waste Forms,” funded in FY12 by the Nuclear Energy University Program (NEUP Project # 12-3809) being led by Alfred University in collaboration with Savannah River National Laboratory (SRNL). The overall focus of the project is to advance fundamental understanding of crystalline ceramic waste forms and to demonstrate their viability as alternative waste forms to borosilicate glasses. We processed single- and multiphase hollandite waste forms based on simulated waste streams compositions provided by SRNL based on the advanced fuel cycle initiative (AFCI) aqueous separation process developed in the Fuel Cycle Research and Development (FCR&D). For multiphase simulated waste forms, oxide and carbonate precursors were mixed together via ball milling with deionized water using zirconia media in a polyethylene jar for 2 h. The slurry was dried overnight and then separated from the media. The blended powders were then subjected to melting or spark plasma sintering (SPS) processes. Microstructural evolution and phase assemblages of these samples were studied using x-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersion analysis of x-rays (EDAX), wavelength dispersive spectrometry (WDS), transmission electron spectroscopy (TEM), selective area x-ray diffraction (SAXD), and electron backscatter diffraction (EBSD). These results showed that the processing methods have significant effect on the microstructure and thus the performance of these waste forms. The Ce substitution into zirconolite and pyrochlore materials was investigated using a combination of experimental (in situ XRD and x-ray absorption near edge structure (XANES)) and modeling techniques to study these single phases independently. In zirconolite materials, a transition from the 2M to the 4M polymorph was observed with increasing Ce content. The resulting powders were consolidated via SPS. Ce was reduced to the trivalent oxidation state and the zirconolite was converted into undesirable perovskite. The zirconolite polymorphs found in the synthesized powders were recovered after a post-SPS heat treatment in air. These results demonstrated the potential of processing in controlling the phase assemblage in these waste forms. Hollandites with Cr 3+ trivalent cations were identified as potential hosts for Cs immobilization and are being investigated for Cs retention properties. Series of compositions Ba 1.15-x Cs 2x Cr 2.3 Ti 5.7 O 16 , with increasing Cs loadings, were prepared by sol-gel process and characterized for structural parameters. Structural characterization was performed by a combination of powder XRD and neutron powder diffraction. Phase pure hollandite adapting monoclinic symmetry (I2/m) was observed for 0 ≤ x ≤ 0.55. These results were used to develop a new structural model to interpret Cs immobilization in these hollandites. Performance of these waste forms were evaluated for chemical durability and radiation resistance. Product consistency testing (PCT) and vapor hydration testing (VHT) were used for testing of chemical durability. Radiation resistance was tested using He + ions to simulate $\alpha$ particles and heavy ions such as Au 3+ to simulate a recoil. These results showed that these waste forms were chemically durable. The waste forms also amorphized to various degrees on exposure to simulated radiation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Status Report on Laboratory Testing and International Collaborations in Salt.

This report is a summary of the international collaboration and laboratory work funded by the US Department of Energy Office of Nuclear Energy Spent Fuel and Waste Science & Technology (SFWST) as part of the Sandia National Laboratories Salt R&D work package. This report satisfies milestone levelfour milestone M4SF-17SN010303014. Several stand-alone sections make up this summary report, each completed by the participants. The first two sections discuss international collaborations on geomechanical benchmarking exercises (WEIMOS) and bedded salt investigations (KOSINA), while the last three sections discuss laboratory work conducted on brucite solubility in brine, dissolution of borosilicate glass into brine, and partitioning of fission products into salt phases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Self-powered Wireless Dual-mode Langasite Sensor for Pressure/Temperature Monitoring of Nuclear Reactors

Safety issues in nuclear power plants are of extreme importance. Numerous sensors are used within nuclear power plants for sensing and monitoring of its critical operation parameters. As currently implemented, during massive losses of power across the plant in accidents, the backup batteries for the monitoring sensors will ultimately be drained and can cease to operate. The overall objective of this NEUP project is to develop a novel self-powered wireless hybrid sensor which can accurately monitor both pressure and temperature using a single device, even in the extreme harsh environments of severe nuclear accidents, without the requirement of external electricity. At Virginia Tech side, a heat pipe assisted thermoelectric generator (TEG) energy harvester and associated power management and data transmission circuits were developed. The energy harvester can produce electrical power continuously, even in loss of plant and external power situations, providing power for important data transmission for accident diagnosis. The self-powered sensing system could be integrated directly onto key nuclear components including pipes, pump housings, heat exchangers, reactor vessels, and shielding structures inside and outside of the reactor core. Two TEG based energy harvesters which can work in relatively low (50-250 ºC) and high temperature ranges (250-350 ºC) were established and tested. In the prototypes, heat pipes were introduced to reduce the heat resistances of the device at the hot and cold ends. The power output of the heat pipe assisted TEG module is 2.22 W, which is 6 times more than one using an aluminum rod. In-lab tests showed that these devices canmeet the requirement to power the sensors and circuit during normal and off-normal conditions.Amodel was then built to analyze the thermal network in the energy harvester, and was used to optimize its performance and reduce its geometry size. The design and testing of the vibrational energy harvester were completed. The harvester, has shown to effectively increase the vibrational potential of the main coolant pump, though it has been shown that thermal energy has a much higher potential for the powering of sensors. In this project, a self-start charger circuit for the energy harvester was designed to regulate and manage the power. An energy storage element was incorporated into the energy harvesting module for sensors and wireless transceivers in an off-normal situation. The signal conditioning and wireless communication electronic circuits were developed and tested in the lab. An important consideration for an energy harvester within a nuclear power plant is the level of radiation it will encounter during operation. The two main sources of radiation in a nuclear power plant are gamma and neutron radiation. Aradiation experiment was conducted in the Westinghouse Electric Company during which the prototypes were placed in a 106 rad radiation environment to test their ability to operate in the extreme environment. The results showed that this level of radiation had little effect on the performance of the TEGmaterial and heat pipe heat exchanging system. Its influence on the circuit was still under research, however the need for more development on radiation hardened electronics is needed. Pressure measurement based on piezoelectric crystal resonators has advantages over the commercially available methods like capacitive, electromagnetic, optical, potentiometric, and piezo resistive strain gauges. Since the output of piezoelectric based sensors are digital in format, it has a very high resolution, high accuracy, and long-term stability. Quartz is one of the commonly used piezoelectric material in digital pressure sensors design. This material is elastic in nature, providing high stability, high repeatability, high elasticity, repeatable mechanical behavior for many cycles of operation, and is free of hysteresis. The quartz resonator has a high Q, which means that very high vibration can be driven with the very low electric power. Langasite (LGS) is a new promising piezoelectric material that combines the advantageous properties of quartz with a better performance at high temperatures. LGS will not undergo any phase transitions up to its melting temperature of 1473 C, and hence, the application of Langasite in measuring pressure at high temperatures is promising. In this project, the design and fabrication of the piezo oscillator crystal for temperature and pressure measurement has been completed. The entire sensor has been fabricated and tested to see its sensitivity to temperature and pressure changes. The design and optimization of the radiation shielding systems that can effective protect the duel-mode Langasite sensor inside reactor core were demonstrated. To maximize the radiation shielding effectiveness, different types of materials are investigated based upon recent developments of radiation shielding systems including aluminum + Boron carbide and bismuth borosilicate glass B2O3 in addition to tungsten/B4C. New materials based upon metatheses is included as potential shielding to mitigate neutron fluencies. The radiation shielding effectiveness of selected composites are evaluated within a broader neutron spectrum from thermal, epithermal, fast (1 MeV) and 15 MeV neutrons. Performance analysis was also conducted to evaluate the effects of selected composite systems.Aconceptual design was also proposed for the packaging and integration of the radiation shielding system with the sensor, and its applicability within the reactor core was discussed. At end of the project, all components necessary for a complete sensing and monitoring system, including a langasite sensor, electrodes, the TEG harvester, an energy storage device, and power management and transmission electronics were integrated to demonstrate feasibility in powering the sensor. Finally, integration of each component into a full package, and a full demonstration were done.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Vapor-Liquid Partitioning of Methylmercury Compounds: Fundamental Data to Support the Savannah River Site Liquid Waste System: Henry's Law, Solubility and Vapor Pressure Determination for Representative Methylmercury Compounds

The Savannah River Site (SRS) Liquid Waste System (LWS) contains approximately 66 tons of mercury within the liquids, salts, and sludges that are currently being processed into final wasteforms for disposal. Mercury concentrations within the system exceed those typically experienced in environmental or industrial systems; thus, management of mercury compounds continues to be a priority for SRS. In the LWS, waste is vitrified into a borosilicate glass wasteform that contains most of the radioactivity, while the lower activity solutions are dispositioned in a low-level grout wasteform, or “saltstone”. The alkaline, high ionic strength caustic wastes are pumped, evaporated, and otherwise managed throughout the LWS and Defense Waste Processing Facility (DWPF) as they are stored and prepared for conversion to the final wasteforms. Because of the complexity of this system, a key component of effective mercury management in the LWS requires analysis of mercury in various physical phases. The high concentration of mercury within the SRS LWS has the potential to generate vapor-phase contamination. Elemental mercury (Hg 0 ), dimethylmercury ((CH 3 ) 2 Hg), and methylmercury (CH 3 Hg + ) are among species known or suspected to contribute to the flux of mercury from liquid to vapor phase (Iverfeldt and Lindquist, 1982). Chemical speciation affects not only mercury behavior in LWS operations but may also affect the performance of mercury treatment and removal technologies in the LWS.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

An Evaluation of the Impact of Glycolate and Glycolate Mitigation on the Defense Waste Processing Facility Recycle Diversion Project Flowsheet

The Savannah River Site (SRS) Defense Waste Processing Facility (DWPF) processes radioactive High Level Waste (HLW) sludge solids from the Concentration, Storage, and Transfer Facilities (CSTF); which includes the SRS Tank Farm and Evaporator facilities, and a concentrated Cs-137 laden stream and a Monosodium Titanate (MST) and sludge solids stream from the SRS Salt Waste Processing Facility (SWPF). The waste is chemically adjusted with acids and reductant (currently with 50 wt.% nitric acid and ~90 wt.% formic acid, but eventually formic acid will be substituted with ~70 wt.% glycolic acid), and frit is added so that a durable, borosilicate glass waste form can be produced when the material is vitrified in the melter. As a result of the evaporation of water during both the melter feed preparation and the melter feed vitrification steps in DWPF, a recycle waste stream is generated, neutralized, and sent back to the CSTF. The recycle waste is a dilute aqueous stream originating from the collection of condensate liquids containing some minor sludge, MST, and frit solids and other waste components resulting from melter feed entrainment during foamover events and transfer of volatile species into the condensate. The recycle stream volume is significant and is expected to approach 3 million gallons per year once SWPF reaches full operation, requiring the use of multiple large CSTF tanks for storage. The recycle waste is currently collected in the SRS Tank Farm and periodically evaporated in the 242-16H (2H) Evaporator to conserve storage space.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

T-1075: Large Area Fast Timing Beam Time of Flight (LAFTBToF) for ProtoDUNE

Large-area Picosecond Photodetectors (LAPPDs), developed at Argonne National Laboratory (ANL), present an opportunity to provide identification of charged particles in the 2-10 GeV/c range. Traditional methods using ionization or Cherenkov detectors require large amounts of material or pathlength for the particle to traverse in order to get a clean measurement, and are ill suited for particle beam identification in fixed-target experiments. The 6x6 cm 2 LAPPD uses mm-thick borosilicate glass micro-channel plates with a resistive surface coating added via atomic layer deposition. An electrical connection schematic of the LAPPD is shown in Figure 1. Electrons emitted by the photocathode are accelerated through the MCPs, which have µm-sized capillaries, and an avalanche of electrons is created as the electrons collide against the walls of the capillaries of the MCPs. The resulting electron avalanche is collected on anode strip lines and the signal may be read out on both ends of the stipline. The resistive coating of the thin MCPs and the short path length of the electrons to the readout results in fast rise times, gains of greater than 10 6 and typical timing resolutions of 50 ps. Differential timing on the ends of the strip lines can provide mm-level position measurements. The material of the bare LAPPD presents less than 0.05 of an interaction length and approximately 0.12 of a radiation length for a charged particle of I GeV/c. In our application, two large-area photodetectors separated by 5-10 meters can be used in a time-of-flight (ToF) measurement for 3σ separation of2-7 GeV/c charged pions, kaons and protons with minimal impact on the particle's trajectory and momentum.

43 PARTICLE ACCELERATORS↗

T-1065: Secondary Emitters Study

One possibility to make a fast and radiation resistant shower maximum (SM) detector or preshower detector is to use a secondary emitter (SE) as an active element. This method was proposed in 1990. Micro channel plates (MCP) were used as SE in the SM. The attractive properties of such SM are: 1) a two-dimensional map of energy at the SE location; 2) timing information at few tens of picosecond level, also as transverse shower size and 3) possible separation of electromagnetic and hadronic energy based on the differences of the shower size and timing. An electron-multiplier-based sampling calorimeter requires thin planar detectors at an affordable cost. Large-area photo detectors based on ALD-functionalized 20-cm-square borosilicate glass capillary micro-channel plates (MCPs), currently being developed by the LAPPD Collaboration, are candidates for the active elements. The first results of the new shower maximum detector with the micro channel plate photomultiplier (MCP-PMT) as active elements are described. The current proposal is the next natural step in this direction. The experimenters propose using large-area MCPs assembled without the usual bialkali photocathodes as the active element in sampling calorimeters. LAPPD modules without photocathodes can be economically assembled in a glove box and then pumped and sealed using the process to construct photomultipliers, bypassing the slow and expensive vacuum-transfer process required by bialkali photocathodes. The first use of electron multipliers, in this case MCPs (Fig. 1, left) as an active element in multi-layer sampling calorimeters is described. A chevron of two MCPs in vacuum, was located behind a tungsten plate on which 5 GeV and 26 GeV electrons were incident (Fig. 1, right). The amplitude of the MCP signal (Fig. 2) as a function of the tungsten thickness was measured. The primary electrons produce a shower of secondary particles, including positron-electron pairs and gammas; the response of the MCPs (Fig. 2, left) is proportional to the number of particles in the shower, which is dependent on the initial particle energy. The MCP signal shape is presented in the Fig. 2, right). The FWHM of the signal is 1 ns.

43 PARTICLE ACCELERATORS↗

Vitrification Testing of HLW with High Phosphate

Projections of the number of high level waste (HLW) canisters to be produced in the Hanford Tank Waste Treatment and Immobilization Plant (WTP) (e.g., [1]) are based upon the inventory of the tank wastes, the anticipated performance of the sludge treatment processes, and current understanding of the capability of the borosilicate glass waste form. The WTP HLW melter design, unlike earlier Department of Energy (DOE) melter designs, incorporates a glass bubbler system. The bubblers create active glass pool mixing and thereby improve heat and mass transfer and glass melting rate. The WTP HLW melters each have a glass surface area of 3.75 m 2 and depth of ~1.1 m. The two melters in the HLW facility together are designed to produce up to 7.5 MT of glass per day at 100% availability. Further increases in HLW waste processing rates can potentially be achieved by optimization of the feed and glass formulations, increasing the melter operating temperature above 1150⁰C, and by increasing the waste loading in the glass product. Increasing the waste loading also has the added benefit of decreasing the number of canisters for storage.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effect of Form of Chromium on Spinel Formation

A number of Hanford high level waste (HLW) streams contain sufficiently high concentrations of chromium for it to become the waste loading limiting component in the waste. Chromium has relatively low solubility in borosilicate glasses and leads to the formation of various crystal phases including spinels. The extent of crystal formation must be managed during melter processing to prevent operational issues and potential premature melter failure that can result from excessive accumulation of crystals in the melter. In previous work for the Department of Energy (DOE) Office of River Protection (ORP), high-waste loading glass formulations were developed for representative HLW streams that are high in chromium. Results from those studies suggested that there may be differences in the crystallization behavior between glasses prepared in crucible melts and those prepared in DuraMelter 100 (DM100) joule heated melter runs. Understanding the cause of those differences has the potential to lead to the development of methods to further increase waste loadings for high chromium HLW streams through control of the formation of chromium-bearing crystals. As noted previously, the potential causes include differences in the form of components in the batch, including the form of chromium, as well as redox effects. This report describes the results from work to elucidate the origins of the observed differences and to identify melter feed composition modifications to control the formation of chromium-bearing crystal phases. The work focused on determining the effects of the form of chromium and the concentrations of oxidants in feed batches on spinel crystallization. Also evaluated was the use of potential melter feed additives to influence the redox state of chromium in the melt and its effect on spinel crystallization. As described in the Test Plan for this work, the objectives were accomplished through a combination of crucible-scale tests, small-scale tests with additives to influence redox state, and melter tests. This work builds on previous work performed at the Vitreous State Laboratory (VSL) of The Catholic University of America (CUA) for ORP to increase the waste loadings and processing rates of HLW glass formulations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

THERMAL DECOMPOSITION OF HYDRAZINE

The Thermal Stability of Hydrazine has been studied in the temperature and pressure intervals of 175" to 250"C. and 300 to 430 p.s.i., Respectively. Previous studies of the decomposition of hydrazine indicated that several factors affect its stability (2, 5, 7). the rate of decomposition is increased by the presence of certain surfaces (especially metals and salts). pH, oxygen, and carbon dioxide. Further explosive decomposition Is attributable to the uncontrolled heterogeneous, gas-phase decomposition. These factors were considered in selecting the following experimental conditions: highly purified hydrazine was prepared in a nitrogen atmosphere, and this product was decomposed over triply distilled mercury in outgassed borosilicate glass tubes at ullages that were initially zero. This study also included the effects of added quantities of ammonia on the rate of decomposition and an investigation of the products of the decomposition.

Harold W. Lucien↗

Electrodeless discharge lamp is easily started, has high stability

Electrodeless discharge borosilicate glass lamp is used in various high-resolution optical systems. It is partially charged with krypton, contains small amounts of rubidium, and is enclosed in a hermetically sealed envelope that maintains the lamp at an optimum temperature during discharge. The lamp is quickly started by its excitation coil.

Bell, W. E.↗

Protective coating for laser diodes

Coating for GaAs laser diodes should not alter optical and electrical properties. Borosilicate glass coating is easy to apply, breaks evenly when cleaved, and is abrasion and moisture resistant. Its low index of refraction makes thickness less critical when depositing half-wavelength coating.

Ladany, I.↗

Solar cells for solar power satellites

The concept of a solar-cell array for a solar power satellite is developed to permit evaluation of its economic feasibility for generating power for delivery to public utilities on earth. Gallium arsenide solar cells were considered but it could not be assured that the world gallium resources could support constructions of two solar power satellites per year. Therefore, for preliminary design an array blanket made from 5 by 10 cm silicon solar cells, 50 microns thick, and electrostatically bonded between borosilicate glass sheets was adopted. In annealing experiments, a radiated 50 microns thick cell was restored to its initial performance in a 500 C. Solar-cell efficiency effects significantly the solar power satellite mass, which varies from 90,000 metric tons for 20 percent cells to 120,000 metric tons for 12 percent cells. The anticipated cost of delivered power, based on 1977 dollars, varies from 4 cents per kWh with 18 percent cells, to 5 cents per kWh for 12 percent efficient cells.

Oman, H.↗

Secondary Electron Emission Yields

The secondary electron emission (SEE) characteristics for a variety of spacecraft materials were determined under UHV conditions using a commercial double pass CMA which permits sequential Auger electron electron spectroscopic analysis of the surface. The transparent conductive coating indium tin oxide (ITO) was examined on Kapton and borosilicate glass and indium oxide on FED Teflon. The total SEE coefficient ranges from 2.5 to 2.6 on as-received surfaces and from 1.5 to 1.6 on Ar(+) sputtered surfaces with 5 nm removed. A cylindrical sample carousel provides normal incidence of the primary beam as well as a multiple Faraday cup measurement of the approximately nA beam currents. Total and true secondary yields are obtained from target current measurements with biasing of the carousel. A primary beam pulsed mode to reduce electron beam dosage and minimize charging of insulating coatings was applied to Mg/F2 coated solar cell covers. Electron beam effects on ITO were found quite important at the current densities necessary to do Auger studies.

Krainsky, I.↗

Adjustable high emittance gap filler

A flexible, adjustable refractory filler is disclosed for filling gaps between ceramic tiles forming the heat shield of a space shuttle vehicle, to protect its aluminum skin during atmospheric reentry. The easily installed and replaced filler consists essentially of a strip of ceramic cloth coated, at least along both its longitudinal edges with a room temperature vulcanizable silicone rubber compound with a high emittance colored pigment. The filler may have one or more layers as the gap width requires. Preferred materials are basket weave aluminoborosilicate cloth, and a rubber compounded with silicon tetraboride as the emittance agent and finely divided borosilicate glass containing about 7.5% B2O3 as high temperature binder. The filler cloth strip or tape is cut to proper width and length, inserted into the gap, and fastened with previously applied drops of silicone rubber adhesive.

Leiser, D. B.↗