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Quantitative U=O bond activation in uranyl complexes via silyl radical transfer

Reductive silylation of the uranyl dication with 1,4-bis(trimethylsilyl)dihydropyrazine, or “Mashima's reagent”, is detailed. The reagent simultaneously delivers silylium ions and electrons to multiple uranyl complexes, i.e. a pyridine dipyrrolide uranyl complex and a common uranyl-containing starting material, UO 2 Cl 2 (OPPh 3 ) 2 . This reaction results in quantitative activation of thermodynamically robust U=O bonds. Furthermore, the reductive functionalization of environmentally persistent actinyl species with Mashima's reagent is seen as a promising solution for nuclear waste remediation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Supplemental Environmental Baseline Survey for Proposed Land Use Permit Modification for Expansion of the Dynamic Explosive Test Site (DETS) 9940 Main Complex Parking Lot

The “subject property” is comprised of a parcel of land within the Kirtland Military Reservation, Bernalillo County, New Mexico, as shown on the map in Appendix B of this document. The land requirement for the parking lot addition to the 9940 Main Complex is approximately 2.7 acres. The scope of this Supplemental Environmental Baseline Survey (SEBS) is for the parking lot addition land transfer only. For details on the original 9940 Main Complex see Environmental Baseline Survey, Land Use Permit Request for the 9940 Complex PERM/0-KI-00-0001, August 21, 2003, and for details on the 9940 Complex Expansion see Environmental Baseline Survey, Proposed Land Use Permit Expansion for 9940 DETS Complex, June 24, 2009. The 2.7-acre parcel of land for the new parking lot, which is the subject of this EBS (also referred to as the “subject property”), is adjacent to the southwest boundary of the original 12.3- acre 9940 Main Complex. No testing is known to have taken place on the subject property site. The only activity known to have taken place was the burial of overhead utility lines in 2014. Adjacent to the subject property, the 9940 Main Complex was originally a 12.3-acre site used by the Department of Energy (DOE) under a land use permit from the United States Air Force (USAF). Historical use of the site, dating from 1964, included arming, fusing, and firing of explosives and testing of explosives systems components. In the late 1970s and early 1980s experiments at the 9940 Main Complex shifted toward reactor safety issues. From 1983 to 1988, fuel coolant interaction (FCI) experiments were conducted, as were experiments with conventional high explosives (HE). Today, the land is used for training of the Nuclear Emergency Response community and for research on energetic materials. In 2009, the original complex was expanded to include four additional 20-acre areas: 9940 Training South, 9940 Training East, T-Range 6, and Training West Landing Zone. The proposed use of the subject property is for the purpose of adding a parking lot to serve the increase in customer vehicles that is occurring as the 9940 Main Complex is more heavily utilized, and as the 2009 Expansion areas come online as operational training facilities. The subject property would be used only for parking, not for testing or training activities. The parking lot would have a gravel surface. Current and future work at the 9940 Main Complex involves arming, fuzing, and firing of explosives and the testing of explosive systems components in both terrestrial and aquatic settings. It also involves specialized training activities for a variety of first responder customers, both DOE and non-DOE agencies. The approach was to perform a document search, supplemented by a visual site inspection, to identify potential environmental contamination associated with the property. Factors evaluated included hazardous substances; petroleum products and derivatives; environmental restoration sites; areas of concern; storage tanks; oil/water separators; grease traps; wash racks; waste tanks; pesticides; military munitions/ordnance; medical or bio-hazardous waste; radioactive waste; solid/municipal waste; indoor air quality; groundwater; wastewater treatment, collection, and disposal/discharge; drinking water quality; utilities; asbestos; polychlorinated biphenyls (PCBs); radon; lead-based paint; cultural resources; floodplains; and natural/biological resources. Each of these factors is evaluated separately in Section 5, Findings for Subject Property. The property categorization for this subject property would be considered Category 1- “An area or real property where no storage, release, or disposal of hazardous substances or petroleum products or their derivatives has occurred into the environment or structures or disposed on the subject property (including no migration of these substances from adjacent properties).” There appears to be sufficient information to categorize the subject property and it appears that no further effort needs to be made to obtain additional information. There are no findings of an adverse nature on the subject property itself or from adjacent properties. It is recommended that the proposed transfer of the subject property from the USAF to DOE proceed.

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Iodobutane Deep Bed Adsorption Test Report

The Department of Energy (DOE) Nuclear Technology Research and Development (NTRD) Program Material Recovery and Waste Form Development (MRWFD) Campaign Off-gas Sigma Team has supported research and development on iodine control and iodine waste forms for the past several years. As a part of this on-going research, two deep-bed iodobutane adsorption tests have been performed with higher NO x levels. High (>1,000) iodine decontamination factors (DFs, the ratios of the inlet iodine concentrations divided by the outlet iodine concentrations, when the gas flowrate is constant) were achieved with both the silver aerogel and silver zeolite sorbents. The iodine adsorption mass transfer zone (the depth of the sorbent bed in which adsorption is occurring at any specific time) for these tests was estimated at 4 inches for both sorbents under the test conditions. Silver utilization for silver aerogel sorbent reached 41% (up to 12 g adsorbed iodine per 100 g silver aerogel sorbent), while silver utilization reached 43% (up to 6.8 g adsorbed iodine per 100 g silver zeolite sorbent). These values are generally consistent with results for prior methyl iodide adsorption tests. The results also indicate that, during iodine adsorption process, the organic iodide molecule decomposes so that the iodine can be adsorbed. Even when sorbent breakthrough is reached, the organic iodide molecule continues to decompose; and the unadsorbed iodine that passes through bed is no longer in the form of the original organic iodide; but in the form of iodine compounds that are soluble in NaOH solutions, such as HI or I 2 . This research and development has included iodine adsorption tests using a laboratory-scale test system containing segmented fixed beds of iodine adsorbents in series. Non-radioactive synthetic gas mixtures were blended from air, nitrogen, NO, NO 2 , water, and the target iodine compounds to represent dissolver off-gas (DOG) streams from used nuclear fuel aqueous reprocessing.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Thermodynamic analysis on heavy metals partitioning impacted by moisture during the MSW incineration

Highlights: Black-Right-Pointing-Pointer Partitioning of HMs affected by moisture was investigated by thermodynamic analysis. Black-Right-Pointing-Pointer Increase in moisture and in temperature was opposite impact on HMs contribution. Black-Right-Pointing-Pointer The extent of temperature decreased by increase in moisture determines the impact. - Abstract: A thermodynamic calculation was carried out to predict the behavior and speciation of heavy metals (HMs), Pb, Zn, Cu, and Cd, during municipal solid waste (MSW) incineration with the different moisture levels. The calculation was based on the minimization of the total Gibbs free energy of the multi-components and multi-phases closed system reaching chemical equilibrium. The calculation also indicated the reaction directions and tendencies of HMs components. The impacts of chlorine additives (No PVC, 1%PVC, and 5%PVC) and moisture on the behavior of HMs were investigated at different temperature levels in the system (750 Degree-Sign C, 950 Degree-Sign C, and 1150 Degree-Sign C). Furthermore, because the incineration temperature falls down with the increase in moisture in waste, the co-influence of moisture and temperature in combusting MSW on the HMs was also studied with the given chlorine (as 1%PVC + 0.5%NaCl). The results showed that in the non-chlorine system, the impact of the moisture on Pb, Zn, and Cu was not significant, and the ratio of compound transformation was less than 10%, except the Cd compounds at 950 Degree-Sign C and 1150 Degree-Sign C. In the system with low chlorine (as 1%PVC) at constant temperature, the chlorides of HMs (Cd, Pb, Zn, and Cu) transferred to oxides, and when the content of chlorine rose up (as 5%PVC), the ratio of the chlorides of HMs (Cd, Pb, Zn, and Cu) transferring to oxides fell down noticeably. When the moisture varied together with the temperature, the Zn and Cu compounds transferred from chlorides to oxides with increase in moisture as well as decrease in temperature. At the temperature of 700-1000 Degree-Sign C, the impact of temperature on Pb and Cd was little and the moisture was the main factor; while at the temperature of 1000-1200 Degree-Sign C, the impact of increase in moisture and decrease in temperature on Pb and Cd was almost equal and reversed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An innovative implementation of LCA within the EIA procedure: Lessons learned from two Wastewater Treatment Plant case studies

Life Cycle Assessment (LCA) has been identified in the literature as a promising tool to increase the performance of environmental assessments at different steps in the Environmental Impact Assessment (EIA) procedure. However, few publications have proposed a methodology for an extensive integration, and none have compared the results with existing EIA conclusions without LCA. This paper proposes a comprehensive operational methodology for implementing an LCA within an EIA. Based on a literature review, we identified four EIA steps that could theoretically benefit from LCA implementation, i.e., (a) the environmental comparison of alternatives, (b) the identification of key impacts, (c) the impact assessment, and (d) the impact of mitigation measures. For each of these steps, an LCA was implemented with specific goal and scope definitions that resulted in a specific set of indicators. This approach has been implemented in two contrasting Wastewater Treatment Plant (WWTP) projects and compared to existing EIA studies. The results showed that the two procedures, i.e., EIAs with or without inputs from LCA, led to different conclusions. The environmental assessments of alternatives and mitigation measures were not carried out in the original studies and showed that other less polluting technologies could have been chosen. Regarding the scoping step, the selected environmental concerns were essentially different. Global impacts such as climate change or natural resource depletion were not taken into account in the original EIA studies. Impacts other than those occurring on the project site (off-site impacts) were not assessed, either. All these impacts can be significant compared to those initially considered. On the other hand, unlike current LCA applications, EIAs usually address natural and technological risks and neighbourhood disturbances such as noises or odours, which are very important for the public acceptability of projects. Regarding the impact assessment, even if the conclusions of the EIAs with or without LCA were partially common for local on-site impacts, LCA gives crucial additional information on global and off-site impacts and highlights the processes responsible for them. Finally, for all EIA steps investigated, interest in LCA was demonstrated for both WWTP case studies. The feasibility in terms of skills, time and cost of such implementation has also been assessed. - Highlights: • An innovative methodology for a first-stage implementation of LCA in EIA is proposed. • Its applicability is demonstrated on two Wastewater Treatment Plant case studies. • The conclusions for the four EIA steps investigated differ with or without LCA. • LCA provides valuable additional information on 1) global and 2) off-site impacts. • LCA identifies pollution transfers towards a life cycle perspective.

54 ENVIRONMENTAL SCIENCES↗

US Department of Energy's Efforts in Intelligent Processing Equipment

The Department of Energy (DOE) uses intelligent processing equipment (IPE) technologies to conduct research and development and manufacturing for energy and nuclear weapons programs. This paper highlights several significant IPE efforts underway in DOE. IPE technologies are essential to the accomplishment of DOE's missions, because of the need for small lot production, precision, and accuracy in manufacturing, hazardous waste management, and protection of the environment and the safety and health of the workforce and public. Applications of IPE technologies include environmental remediation and waste handling, advanced manufacturing, and automation of tasks carried out in hazardous areas. DOE laboratories have several key programs that integrate robotics, sensor, and control technologies. These programs embody a considerable technical capability that also may be used to enhance U.S. industrial competitiveness. DOE encourages closer cooperation with U.S. industrial partners based on mutual benefits. This paper briefly describes technology transfer mechanisms available for industrial involvement.

Peavy, Richard D.↗

Application of the FW-CADIS variance reduction method to calculate a precise N-flux distribution for the FRJ-2 research reactor - 15603

In order to avoid unnecessary radiation exposure and to minimize the radioactive waste and respectively cost by the decommissioning of nuclear facilities, the radiological characteristics and the activity atlases are required. Therefore, a significant step is the accurate determination of the neutron fluence distribution resulting from the operation of a reactor. For this purpose, computer codes based on the Monte-Carlo method are employed because of the flexibility in the modelling of the complex structures and physical processes. In the scope of the research project founded by the German Federal Ministry of Education and Research (BMBF), and implemented by the Institute of Nuclear Engineering and Technology Transfer (NET) -RWTH Aachen, sophisticated simulation tools are developed, which have the capability to cover the range of demands for activity and dose rate distribution using the example of the German research reactor FRJ-2. Due to the complex geometry of FRJ-2, which consists of different structures and configuration, the MCNP5 Monte Carlo Code is the optimal method for a precise neutron transport simulation. This work presents a method to achieve a precise N-Flux distribution for the FRJ-2 research reactor using hybrid deterministic Monte Carlo method. (authors)

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Glycolate Analysis in Tank 22: Developing and Testing Analytical Methods for the Savannah River Site Liquid Waste System

Researchers developed and tested a range of techniques to support a low mg/L Limit of Quantitation (LOQ) of glycolate in radioactive Tank 22 waste solution by Ion Chromatography (IC) and by proton NMR. For the IC method, Dionex OnGuard II cartridges were tested as a means of removing alkali earth and transition metals that can interfere during ion chromatography applications especially when analyzing for low-concentration, chelating analytes. Additionally, concentrations of nitrate in the raw Tank 22 sample (5,000 to 10,000 mg/L) were managed by using reasonable levels of sample dilution. The resulting IC performance quality was enhanced by improving the baseline, increasing sensitivity [Limit of Quantitation (LOQ) of 12 mg/L and Limit of Detection (LOD) of 4.0 mg/L], and resolving analytes into well-defined Gaussian peaks when using the Dionex OnGuard II H⁺ cartridges to remove matrix interferences. High concentrations of nitrate limited the performance of the IC method. To achieve an acceptable baseline, samples with high nitrate content require more dilution, resulting in higher detection limits. Tests on samples with higher concentrations of nitrate (Tank 30 and 32 supernate with approximately 150000 mg/L nitrate) suggested that IC detection limits for glycolate in these samples would be > 500 mg/L. Thus, an LOQ of 12 mg/L is not feasible by this IC method on evaporator feed samples. An alternative method of glycolate analysis, using proton nuclear magnetic resonance (H NMR), was developed by the research team. In initial tests, the H NMR technique provided reasonable quantitation of glycolate in Tank 22 conditions by direct observation of the liquid. The H NMR method may provide improved detection limits for solutions with higher nitrate concentrations. We recommend further development of this analysis for high nitrate LWS samples such as evaporator feed and evaporator drop tank content. A method for pretreatment of samples using crystalline silicotitanate (CST) was developed and tested. The objective of the pretreatment was to facilitate analysis of samples with higher levels of radioactivity. The pretreatment did not influence the glycolate concentration in solution, and the pretreatment is projected to reduce Cs 137 activity in a sample by a factor of 16,200. The double strike CST pretreatment was demonstrated and would allow milliliters of higher activity samples to be transferred from the Shielded Cells and handled in a containment unit for glycolate analysis. The various studies validated IC and H NMR methods for glycolate analysis, defined the range of applicability, and demonstrated key supporting analytical protocols. Based on the results, high quality glycolate analysis of Tank 22 is feasible down to approximately 12 mg/L, with the potential for broader applicability of the methods to other conditions in the Savannah River Site Liquid Waste System (LWS).

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Gas Retention and Release from Nuclear Legacy Waste - 16449

The retention of gas within corroded magnox sludge waste at Sellafield, UK and secondary reprocessing waste at Hanford, USA has significant economic and safety implications for decommissioning various nuclear legacy buildings, including the magnox swarf storage silos and first generation magnox storage pond. A series of laboratory scale gas retention tests within magnesium hydroxide soft sediments have revealed a 4-51 Pa yield stress range where consolidated beds could retain sufficient gas to become buoyant with respect to a water supernatant. Density inversion could lead to a Rayleigh-Taylor style instability which could result in an upward transfer of radioactive material from the consolidated bed. The applicable yield stress range suggests that such rollover events may occur in weaker sediment than previously hypothesized, based on current understanding of the fluidization and stable channel mechanisms for gas release from weak and very strong sediments respectively. X-ray computed tomography images of gas retained by 7 Pa yield stress soft sediment reveal both a stable foam layer at the top of the bed and regions dense with micro-bubbles which could provide pathways for gas transport through the bed. Extension of these pathways, hidden below the surface of the sediment, to the container walls and the foam layer could represent a novel mechanism for gas release from intermediate strength sediments of <100 Pa yield stress. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

CO 2 utilization in built environment via the P CO 2 swing carbonation of alkaline solid wastes with different mineralogy

Carbon mineralization to solid carbonates is one of the reaction pathways that can not only utilize captured CO 2 but also potentially store it in the long term. In this study, the dissolution and carbonation behaviors of alkaline solid wastes (i.e., waste concrete) was investigated. Concrete is one of the main contributors to a large carbon emission in the built environment. Thus, the upcycling of waste concrete via CO 2 utilization has multifaceted environmental benefits including CO 2 emission reduction, waste management and reduced mining. Unlike natural silicate minerals such as olivine and serpentine, alkaline solid wastes including waste concrete are highly reactive, and thus, their dissolution and carbonation behaviors vary significantly. Here, both conventional acid (e.g., hydrochloric acid) and less studied carbonic acid (i.e., CO 2 saturated water) solvent systems were explored to extract Ca from concrete. Non-stoichiometric dissolution behaviors between Ca and Si were confirmed under far-from-equilibrium conditions (0.1 wt% slurry density), and the re-precipitation of the extracted Si was observed at near-equilibrium conditions (5 wt% slurry density), when the Ca extraction was performed at a controlled pH of 3. These experiments, with a wide range of slurry densities, provided valuable insight into Si re-precipitation phenomena and its effect on the mass transfer limitation during concrete dissolution. Next, the use of the partial pressure of CO 2 for the pH swing carbon mineralization process was investigated for concrete, and the results were compared to those of Mg-bearing silicate minerals. In the P CO 2 swing process, the extraction of Ca was significantly limited by the precipitation of the carbonate phase (i.e., calcite), since CO 2 bubbling could not provide a low enough pH condition for concrete–water–CO 2 systems. Furthermore, this study showed that the two-step carbon mineralization via P CO 2 swing, that has been developed for Mg-bearing silicate minerals, may not be viable for highly reactive Ca-bearing silicate materials (e.g., concrete). The precipitated calcium carbonate (PCC) derived from waste concrete via a pH swing process showed very promising results with a high CO 2 utilization potential as an upcycled construction material.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Numerical Investigation of Susceptor-Catalyst Design for Ethylene Generation in Radio Frequency Based Reactors

Ethylene is the most widely produced petrochemical component in the world. Whether reactors are heated directly or indirectly via steam, manufacturers use economies of scale to overcome inherent thermodynamic inefficiencies when burning fossil fuels. While allowing large-scale operations to use alternative sources of energy and raw materials, new methods of supplying energy to chemical reactor systems can reduce the energy waste produced by conventional processes. One viable method for effectively supplying energy to reactor systems is electromagnetic (EM) induction heating. Using the properties of radio frequency (RF) waves, heterogeneous catalysts can be precisely targeted for heating inside reactors. Site-selective heating can greatly lower the energy requirements of the process by supplying heat to reaction sites while reducing needless heat transfer elsewhere. In this study, a microscale model was used to help create guidelines for susceptors and catalysts to improve ethylene production. The oxidative dehydrogenation of ethane is investigated by utilizing several catalysts and potential catalyst/susceptor combinations, with heat provided by an EM susceptor. Having the susceptors and catalyst function separately results in higher gradients in both heat and mass transfer, which drives transport through the catalyst region, while still providing adequate heating for endothermic reactions. However, using a susceptive core with a catalyst covering produces the maximum ethylene concentration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Managing Zirconium Chemistry and Phase Compatibility in Combined Process Separations for Minor Actinide Partitioning

In response to the NEUP Program Supporting Fuel Cycle R&D Separations and Waste Forms call DEFOA- 0000799, this report describes the results of an R&D project focusing on streamlining separation processes for advanced fuel cycles. An example of such a process relevant to the U.S. DOE FCR&D program would be one combining the functions of the TRUEX process for partitioning of lanthanides and minor actinides from PUREX(UREX) raffinates with that of the TALSPEAK process for separating transplutonium actinides from fission product lanthanides. A fully-developed PUREX(UREX)/TRUEX/TALSPEAK suite would generate actinides as product(s) for reuse (or transmutation) and fission products as waste. As standalone, consecutive unit-operations, TRUEX and TALSPEAK employ different extractant solutions (solvating (CMPO, octyl(phenyl)-N,Ndiisobutylcarbamoylmethylphosphine oxide) vs. cation exchanging (HDEHP, di-2(ethyl)hexylphosphoric acid) extractants), and distinct aqueous phases (2-4 M HNO 3 vs. concentrated pH 3.5 carboxylic acid buffers containing actinide selective chelating agents). The separate processes may also operate with different phase transfer kinetic constraints. Experience teaches (and it has been demonstrated at the lab scale) that, with proper control, multiple process separation systems can operate successfully. However, it is also recognized that considerable economies of scale could be achieved if multiple operations could be merged into a single process based on a combined extractant solvent. The task of accountability of nuclear materials through the process(es) also becomes more robust with fewer steps, providing that the processes can be accurately modeled. Work is underway in the U.S. and Europe on developing several new options for combined processes (TRUSPEAK, ALSEP, SANEX, GANEX, ExAm are examples). There are unique challenges associated with the operation of such processes, some relating to organic phase chemistry, others arising from the variable composition of the aqueous medium. This project targets in particular two problematic issues in designing combined process systems: managing the chemistry of challenging aqueous species (like Zr 4+ ) and optimizing the composition and properties of combined extractant organic phases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Water vapor diffusion membrane development

An application of the water vapor diffusion technique is examined whereby the permeated water vapor is vented to space vacuum to alleviate on-board waste storage and provide supplemental cooling. The work reported herein deals primarily with the vapor diffusion-heat rejection (VD-HR) as it applies to the Space Shuttle. A stack configuration was selected, designed and fabricated. An asymmetric cellulose acetate membrane, used in reverse osmosis application was selected and a special spacer was designed to enhance mixing and promote mass transfer. A skid-mount unit was assembled from components used in the bench unit although no attempt was made to render it flight-suitable. The operating conditions of the VD-HR were examined and defined and a 60-day continuous test was carried out. The membranes performed very well throughout the test; no membrane rupture and no unusual flux decay was observed. In addition, a tentative design for a flight-suitable VD-HR unit was made.

Tan, M. K.↗

Ultra-fast Boriding for Improved Energy Efficiency and Reduced Emissions in Materials Processing Industries (Final Report)

High-temperature treatment processes (such as nitriding, carburizing, and boronizing) are well-established and used widely by numerous industrial sectors to achieve superior mechanical and tribological properties on all kinds of engineering components made out of ferrous materials. Unfortunately, these traditional processes are very slow and energy intensive, and they produce large amounts of CO 2 emissions and liquid/solid wastes to deal with during and after each process run. From economic and environmental points of views, it is highly desirable to develop and implement novel surface treatment technologies that are quick, cheap, clean, and energy efficient. The main objective of this project was to develop an industrial-scale ultra-fast boriding process that realizes all of these desirable attributes. The other objectives of the project were to demonstrate the superior performance, properties, and durability of borided surfaces under relevant test conditions and to transfer optimized technology to industry for large-scale practice. Major research activities included process design, modeling, product optimization, and scale-up. This project has achieved all of its stated objectives, and the industrial-scale boriding process has been successfully transferred to industry. Specifically, all of the original tasks have been completed, and the milestones have been met by scaling up from a small proof-of-concept system (which could only handle about 0.25 kg melt) to a commercial-scale boriding unit that can handle up to 4,000 kg melt. Mechanical and tribological testing of borided test samples and industrial parts has also been carried out, and their superior performance over a broad range of test conditions has been validated. With the large-scale, ultra-fast boriding process, we could achieve thick, hard, and uniform boride layers on all kinds of steel components, even after only 5 min of treatment time. We could also attain excellent uniformity in thickness over the entire exposed surfaces — even in the very sharp corners or interior sections of odd-shaped workpieces. Boriding of numerous nonferrous materials was also demonstrated, and thick boride layers (up to 300 µm in thickness) were achieved on their outer surfaces. With the use of a large-scale boriding unit at Argonne National Laboratory, our research team has successfully treated large numbers of industrial components in a batch-to-batch operation without creating any in-house gaseous emissions or producing solid and/or liquid wastes. With the use of this large unit, our team achieved surface hardness values of 15 to 45 GPa, depending on the type of metal or alloy being treated. The thick boride layers attained on steel components consisted of FeB, Fe 2 B, and Fe 3 B phases, and their hardness values ranged from 16 to 22 GPa. Layers consisting of Fe 2 B phase alone are also possible with this process, and in the case of nonferrous materials. Overall, because of the much superior property and performance improvements in treated products, much lower energy consumption, and nearly zero environmental waste and emissions, the demonstrated boriding technology may find broad applications in many cross-cutting industries. Mechanical wear, abrasion, erosion, corrosion, and scuffing are often life-limiting factors in mechanical systems that are used in manufacturing, transportation, aerospace, agricultural, earth-moving, and mining equipment; but the machine components treated by ultra-fast boriding can effectively prevent such degradations. In this project, the ultra-fast boriding was proven to be most ideal for the treatment of iron and many other ferrous alloys, like stainless steel. We have shown through our experimental studies that our method can also be used for the treatment of many nonferrous metals and alloys. In the case of superalloys and Ni 3 Al intermetallic materials, more than a 300-µm thick boride layer can be achieved with our boriding furnace within 15 to 30 min (which results in five times the hardness of the base materials). Pre-carburized steels and nonferrous alloys can also be treated by the new boriding technique. Overall, very thick (more than a quarter millimeter) and hard surface layers produced by ultra-fast boriding are expected to have a positive impact on the performance and durability of all types of machine components that are subject to corrosive, erosive, abrasive, and adhesive wear. Since the focus of our project was primarily on the large-scale boriding of ferrous materials, in this report, we will broadly cover the results from various ferrous materials that were used in our experiments. Another transformational feature of ultra-fast boriding is that it does not create any greenhouse gas emissions or solid and/or liquid wastes to deal with during or after the treatment; hence, it is an ultra-green technology (no need for expensive waste disposal and/or treatment facilities). It may eliminate the use of natural gas and other carbon-based fuels as the primary energy source in the heat treatment industry (which is the most common practice at present), thus, minimizing the CO 2 , NO x , CO, and SO x emissions that are generated in large quantities by current heat treatment practices. The main ingredient used during boriding is borax, which is a natural mineral. Our demonstrated and scaled-up technology can now be used in a wide range of manufacturing and transportation applications. It can deliver thick and uniform boride layers of more than 200 µm in steels, if needed, over the entire exposed surfaces — even in the very sharp corners or interior sections of workpieces (which are typical of gears, tools, pipes, and other components). Beneath the distinct boride layers is an equally-thick boron diffusion layer or zone, which is comparable to the diffusion zones achieved by carburizing and nitriding processes. In the cases of traditional boriding, nitriding, and/or carburizing methods, achieving such layer thickness and case depths would have taken several hours, and these surfaces would not have achieved the same levels of hardness and other desirable properties as they do with ultra-fast boriding. Some of the key stakeholders of ultra-fast boriding technology include companies that are active in heat-treatment, thermal-diffusion, and hard-coating processes; metal-forming, machining, and other manufacturing processes; and technologies related to transportation (including original equipment manufacturers for autos), mining and oil exploration, agricultural and heavy equipment. Bodycote Thermal Processing was the cost-sharing industrial partner and licensee in this project. They also provided test components and technical and commercial information pertaining to industrial components that are most suitable for ultra-fast boriding. Bodycote also coordinated some of the field tests and metallurgical examinations. Overall, ultra-fast boriding is a transformational technology that can complement, if not replace, many of the energy- and carbon-intensive surface treatment processes that are in use today, such as conventional boriding, carburizing, nitriding, carbo-nitriding, and physical and chemical vapor deposition. In our project, the developed technology was scaled-up and proven to be an ultra-green, ultra-efficient process that can drastically reduce costs, increase productivity, and improve the performance and reliability of machine components used in cross-cutting industrial applications.

Erdemir, Ali↗

Ab initio calculation of excess properties of La{sub 1−x}(Ln,An){sub x}PO{sub 4} solid solutions

We used ab initio computational approach to predict the excess enthalpy of mixing and the corresponding regular/subregular model parameters for La{sub 1−x}Ln{sub x}PO{sub 4} (Ln=Ce,…, Tb) and La{sub 1−x}An{sub x}PO{sub 4} (An=Pu, Am and Cm) monazite-type solid solutions. We found that the regular model interaction parameter W computed for La{sub 1−x}Ln{sub x}PO{sub 4} solid solutions matches the few existing experimental data. Within the lanthanide series W increases quadratically with the volume mismatch between LaPO{sub 4} and LnPO{sub 4} endmembers (ΔV=V{sub LaPO{sub 4}}−V{sub LnPO{sub 4}}), so that W(kJ/mol)=0.618(ΔV(cm{sup 3}/mol)){sup 2}. We demonstrate that this relationship also fits the interaction parameters computed for La{sub 1−x}An{sub x}PO{sub 4} solid solutions. This shows that lanthanides can be used as surrogates for investigation of the thermodynamic mixing properties of actinide-bearing solid solutions. - Highlights: • The excess enthalpies of mixing for monazite-type solid solutions are computed. • The excess enthalpies increase with the endmembers volume mismatch. • The relationship derived for lanthanides is transferable to La{sub 1−x}An{sub x}PO{sub 4} systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A simple primary amide for the selective recovery of gold from secondary resources

Waste electrical and electronic equipment (WEEE) such as mobile phones contains a plethora of metals of which gold is by far the most valuable. Herein a simple primary amide is described that achieves the selective separation of gold from a mixture of metals typically found in mobile phones by extraction into toluene from an aqueous HCl solution; unlike current processes, reverse phase transfer is achieved simply using water. Phase transfer occurs by dynamic assembly of protonated and neutral amides with [AuCl 4 ]– ions through hydrogen bonding in the organic phase, as shown by EXAFS, mass spectrometry measurements, and computational calculations, and supported by distribution coefficient analysis. In conclusion, the fundamental chemical understanding gained herein should be integral to the development of metal-recovery processes, in particular through the use of dynamic assembly processes to build complexity from simplicity.

36 MATERIALS SCIENCE↗

Performance Specification for Standardized Transportation, Aging, and Disposal Canister Systems (Rev.2)

This performance specification document addresses use of a standardized transportation, aging, and disposal (STAD) canister system in the spent nuclear fuel (SNF) waste management system. This document was developed to support STAD canister system studies and potential research, development, and demonstration activities. Requirements in this specification may evolve with time based on results from analyses, experiments, design studies, system evaluations and demonstrations, as well as other factors. A STAD canister system consists of a canister, together with a storage or aging overpack/module/vault, a shielded transfer cask (STC), a site transporter, a transportation overpack, and a transportation skid. Three sizes of circular cross section STAD canister variants are specified in this document. The small STAD canister capacity is four pressurized water reactor (PWR) or nine boiling water reactor (BWR) SNF assemblies. The medium STAD canister capacity is 12 PWR or 32 BWR SNF assemblies. The large STAD canister capacity is 21 PWR or 44 BWR SNF assemblies. Using standardized canisters for SNF facilitates the interface between storage at an independent spent fuel storage installation (ISFSI) or a DOEowned interim storage facility (ISF), transportation between facilities, and disposal at a repository. Multiple STAD canisters may be stored in a single storage overpack and/or a single transportation overpack. The US Nuclear Regulatory Commission (NRC) requirements currently used for storage and transportation are adopted for the STAD canister system. Approved approaches (guidance) in NRC storage and transportation documents are also adopted as requirements for the STAD canister system to facilitate obtaining NRC Certificates of Compliance (CoCs) for STAD canister systems. Performance specifications in this document are also informed by STAD canister disposability in various geologic media and consideration of ISF (and geologic repository) handling facility design, operations, and licensing requirements.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗