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At least 1,675 records · Page 93

Machine learning defect properties in Cd-based chalcogenides

Impurity energy levels in the band gap can have serious consequences for a semiconductor's performance as a photovoltaic absorber. Data-driven approaches can help accelerate the prediction of point defect properties in common semiconductors, and thus lead to the identification of potential deep lying impurity states. In this work, we use density functional theory (DFT) to compute defect formation energies and charge transition levels of hundreds of impurities in CdX chalcogenide compounds, where X = Te, Se or S. We apply machine learning techniques on the DFT data and develop on-demand predictive models for the formation energy and relevant transition levels of any impurity atom in any site. The trained ML models are general and accurate enough to predict the properties of any possible point defects in any Cd-based chalcogenide, as we prove by testing on a few selected defects in mixed chalcogen compounds CdTe 0.5 Se 0.5 and CdSe 0.5 S 0.5 . The ML framework used in this work can be extended to any class of semiconductors.

density functional theory↗

Magnetism of MnBi-Based Nanomaterials

Nanostructured MnBi ribbons doped with impurity elements including B, C, Fe, Hf, Sm and Tb were prepared using the arc melting and melt-spinning techniques. The melt-spun ribbons were annealed in vacuum furnace at 350 degrees C to obtain the intended hexagonal structure. The external impurity doping made a significant change in the magnetic properties of the nanostructured MnBi ribbons including a decrease in saturation magnetization (M-s) and anisotropy energy (K) and an increase in coercivity H-c. However, Hf and C co-doping showed the opposite effect with a small increase in both M-s and K. Interestingly, the anisotropy energy of the boron doped sample increased by about 15% irrespective of the small decrease in magnetization. A significant increase in H-c of MnBi ribbons was found due to Hf, Tb and Sm doping. H-c as high as 13 kOe was achieved in Hf-doped sample after the sample was aligned in a magnetic field. A thermal hysteresis was observed at the structural phase transition of MnBi, which shifts by about 5 K towards higher temperatures due to impurity doping. The observed magnetic properties of the impurity doped MnBi ribbons are explained as the consequences of the disorder and the competing ferromagnetic and antiferromagnetic interactions.

Kharel, P↗

Computational Study of a Cryopump Design for Fusion Exhaust Gas Purification Using Direct Simulation Monte Carlo

Cryopump-based direct internal recycling (DIR) of fusion fuel is an attractive prospect because it provides pumping of helium ash from a reactor along with separation of helium and other impurities from the fuel. Previous studies have demonstrated a continuously regenerating cryopump, referred to as the Snail pump, that separates helium ash from fusion fuel for reactor-relevant flow rates. Here, in this study, a conceptual cryopump was designed as a proof-of-principle study to target other impurities, besides helium ash, from the fusion exhaust that would complement the Snail pump. The impurity-removal cryopump consists of four sets of chevron fins, two sets operating at 80 K and the other two at 30 K. A computational study using direct simulation Monte Carlo (DSMC) was performed with a gas mixture of 96.5% D2, 2.0% He, and 0.5% each of CO2, N2, and CH4. In this configuration, 80 K chevron fin sets are capable of capturing CO2 and 30 K sets capable of capturing CO2, N2, and CH4. The computational study showed that the cryopump is capable of reducing the impurity content by more than two orders of magnitude from the flow.

Adhikari, Nirajan [Oak Ridge National Laboratory (↗

Preliminary Testing of a Continuous Cryopump for Primary Fusion Device Pumping and Direct Internal Recycling

Here, the concept of directly recirculating fusion machine exhaust gas, bypassing the tritium plant, to make fuel pellets was proposed in the 1990s and later termed direct internal recycling (DIR). In the DIR concept, the residual fusion fuel in the machine exhaust stream is separated from impurities locally and diverted directly to the fueling systems, bypassing isotopic separation and other processing equipment, and therefore significantly reducing the required size of the fuel processing plant, reducing plant inventory, and thus increasing the economic viability of fusion as an energy source. One concept for DIR consists of a series of cryogenic pumps to separate the impurities from the machine exhaust gas using different triple point temperatures and saturation curves of exhaust constituents. In this concept, the plasma exhaust is initially passed through an impurity trap operating at ~25–30 K to desublimate impurities such as hydrocarbons, argon, oxygen, and nitrogen. The resulting process stream will consist of DT fuel and helium. The process stream is then pumped by a continuous cryopump known as a “snail pump.” This pump is a steady-state continuous cryopump that desublimates all remaining exhaust gas constituents while allowing helium, a byproduct of the fusion reaction, to pass through. The helium is pumped to the tritium plant for processing while the desublimated material is continuously scraped off, heated up, and transported to the fueling system. This article will present the cryogenic DIR concept and outline the design and operation of the snail pump, along with results from preliminary testing. Tests to assess pumping and separation efficiency found that at D2 flows below 50.7 Pa ⋅ m3/s with 1% helium, the pump is capable of pumping and separating the gas with a resulting DIR fraction of >99%, with no helium entrained in the primary fuel exhaust stream. The main limitation is due to the thermal performance of the cryogenic circuits of the pump, which will be addressed in future testing.

Gebhart III, Trey E. [Oak Ridge National Laborator↗

Diagnostics for molybdenum and tungsten erosion and transport in NSTX-U

A comprehensive set of spectroscopic diagnostics is planned in the National Spherical Torus Experi- ment Upgrade to connect measurements of molybdenum and tungsten divertor sources to scrape-off layer (SOL) and core impurity transport, supporting the installation of high-Z plasma facing compo- nents which is scheduled to begin with a row of molybdenum tiles. Imaging with narrow-bandpass interference filters and high-resolution spectroscopy will be coupled to estimate divertor impurity influxes. Vacuum ultraviolet and extreme ultraviolet spectrometers will allow connecting high-Z sources to SOL transport and core impurity content. The high-Z diagnostics suite complements the existing measurements for low-Z impurities (carbon and lithium), critical for the characterization of sputtering of high-Z materials.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Optimization of laser-induced breakdown spectroscopy for liquid sodium analysis

Next-generation nuclear power reactors based on liquid sodium coolant are in development to improve efficiency and safety. Fast breeder reactors could potentially achieve considerably higher fuel burn-up while producing less nuclear waste compared with current commercial technology. Monitoring of impurities in these types of reactors is important in order to prevent blockage of the cooling system or hazardous reactions due to the high reactivity of sodium with water. In this work, laser-induced breakdown spectroscopy is performed on a liquid sodium sample using a custom-built immersion probe system. The probe provides direct line of sight to the sample vessel in argon atmosphere for laser delivery and signal collection. Signatures of sodium, and impurities such as potassium and oxygen have been obtained. The probe height and immersion have a strong influence on the signal level and stability. Argon flow rates of 2 to 5 liters per minute produce no substantial change in signal, suggesting a steady laminar flowing regime. A high signal-to-noise ratio for impurity elements confirms the suitability of this technique for reliable impurity detection and monitoring in the reactor environment.

Gardette, V. [University of Michigan, Ann Arbor, M↗

How nitrogen and oxygen shape SRF cavity performance

Nitrogen and oxygen-based surface treatments have revolutionized the performance of superconducting radiofrequency (SRF) cavities, enabling them to reach higher gradients and lower losses. However, the exact mechanisms by which these treatments improve cavity performance remain largely unknown. This work provides new insights into the role of nitrogen and oxygen in SRF cavity performance by using time-of-flight secondary ion mass spectrometry (TOF-SIMS) to precisely quantify the concentrations and depth profiles of these impurities within niobium cutouts. We correlate these impurity profiles with detailed cavity performance measurements, including surface resistance and quality factor, and compare our findings with predictions from BCS theory. The results demonstrate that while both nitrogen and oxygen enhance performance, ten times more oxygen is required to achieve the same reduction in BCS resistance as interstitial nitrogen. We present a potential model in which the observed variation arises from nitrogen's greater effectiveness in trapping hydrogen, thus reducing the formation of niobium hydrides and enhancing superconducting gap.

Hu, Hannah [Chicago U.]↗

Purification of Degraded Aqueous Piperazine by Ion Exchange and Carbon Treating

Amine purification by ion exchange and carbon treating has been performed for decades to maintain low solvent impurity levels in amines used in natural gas sweetening. The use of these purification methods to remove dissolved metal catalysts and other impurities from amines used in post-combustion carbon capture is less well known. This report presents batch experiments testing the equilibrium adsorption of impurities from degraded piperazine (PZ) onto activated carbon and various ion exchange resins. Compared to cationic exchange, anionic exchange was found to better remove catalytic Fe and UV active species, making it a better candidate for large-scale PZ purification. Carbon treating greatly outperforms anion exchange in the removal of UV active species, but the adsorbents’ difference is less pronounced for the removal of other impurities. Equilibrium adsorption was determined by the UV absorption of the PZ solution at 320 nm, and the results will show this may not be an accurate way to determine equilibrium. Further bench-scale experiments comparing ion exchange and carbon treating are necessary before advancing to larger-scale testing.

amine purification↗

Scrape-Off-Layer Flow Studies in Tokamaks (Final Report of LDRD Project 09-ERD-025)

A summary is given of the work carried out under the LDRD project 09-ERD-025 entitled Scrape-Off-Layer Flow Studies in Tokamaks. This project has lead to implementation of the new prototype Fourier Transform Spectrometer edge plasma flow diagnostic on the DIII-D National Fusion Facility at General Atomics, acquisition of carbon impurity concentration and flow data, and demonstration that the resulting data compare reasonably well with LLNL's edge plasma transport code UEDGE. Details of the work are contained in attached published papers, while the most recent results that are being written-up for publication are summarized in the report. Boundary plasma flows in tokamak fusion devices are key in determining the distribution of fuel and impurity ions, with tritium build-up in the walls an especially critical operational issue. The intrusion of impurity ions to the hot plasma core region can result in serious energy-loss owing to line radiation. However, flow diagnostic capability has been severely limited in fusion-relevant hot edge plasmas where Langmuir-type probes cannot withstand the high heat flux and traditional Doppler spectroscopy has limited resolution and signal strength. Thus, new edge plasma flow diagnostic capabilities need to be developed that can be used in existing and future devices such as ITER. The understanding of such flows requires simulation with 2-dimensional transport codes owing to the geometrical complexity of the edge region in contact with material surfaces and the large number of interaction physical processes including plasma flow along and across the magnetic field, and coupling between impurity and neutral species. The characteristics of edge plasma flows are substantially affected by cross-magnetic-field drifts (ExB/B 2 and BxVB/B 2 ), which are known to introduce substantial convergence difficulty for some cases. It is important that these difficulties be overcome so that drifts can be included in transport models, both for validation with existing data and for projection to future devices.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Zone Refining for Low Loss Plutonium Purification

In an effort to enhance plutonium purification capabilities at Los Alamos National Laboratory, further develop of the currently existing zone refining capabilities is needed to create a functional low loss processing option in support of programmatic and materials science research activities. Currently, the most effective process for converting impure plutonium dioxide (~96% pure) to high-purity plutonium metal (>99.9%), consists of the following steps: (1) reducing the dioxide to an impure Plutonium metal with calcium metal in molten calcium chloride, (2) casting the impure metal into an anode and (3) electrorefining the impure metal to produce high-purity plutonium metal. The final step in this method is only 83% efficient as compared to the >95% efficiency of the other processing steps. Other more efficient processing methods are desirable to enhance current purification activities, thereby, reducing waste generation and conserving precious materials in need of purification. Although zone refining has been used extensively to purify many lanthanides and actinides, its usefulness in purifying plutonium has yet to be fully realized.

36 MATERIALS SCIENCE↗

Functional Bounding Content Envelope for Gamma and Neutron Emitting Isotopes in the Model 9977 Packaging

The contents approved for shipment in a Type B radioactive material transportation package have historically been descriptions of discrete items, or groupings of well-defined similar items, in the package safety basis documentation. The need for a comprehensive functional content envelope of both gamma and neutron emitting nuclides compliant with regulatory limits has become necessary as the DOE complex requires shipments of unique mixtures of radionuclides and impurities. Recent publications have presented a calculational model and a corresponding content envelope intended to be compliant with federal regulatory external radiation limits as well as design decay heat limits based on the Model 9977 Packaging. The methodology used to develop this content envelope consisted of determining the external radiation dose rates based on one gram of a given isotope combined, in the case of actinides, with various levels of light element impurities and determining the allowable mass to the regulatory limits based on these dose rates. The method of ratioing from these calculations to the masses that meet the regulatory limits fails in the case of some combinations of actinides and light element impurities because of the effect of subcritical multiplication, resulting in non-conservative and non-compliant dose rates in some cases. This is particularly true for many actinides combined with beryllium, boron, fluorine, lithium, and sodium. In this study, the source was modeled as a sphere with the appropriate dimensions based on the actinide or gamma source density and placed at the bottom of the containment vessel for maximum conservatism. The results presented in this report rectify the above-noted deficiencies by adjusting the previously determined mass limits so that the resulting dose rates are compliant with regulatory limits. Some amount of iteration was required in some instances to adjust the masses for dose compliance. In some instances the masses were increased since they were too conservative. In addition, the method of ratioing the masses when applied to several gamma emitting isotopes also resulted in either non-conservative or overly conservative data. The mass imits presented here are for bare sources and are complaint with the design decay heat limit of 19W. The masses are based on package surface dose rates (the limiting dose rate) that fall in the range 185-195 mrem/h, thus giving an additional margin of between 7.5% and 2.5% to the regulatory limit of 200 mrem/h. This report presents a revised set of mass limits (i.e., content envelope) for several neutron emitting actinides with varying levels of light element impurities compliant with both external radiation and design decay heat limits. In addition, revised limits for gamma sources are also presented. The neutron emitter mass limits are in Tables 1 through 9 and the gamma emitter mass limits are in Table 10. The revised content envelope covering a wide range of materials present in the DOE complex, was developed for the Model 9977 Packaging, providing conservative limits for other commonly-used Type B Packagings such as the Models 9975 and 9978. It should be noted that for the Model 9977 package, shipment is also possible with three shielded containers – lead or tungsten for gamma sources and polyethylene for neutron emitters. The design decay heat limits for these are as follows: 19W for tungsten, 6W for lead and 3W for polyethylene. The limits presented in this report would need to be checked against the lower decay heat limits for the lead and polyethylene and adjusted as required for compliance. Criticality safety is not factored into these limits and should be evaluated on a case by case basis.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Carrier Transport and Related Effects in Detectors of the Cryogenic Dark Matter Search

The Cryogenic Dark Matter Search (CDMS) is searching for weakly-interacting massive particles (WIMPS), which could explain the dark matter problem in cosmology and particle physics. By simultaneously measuring signals from deposited charge and the energy in nonequilibrium phonons created by particle interactions in intrinsic germanium crystals at a temperature of 40 mK, a signature response for each event is produced. This response, combined with phonon pulse-shape information, allows CDMS to actively discriminate candidate WIMP interactions with nuclei from electromagnetic radioactive background which interacts with electrons. The challenges associated with these techniques are unique. Carrier scattering is dominated by the spontaneous emission of Luke-Neganov phonons due to zeropoint fluctuations of the lattice ions. Drift fields are maintained at only a few V/cm, else these emitted phonons would dominate the phonons of the original interaction. The dominant systematic issues with CDMS detectors are due to the effects of space charge accumulation. It has been an open question how space charge accrues, and by which of several potential recombination and ionization processes. In this work, we have simulated the transport of electrons and holes in germanium under CDMS conditions. We have implemented both a traditional Monte Carlo technique based on carrier energy, followed later by a novel Monte Carlo algorithm with scattering rates defined and sampled by vector momentum. This vector-based method provides for a full anisotropic simulation of carrier transport including free-fight acceleration with an anisotropic mass, and anisotropic scattering rates. With knowledge of steady state carrier dynamics as a function of applied field, the results of our Monte Carlo simulations allow us to make a wide variety of predictions for energy dependent processes for both electrons and holes. Such processes include carrier capture by charged impurities, neutral impurities, static dipoles, and capture forming "anion" (D - /A + ) states. We also generate predictions for impact ionization of shallow impurities and of impact "neutralization" of D - /A + states. We use measurements of carrier capture performed on CDMS detectors to validate a plausible model for electron and hole capture due to neutral shallow impurities and their charged D - /A + states. This model, along with carrier drift and diffusion parameters from Monte Carlo simulation, can be used as the foundation for simulations of space charge evolution in CDMS detectors, simultaneously solving continuity equations with Poisson's equation.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Insights to Superconducting Radio-Frequency Cavity Processing from First Principles Calculations and Spectroscopic Techniques

Insights to the fundamental processes that occur during the manufacturing of niobium superconducting radio-frequency (SRF) cavities are provided via analyses of density functional theory calculations and Raman, infrared, and nuclear magnetic resonance (NMR) spectra. I show that during electropolishing fluorine is bound and released by the reaction of the acid components in the solution: HF + H 2 SO 4 <-> HFSO 3 + H 2 O. This result implies that new recipes can possibly be developed on the principle of controlled release of fluorine by a chemical reaction. I also show that NMR or Raman spectroscopy can be used to monitor the free fluorine when polishing with the standard electropolishing recipe. Density functional theory was applied to calculate the properties of common processing impurities – hydrogen, oxygen, nitrogen, and carbon – in the niobium. These impurities lower the superconducting transition temperature of niobium, and hydride precipitates are at best weakly superconducting. I modeled several of the niobium hydride phases relevant to SRF cavities, and explain the phase changes in the niobium hydrogen system based on the charge transfer between niobium and hydrogen and the strain field inside of the niobium. I also present evidence for a niobium lattice vacancy serving as a nucleation center for hydride phase formation. In considering the other chemical impurities in niobium, I show that the absorption of oxygen into a niobium lattice vacancy is preferred over the absorption of hydrogen, which indicates that oxygen can block these phase nucleation centers. I also show that dissolved oxygen atoms can trap dissolved hydrogen atoms to prevent niobium hydride phase formation. Nitrogen and carbon were studied in less depth, but behaved similarly to oxygen. Based on these results and a literature survey, I propose a mechanism for the success of the low-temperature anneal applied to niobium SRF cavities. Finally, I present the beginning of a model to describe magnetic impurities in niobium SRF cavities, which can cause a loss of local superconductivity. I calculated magnetic configurations of niobium hydrides and oxides, and show that stoichiometric hydride and oxide structures are nonmagnetic, but defective oxide structures retain local magnetic moments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

XPS and IR Characterization of Ultra-High Molecular Weight Polyethylene

We used x-ray photoelectron spectroscopy (XPS) and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) to characterize samples of 3-mil thick rolled sheets of ultrahigh molecular weight polyethylene (UHMWPE). The purpose of the XPS work was to determine the surface composition of the UHMWPE and determine if any impurities (particularly halogens) were consistently present of the surface of the sheet. XPS results indicate as-received UHMWPE is reasonably clean, but somewhat inhomogeneous. Some as-received samples contain small amounts of silicon, chlorine, and sodium, while others only contain carbon and oxygen (as expected for ambient exposed plastic). Both ethanol wiping and ethanol sonication effectively remove the Si, Cl, and Na impurities. Additionally, these impurities are not detected by XPS after the top 20nm of material is ablated from as-received sample surfaces. These results suggest the impurities are surface contaminants arising from sample handling and/or ambient exposure. The purpose of the IR work was to collect baseline spectra of the UHMWPE for match factor comparison against known polyethylene materials. The IR spectra for all UHMWPE samples are similar to one another and to known polyethylene materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of Gas Membrane Ultra-High Purification of Small Quantities of Mono-Isotopic Silane

A small quantity of high-value, crude, mono-isotopic silane is a prospective gas for a small-scale, high-recovery, ultra-high membrane purification process. This is an unusual application of gas membrane separation for which we provide a comprehensive analysis of a simple purification model. The goal is to develop direct analytic expressions for estimating the feasibility and efficiency of the method, and guide process design; this is only possible for binary mixtures of silane in the dilute limit which is a somewhat realistic case. Among the common impurities in crude silane, methane poses a special membrane separation challenge since it is chemically similar to silane. Other potential problematic surprises are: ethylene, diborane and ethane (in this order). Nevertheless, we demonstrate, theoretically, that a carefully designed membrane system may be able to purify mono-isotopic, crude silane to electronics-grade level in a reasonable amount of time and expenses. We advocate a combination of membrane materials that preferentially reject heavy impurities based on mobility selectivity, and light impurities based on solubility selectivity. We provide estimates for the purification of significant contaminants of interest. To improve the separation selectivity, it is advantageous to use a permeate chamber under vacuum, however this also requires greater control of in-leakage of impurities in the system. In this study, we suggest cellulose acetate and polydimethylsiloxane as examples of membrane materials on the basis of limited permeability data found in the open literature. We provide estimates on the membrane area needed and priming volume of the cell enclosure for fabrication purposes when using the suggested membrane materials. These estimates are largely theoretical in view of the absence of reliable experimental data for the permeability of silane. Last but not least, future extension of this work to the non-dilute limit may apply to the recovery of silane from rejected streams of natural silicon semi-conductor processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solvent hold tank sample results for MCU-16-1488-1493 (December 2016), MCU-17-86-88 (January 2017), and MCU-17-119-121 (February 2017): Quarterly Report

A trend summary of three Solvent Hold Tank (SHT) monthly samples; MCU-16-1488-1493 (December 2016), MCU-17-86-88 (January 2017), and MCU-17-119-121 (February 2017) are reported. Analyses indicate that the modifier (CS-7SB) and the extractant (MaxCalix) concentrations are at their nominal recommended levels (169,000 mg/L and 46,300 mg/L respectively). The suppressor (TiDG) level has decreased to a steady state level of 673 mg/L well above the minimum recommended level (479 mg/L). This analysis confirms the Isopar™ addition to the solvent in January 18, 2017. This analysis also indicates the solvent did not require further additions. Based on the current monthly sample, the levels of TiDG, Isopar™L, MaxCalix, and modifier are sufficient for continuing operation but are expected to decrease with time. Periodic characterization and trimming additions to the solvent are recommended. No impurities above the 1000 ppm level were found in this solvent by the Semi-Volatile Organic Analysis (SVOA). No impurities were observed in the Hydrogen Nuclear Magnetic Resonance (HNMR). Another impurity observed in the samples was mercury. Up to 38 ± 8 micrograms of mercury per mL of solvent was detected in these samples (the average of the CV-AA and XRF methods). The higher mercury concentration in the solvent (as determined in the last three monthly samples) is possibly due to the higher mercury concentration in Salt Batches 8 and 9 (Tank 49H) or mixing of previously undisturbed areas of high mercury concentration in Tank 49H. The gamma level (0.21E5 dpm/mL) measured in the February SHT sample was one order of magnitude lower than the gamma levels observed in the December and January SHT samples. The February gamma level is consistent with the solvent being idle (since January 10, 2017). The gamma levels observed in the December and January SHT samples were consistent with previous monthly measurements where the process operated normally. The laboratory will continue to monitor the quality of the solvent in particular for any new impurities or degradation of the solvent components.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High Quality, Low Cost Bulk Gallium Nitride Substrates Grown by the Electrochemical Solution Growth Method

The objective of this project was to develop the Electrochemical Solution Growth (ESG) method conceived / patented at Sandia National Laboratory into a commercially viable bulk gallium nitride (GaN) growth process that can be scaled to low cost, high quality, and large area GaN wafer substrate manufacturing. The goal was to advance the ESG growth technology by demonstrating rotating seed growth at the lab scale and then transitioning process to prototype commercial system, while validating the GaN material and electronic / optical device quality. The desired outcome of the project is a prototype commercial process for US-based manufacturing of high quality, large area, and lower cost GaN substrates that can drive widespread deployment of energy efficient GaN-based power electronic and optical devices. In year 1 of the project (Sept 2012 – Dec 2013) the overall objective was to demonstrate crystalline GaN growth > 100um on a GaN seed crystal. The development plan included tasks to demonstrate and implement a method for purifying reagent grade salts, develop the reactor 1 process for rotating seed Electrochemical Solution Growth (ESG) of GaN, grow and characterize ESG GaN films, develop a fluid flow and reaction chemistry model for GaN film growth, and design / build an improved growth reactor capable of scaling to 50mm seed diameter. The first year’s project objectives were met in some task areas including salt purification, film characterization, modeling, and reactor 2 design / fabrication. However, the key project objective of the growth of a crystalline GaN film on the seed template was not achieved. Amorphous film growth on the order of a few tenths of a micron has been detected with a film composition including Ga and N, plus several other impurities originating from the process solution and hardware. The presence of these impurities, particularly the oxygen, has inhibited the demonstration of crystalline GaN film growth on the seed template. However, the presence of both Ga and N at the growth surface indicates that the reactor hardware physics is all functioning properly; achieving film growth is a matter of controlling the chemistry at the interface. The impurities originating from the hardware are expected to be straightforward to eliminate. Activities were defined for an extension of budget period 1 to eliminate the undesired impurities originating from the reactor hardware and interfering with crystalline GaN film growth. The budget period 1 extension was negotiated during the 1st half of 2014. The budget period 1 extension spanned approximately from August 2014 to August 2015. The project objective for this extension period was to demonstrate at least 0.5um crystalline GaN film on a GaN seed in the lab scale reactor. The focus of the budget 1 extension period from August 2014 to August 2015 was to eliminate oxygen contamination interference with GaN film growth. The team procured the highest purity lowest oxygen salt for testing. Low oxygen crucible materials such as silicon carbide were installed and evaluated in the laboratory reactor. Growth experiments were performed with high purity salt, high purity hardware, and optimized oxide removal from the seed surface. Experiments were characterized with methods including UV inspection, profilometry, x-ray diffraction (XRD) to determine crystalline structure, optical and scanning electron microscopy, photoluminescence, x-ray photon spectroscopy (XPS), transmission electron microscopy (TEM), and secondary ion mass spectroscopy (SIMS). Despite successfully integrating the low oxygen materials in the laboratory reactor, the goal of depositing 0.5um of crystalline GaN on the MOCVD GaN seed was not met. Very thin (ca. 10nm) cubic phase GaN deposition was observed on the hexagonal MOCVD GaN seeds. But there was a competing etching reaction which was also observed and thought to be related to the presence of metallic lithium, a byproduct of the LiCl-KCl salt used as the process medium. The etching reaction could potentially be addressed by alternate salts not containing lithium, but would necessitate starting all over on the reactor and process design. Further, controlling the reaction of Ga and N in the bulk salt to favor deposition on the seed has proved to be very difficult and unlikely to be solved within the scope of this project in a manner consistent with the original objective for wafer or crystal scale thickness for GaN deposition on a GaN seed. Upon completion of the budget 1 extension period in August 2015 the project partners and DOE agreed to stop work on the project.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Solvent hold tank sample results for MCU-17-150-152 (July 2017) and MCU-17-153-155 (August 2017): Quarterly report

A trend summary that includes the last two Solvent Hold Tank (SHT) monthly samples is shown; MCU- 17-150-152 (July SHT) and MCU-17-153-155 (August SHT). Since the last SHT sample sent for analysis was the August sample the chemical state of the solvent is best approximated by the chemical analysis of the August SHT sample (MCU-17-153-155). This report mainly focused on the chemical analysis of the August SHT sample. The analysis data from the July SHT sample are presented in the “trend” plots of this report. Analysis of the August SHT sample (MCU-17-153-155) indicated that the modifier (CS-7SB) was 2% below but the extractant (MaxCalix) concentration was at its nominal recommended level (169,000 mg/L and 46,400 mg/L respectively). The suppressor (TiDG) level has decreased since the last measurement taken while the Modular Caustic-Side Solvent Extraction unit (MCU) was operating in January 2017, but has remained steady in the range of 666 (observed in April) to 715 mg/L (observed in the August 2017 sample) since February 2017, well above the minimum recommended level (479 mg/L), but below the nominal level. The “flat” trends observed in the TiDG, MaxCalix, modifier, and Gamma measurement are consistent with the solvent being idle since January 10, 2017. A strong correlation between density and modifier concentration in the solvent continues to be observed in the SHT samples. This analysis confirms the Isopar™L addition to the solvent in January 2017. This analysis also indicates the solvent did not require further additions. Based on the current monthly sample, the levels of TiDG, Isopar™L, MaxCalix, and modifier are sufficient for continuing operation but are expected to decrease with time if the Modular Caustic-Side Solvent Extraction Unit (MCU) returns to processing radioactive liquid waste. Otherwise, the levels of these components will remain steady. A future Isopar™L trimming addition to the solvent is recommended when MCU resumes processing waste. Two unknown impurities related to the modifier (but not sec-butyl phenol: a modifier degradation product observed before) at the 290 and 110 mg/L levels were observed in the August SHT sample by the Gas - Chromatography-Mass Spectrometry (GC-MS) method. They were observed in a second GC-MS re-run with a new column. Their identification can’t be ascertained at this time. No impurities were observed in the Hydrogen Nuclear Magnetic Resonance (HNMR). Another impurity observed in the samples was mercury. Based on the August SHT sample, up to 23 ± 5 micrograms of mercury per mL of solvent was detected (the average of the Cold Vapor-Atomic Adsorption [CV-AA] and X-Ray Fluorescence [XRF] methods). The higher mercury concentration in the solvent (as determined in the last three-monthly samples) is possibly due to either a higher mercury concentration in Salt Batches 8 and 9 (Tank 49H) . The gamma level (~ 2.0E4 dpm/mL) measured in the August SHT samples was one order of magnitude lower than the gamma levels observed in the December 2016 and January 2017 SHT samples. A similar level was observed in the July SHT sample (MCU-SHT-150-152). The gamma level has remained consistently steady since January 10, 2017 when MCU stopped processing radioactive liquid waste. The laboratory will continue to monitor the quality of the solvent in particularly for any new impurities or degradation of the solvent components.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗