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At least 73 records · Page 4

Comparison of chromium poisoning between lanthanum strontium manganite and lanthanum strontium ferrite composite cathodes in solid oxide fuel cells

Degradation mechanisms of chromium poisoning have been extensively investigated for last two decades on various cathode materials for solid oxide fuel cells. While most researchers used half-cell experiments to investigate the effects of chromium impurities, this paper compares the degradation phenomena of LSM-YSZ and LSF-GDC cathodes in full cells under different operating conditions, namely polarized current density and humidity over the cathode. Under cathodic load, performance degradation of LSF-GDC cathode is significantly less than that of LSM-YSZ cathode. Most interestingly, under humidified air condition, LSF-based cell hardly experiences performance degradation while LSM-based cell shows a catastrophic degradation. Cr deposition in LSM-based cells occurs mainly near the electrolyte under both dry and humidified air conditions. In contrast, Cr deposition in LSF-based cell concentrates at the cathode surface under dry air condition, but concentrates both at cathode surface and near electrolyte under humidified air condition. Microstructure analysis reveals Mn-associated Cr deposits in LSM-based cathode, and Sr- and Fe-associated Cr deposits in LSF-based cathode. With the help of distribution of relaxation time analysis, the different electrochemical behaviors of LSM- and LSF-based cells are carefully interpreted. The effects of electrochemical deposition, Sr surface segregation, and humidity on LSM- and LSF-based cathodes are discussed.

25 ENERGY STORAGE↗

Acidity of surface-infiltrated binary oxides as a sensitive descriptor of oxygen exchange kinetics in mixed conducting oxides

Improving the kinetics of O 2 reduction on oxide surfaces is critical in many energy and fuel conversion technologies. Here we show that the acidity scale for binary oxides is a powerful descriptor for tuning and predicting oxygen surface exchange kinetics on mixed conducting oxides. By infiltrating a selection of binary oxides from strongly basic (Li 2 O) to strongly acidic (SiO 2 ) onto the surface of Pr 0.1 Ce 0.9 O 2-δ samples, it was possible to vary the chemical surface exchange coefficient k chem by 6 orders of magnitude, with basic oxides such as Li 2 O increasing k chem by nearly 1,000 times, with surface concentrations as low as 50 ppm impacting k chem . Strikingly, although the pre-exponential of k chem scales linearly with the acidity of the infiltrated binary oxide, there is nearly no change in the activation energy. Here, the origin of these dramatic changes is proposed to arise from the systematic increase in electron concentration at the Pr 0.1 Ce 0.9 O 2-δ surface with the decreasing acidity of the infiltrated binary oxide.

30 DIRECT ENERGY CONVERSION↗

Single-step conversion of ethanol into n-butene-rich olefins over metal catalysts supported on ZrO 2 -SiO 2 mixed oxides

With airlines committed to drastically reduce their carbon footprint by 2050, producing jet fuel from renewable ethanol is of particular interest. Here we reported on an Ag/ZrO 2 /SBA-16 catalyst that is very effective for directly converting ethanol into to n-butene-rich olefins jet fuel precursors (i.e., 88% at full conversion). Here, we report on a Cu/ZrO 2 /SBA-16 catalyst that presents remarkable olefins selectivity (i.e., 89% at 96% conversion) and enhanced stability as compared to Ag/ZrO2/SBA-16 catalyst. Under severe operating conditions a conversion loss < 10% was observed with the Cu/ZrO 2 /SBA-16 catalyst as compared to a 50% loss of conversion with the Ag/ZrO 2 /SBA-16 catalyst. Combined experimental and computational tools revealed that replacing Ag with Cu shifts the reaction pathway of crotonaldehyde hydrogenation from 1,3-butadiene (i.e., coke precursor) production to butyraldehyde formation. Experiments conducted with 4%Cu/4%ZrO 2 supported on SBA-16, dealuminated zeolite Beta, and aluminum silicate revealed the performance and stability advantage of the SBA-16-supported catalyst.

09 BIOMASS FUELS↗

Operation of internal combustion engine with improved fuel efficiency

A process of operating a spark-ignited internal combustion engine (SI-ICE) with improved fuel efficiency and reduced emissions including under steady state and under lean-operating conditions at high overall air to fuel (AFR) ratios. A first supply of high octane hydrocarbon fuel, such as gasoline or natural gas, and a first supply of oxidant are fed to a fuel reformer to produce a gaseous reformate with a reforming efficiency of greater than 75 percent relative to equilibrium. The gaseous reformate is mixed with a second supply of oxidant, after which the resulting reformate blended oxidant is fed with a second supply of high octane hydrocarbon fuel to the SI-ICE for combustion. Steady state fuel efficiency is improved by more than 3 percent, when the reformate comprises from greater than about 1 to less than about 18 percent of the total volume of reformate blended oxidant fed to the engine.

33 ADVANCED PROPULSION SYSTEMS↗

Water vapor oxidation of SiC layer in surrogate TRISO fuel particles

Under accidental conditions for high temperature gas-cooled reactors (HTGR), the SiC layer in tri-structural-isotropic (TRISO) fuel particles can be exposed to water vapor. In this study, oxidation behaviors of surrogate TRISO fuel particles were investigated in a He-20 vol% water vapor mixed atmosphere at temperatures up to 1600 °C. The growth of the crystalline oxide passivation layer with cracks and pores followed a parabolic law with time, where the maximum was 2.3 μm at 1600 °C. The oxide layer and the SiC surface under the oxide became flattened with increasing temperature, as a function of the silica viscosity and the diffusion path of water vapor. Volatilization of the oxide layer was analyzed using a mechanistic model that an inert gas in oxidizing atmospheres could influence the magnitude of volatilization. The fracture load and strength of the oxidized and thinned SiC layer were numerically estimated to decrease from 2.27 to 1.69 N and from 317 to 299 MPa, respectively, with the SiC thickness decrease from 35 to 32 μm. This prediction indicates that the oxidized SiC layer should retain fission products. Additionally, the mechanical integrity of each layer in the TRISO fuel particle after oxidation was evaluated. The results in this work provide important data for the safety analysis of accidental scenarios in HTGRs.

36 MATERIALS SCIENCE↗

U Metal Oxidation with Steam (U)

The Savannah Rive National Laboratory 9SRNL) is evaluating a method to produce uranium oxide (UO 2 ) from uranium metal using steam. The typical methods for making UO 2 yield powders with particle-size ranges of 1 to 50 micron. The goal of the steam oxidation is to produce a depleted uranium (DU) product with a larger particle size that can be used as a surrogate for testing physical and mechanical process techniques to refine uranium and/or plutonium bearing residues. Several studies in the literature indicated that reactions between uranium metal and steam will yield UO 2 as fine powders in the 160 to 500 °C range, but granular materials form above 500°C. Above 880 °C, a hard compact scale forms on the U metal. Furthermore, sintering of UO 2 occurs at about 1300 °C, but it has been stated that the presence of steam enhances the sintering characteristics of UO 2 . Initial studies into the oxidation of DU metal in an atmosphere of argon and steam have been completed. Oxidation of depleted uranium metal in Ar/steam at 600, 710, 700, and 830 °C yielded at UO 2 product with little or no impurity at each temperature. Although not enough sample was available to perform sieve analysis for particle size distribution, SEM images reveal that a significant volume fraction of the products at 710, 770, and 830 °C exceeds 100 microns. The material produced at 600 °C was too fine for programmatic needs. Questions associated with the UO 2 include morphology of product, mechanical strength of the particles, and performance in milling operations. The size of the samples produced in these tests did not allow for quantitative assessment of particle size of mechanical strength. A qualitative assessment of the particles formed at 710, 770, and 830 °C was that the samples produced at 710 and 770 °C were friable, and the sample produced 830 °C had more mechanical strength. Sintering of the samples in Ar/steam at 970 °C appeared to increase the strength of the particles without changing their general particle size characteristics. Due to the small sample sizes, the increase in strength could not be quantified. If the sintering at 970 °C is inadequate, higher sintering temperatures in Ar/steam can be evaluated. Future work will increase scale of the steam oxidation conditions which yield the most-favorable particle-size distributions with sufficient mechanical strength for programming usage. Further consideration will be given to oxidation temperature, steam addition to the reaction vessel, U metal pretreatment, and sintering conditions after oxidation. The UO 2 production could involve a two-step process where particles are formed in steam at lower temperatures (700-850 °C) and then sintered in Ar/steam at elevated temperatures (950-1200 °C). Larger samples (50-100 g each) will provide sufficient UO 2 product for sieve analysis and assessment of mechanical strength relatives to subsequent milling operations.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Characteristics of Uranium-Plutonium Mixed Oxide Nondestructive Assay Standards

A set of six well-characterized, homogeneous, mixed HEU-WGPu oxide standards has been manufactured for and are proposed for qualification as NDA working reference standards with SAFE-NMCA. These standards, if approved, will provide the basis for qualifying the FRAM isotopic systems for use in accountability measurements of 235U in the presence of Pu for unknown mixed U-Pu items by nondestructive assay. The U to Pu elemental mass ratios of the six analytical standards are nominally in the proportions 0.1, 0.25, 1.0, 2.5, 10, and 20; these values were chosen to span the U/Pu mass ratios of inventory items that ultimately will be measured by nondestructive assay and which currently reside in long term storage. The measured characteristics, including plutonium and uranium elemental masses and isotopic distribution, of each standard and relevant source documentation are reported here.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Quantifying the Relationship Between Microstructure and Performance in Gadolinium-Doped Ceria Infiltrated Ni/YSZ Symmetric Cells

Infiltration of mixed ionic/electronic conducting (MIEC) nanocatalysts into the anodes of solid oxide fuel cells (SOFCs) allow the hydrogen oxidation reaction (HOR) to occur at double-phase boundaries (DPBs), rather than being confined only to the triple phase boundaries (TPBs). In this research, we use a combination of cross-sectional scanning electron microscopy (SEM), three-dimensional (3-D) reconstruction, and electrochemical methods to characterize both baseline and gadolinium-doped ceria (GDC)-infiltrated symmetric cells, with the goal of establishing a comparison between the density of electrochemically active sites in uninfiltrated and GDC-infiltrated cells. Here, electrochemical impedance spectroscopy (EIS) and distribution of relaxation times (DRT) analysis showed GDC infiltration decreased the overall polarization of the anode by a factor of 8.78 X, and decreased the resistance associated with the reactions at the TPBs/DPBs by a factor of over 21 X. By quantifying expected GDC deposition morphology in the Ni/YSZ anode it is estimated that reactions occur in the baseline cell up to 84 nm from the active TPB lines.

36 MATERIALS SCIENCE↗

Quality Control Methods for Measurement of UCO Kernel Composition and SiC Microstructure

Quality control (QC) is critically important to tristructural-isotropic (TRISO) particle fuels owing to the complexity of and reliance on the fuel form to contain fission products during irradiation. Characterization methods for particle fuel QC have decades of history and have continued to develop as new insights into fuel performance inform revised fuel specifications and as advances in underlying technologies expand the possibilities of what may be characterized. Two relatively new methods for characterization of TRISO fuels have been published in open literature: optical microscopy image analysis for mixed uranium carbide/uranium oxide (UCO) kernel composition analysis and automated grain boundary detection in backscattered electron (BSE) images of the silicon carbide (SiC) layer in TRISO particles for grain size characterization. Suggestions and guidelines for the application of these methods to TRISO fuel qualification are provided in this report.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Numerical and boundary condition effects on the prediction of detonation engine behavior using detailed numerical simulations

High-fidelity numerical simulations of an experimental rotating detonation engine with discrete fuel/air injection were conducted. A series of configurations with different feed-plenum pressures but with constant equivalence ratio were studied. Detailed chemical kinetics for the hydrogen/air system is used. A resolution study for the full rotating detonation engine (RDE) system simulation is also conducted. Two kinds of boundary conditions, a total pressure boundary and a constant mass flow rate boundary, are used to assess the effects of the inlet boundary. As mass flow rate is increased, the total pressure boundary causes more error in the axial pressure distribution while the constant mass flow rate gives a better solution for all cases ran. The simulations confirm experimental findings, and reproduce qualitative as well as some of the quantitative trends. These results demonstrate that a) fuel-air mixing is highly non-uniform within the detonation chamber, leading to variations in local equivalence ratio, b) the fuel and oxidizer injectors experience significant backflow as the detonation wave passes over, but recover at different rates which further augments the inefficiencies in mixing, and c) parasitic combustion in the mixing region makes the detonation wave weak by extending the reaction zone across the wave.

33 ADVANCED PROPULSION SYSTEMS↗

Final CRADA Report: Accelerated Burn-up Accumulation Test of Clean Core Thorium Energy Designated ANEEL Fuel

Clean Core Thorium Energy (CCTE), LLC, located in Oak Brook, Illinois, is committed to the development of alternative nuclear fuels. CCTE is focused on leveraging the inherent benefits of thorium to create a novel nuclear fuel solution for our worlds growing power demand. Unlike some other fuel cycles proposing to use thorium in advanced reactors, CCTE is focused on deploying solid fuel designs (ceramic pellets in metallic cladding) in existing pressurized heavy-water reactors (PHWRs) and Canada deuterium uranium (CANDU) reactors. CCTE’s fuel design, referred to as Advanced Nuclear Energy for Enriched Life (ANEEL), uses mixed thorium-uranium oxide ((Th,U)O2) to enhance reactor operational strategies while producing significantly low attractiveness material in terms of nuclear proliferation. The overall project objective is to investigate the performance of high burnup ANEEL fuel via an irradiation experiment to be performed in the Advanced Test Reactor (ATR) at the Idaho National Laboratory (INL). The scope of work for this CRADA was specifically aimed at performing conceptual design and analysis to support development of an irradiation test rig, development of a fuel fabrication process for the experiment pellets, fabrication and qualification of the pellets, and shipment of the pellets to INL so they can be used to construct experiment rodlets.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The effects of mixture preburning on detonation wave propagation

Pressure gain combustion in the form of continuous detonations can provide a significant increase in the efficiency of a variety of propulsion and energy conversion devices. In this regard, rotating detonation engines (RDEs) that utilize an azimuthally-moving detonation wave in annular systems are increasingly seen as a viable approach to realizing pressure gain combustion. However, practical RDEs that employ non- premixed fuel and oxidizer injection need to minimize losses through a number of mechanisms, including turbulence-induced shock-front variations, incomplete fuel-air mixing, and premature deflagration. In this study, a canonical stratified detonation configuration is used to understand the impact of preburning on detonation efficiency. It was found that heat release ahead of the detonation wave leads to weaker shock fronts, delayed combustion of partially-oxidized fuel-air mixture, and non-compact heat release. Furthermore, large variations in wave speeds were observed, which is consistent with wave behavior in full-scale RDEs. Peak pressures in the compression region or near triple points were considerably lower than the theoretically-predicted values for ideal detonations. Analysis of the detonation structure indicates that this deflagration process is parasitic in nature, reducing the detonation efficiency but also leading to heat release far behind the wave that cannot directly strengthen the shock wave. As a result, this parasitic combustion leads to commensal combustion (heat release far downstream of the wave), indicating that it is the root cause of combustion efficiency losses.

42 ENGINEERING↗

Understanding the ignition process and flame structure of conventional and oxygenated fuels under engine relevant conditions – An optical study

Renewably generated synthetic fuels such as poly-oxymethylene ethers (OME) have a significant potential to effectively break the soot-NOX trade-off in compression ignition engines by using exhaust gas recirculation (EGR) to maintain low nitrogen oxide (NOX) emissions while maintaining good efficiency and simultaneously contributing to circular carbon economy. However, owing to the fundamental differences in properties of OME when compared to fossil-based diesel fuels, it is critical to fully understand its ignition and combustion phenomenology to take advantage of this fuel to its utmost potential. In this context, this work outlines the results of a systematic experimental study performed in a heavy-duty, single-cylinder, optical engine probing the spatial and temporal progression of fuel decomposition and ignition behavior of OME when compared to n-dodecane, a diesel-fuel surrogate. Thermodynamic analysis and optical diagnostics techniques including simultaneous HCHO-PLIF and OH-PLIF complemented by high-speed OH* chemiluminescence were employed along with parametric sweeps of intake temperature and EGR dilution rates. OME does not exhibit any observable low temperature heat release irrespective of the ambient oxygen concentration. Differences in the observed diffusive flame structure such as longer flame lift-off length, less pronounced combustion recession, faster premixed burn at ignition (“volumetric” ignition), non-sooting behavior suggest that the inherent presence of fuel-bound oxygen in OME can skew the air-fuel ratio (AFR) distribution within the jet thereby reducing the reliance of combustion on mixing and air entrainment. This leads to rapid late-cycle oxidation leading to shorter combustion duration and favorable combustion phasing. Results also suggest that OME exhibits relatively weak negative temperature coefficient (NTC) behavior, however, the OME fuel-decomposition kinetic-pathways produce significant concentration of HCHO, which might be erroneously interpreted as a product of cool-flames.

Air-fuel ratio↗

Improving Conversion of Captured CO 2 on Mixed-Oxide Dual-Function Materials by Low-Concentration Metal Promotion

Reactive carbon capture (RCC) is a promising nascent approach to harness the untapped resource of waste CO 2 to produce fuels and platform chemicals. However, process economics relies on the design of dual-function materials (DFMs) that exhibit maximal conversion of captured CO 2 and high selectivity toward valuable carbon products (e.g., CO). Herein, we report the use of low-concentration (ca. 0.5 wt %) metal promotors (Pt and Au) to improve the conversion of captured CO 2 on a Zn-Al mixed-oxide DFM by >30%, while also more than doubling per-cycle CO yield due to enhanced retention of captured CO 2 and H 2 activation. In situ DRIFTS of bound CO 2 on the DFMs showed distinctions in surface carbonate formation for the Pt- and Au-modified materials that were correlated with product evolution during the reactive desorption step of RCC. Particularly, Pt afforded superior H 2 activation but formed irreversibly-bound bicarbonates, compromising overall productivity, while the Na/Au/ZA DFM predominantly adsorbed CO 2 on Na sites, resulting in polydentate carbonates that are retained until higher temperatures before conversion to CO. In conclusion, these results indicate that adding a low concentration of oxidation-resistant noble metals, especially Au, is an effective strategy for improving key performance metrics of Zn-Al mixed-oxide DFMs to further advance the development of scalable RCC technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct Extraction of Uranium-Lanthanide Oxides in Tributyl Phosphate

Abstract Direct extraction of used nuclear fuel (UNF) in an organic solution could be more efficient than the previous practice with aqueous solutions. However, the UNF would need to be treated via voloxidiation before being processed using solvent extraction. The voloxidation process can form oxide and/or nitrate compounds. This work investigated the dissolution of uranium/lanthanide oxides in 30 vol % TBP diluted in dodecane (pre-equilibrated with 4 M nitric acid) in a glass reactor with air sparging to ascertain the uranium/lanthanide oxide dissolution behavior prior to scaling the process. The uranium/lanthanide oxides were prepared by co-precipitating uranium/lanthanide nitrates with hydroxide and then calcined to form a mixed oxide. While the relative concentrations of the lanthanides are not representative of used nuclear fuel, the neodymium and erbium allowed ease of tracking dissolution with visible spectroscopy. Cerium was used as a surrogate for plutonium. The dissolution rate of the oxides was similar but incomplete. A miniscule amount of cerium, as cerium oxide, took several months to slowly dissolve; however, when co-precipitated with uranium and other lanthanides, a significant amount of cerium dissolved readily.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Actinide oxide dissolution in tributyl phosphate

An alternative to dissolving used nuclear fuel (UNF) in an acidic solution during reprocessing is direct dissolution in an organic solution, which would eliminate an aqueous dissolution step, decrease the amount of nitrate needed, and reduce the facility size. The flowsheet for this potentially less expensive alternative is first to voloxidize the UNF to remove fission product gases and form an oxide. After voloxidation, the UNF is then dissolved in an organic solution containing an extractant mixed with an aliphatic diluent and pre-equilibrated with nitric acid. The organic solution then goes through a solvent extraction process to recover the uranium and/or other desired radionuclides. This work qualitatively studied the dissolution of actinide oxides (UO2, NpO2, and PuO2) in tributyl phosphate using UV-Vis-NIR absorbance spectroscopy to ascertain dissolution behavior. Initial studies included material that is otherwise difficult to dissolve in only nitric acid, specifically CeO2, that is sometimes used as a dissolution surrogate for PuO2. This work confirmed that CeO2, NpO2, and PuO2 are difficult to dissolve in 30 vol% TBP-dodecane pre-equilibrated with 10 M HNO3 and will readily dissolve when co-precipitated with U (i.e., the mixed oxides U-Ce, U-Np, and U-Pu), surrogates for voloxidized nuclear fuel.

Gogolski, Jarrod [Savannah River National Laborato↗

Ducted Fuel Injection vs. Free-Spray Injection: A Study of Mixing and Entrainment Effects Using Numerical Modeling

Diesel engines are an important technology for transportation of both people and goods. However, historically they have suffered a significant downside of high soot and nitrogen oxides (NO x ) emissions. Recently, ducted fuel injection (DFI) has been demonstrated to attenuate soot formation in compression-ignition engines and combustion vessels by 50% to 100%. This allows for diesel engines to be run at low-NO x emissions that would have otherwise produced significantly more soot due to the soot/NO x tradeoff. Currently the root causes of this soot attenuation are not well understood. To be able to better optimize DFI for use across a variety of engines and conditions, it is important to understand clearly how it works. This study expands on the current understanding of DFI by using numerical modeling under nonreacting conditions to provide insights about the roles of entrainment and mixing that would have been much more challenging to obtain experimentally. We report this study found that DFI enhances charge gas entrainment upstream of the duct and blocks entrainment inside of the duct. Mixing is enhanced by the duct, which results in lower peak equivalence ratios at the exit of the duct.

42 ENGINEERING↗

A Synchrotron-Based Vacuum Ultraviolet Photoionization Mass Spectrometer-Coupled Microreactor To Probe Thermocatalysis

Vacuum ultraviolet photoionization (VUV-PI) mass spectrometry offers an isomer-selective and universal ionization with minimal fragmentation detection of organics in complex chemical systems such as pyrolysis and combustion. Here, in this study, we report a state-of-the-art experimental setup of a universal catalytic microreactor combined with a molecular beam to investigate the thermocatalytic oxidation of a heterogeneous system relevant for probing reactions at gas–solid interfaces. In strong contrast to traditional off-line analytical methods, this technique is capable of identifying and quantifying short-lived species (radicals) as well as stable products to decipher initial reaction steps via the detection of nascent products. The thermocatalytic oxidative degradation of exo-tetrahydrodicyclopentadiene (JP-10), a high energy-density hydrocarbon fuel, over solid titanium–aluminum–boron reactive mixed metal nanopowder (Ti-Al-B RMNP) is exploited to showcase potential applications. Overall, some 59 nascent gas-phase products are identified via photoionization efficiency (PIE) curves, including oxygenated species and hydrocarbons comprising closed-shell molecules and radicals. The critical temperature for complete oxidative decomposition of JP-10 was lowered by 450 K from 1400 K to 950 K, indicating an efficient thermocatalytic action of Ti-Al-B nanoparticles on JP-10. The enabling of a universal chemical microreactor along with VUV-PI mass spectrometry broadens the applicability of this technique to hydrocarbon fuel oxidation and pyrolysis characterization. This isomer-selective sensitive probing along with the detection of radical transients makes the aforementioned technique superior to other conventional analytical techniques such as microflow tube and pyrolysis-gas chromatography coupled with mass spectrometry for investigating similar pyrolysis reactions and comprehensive quantification.

Paul, Dababrata [Univ. of Hawaii at Manoa, Honolul↗