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All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Unraveling Grain Boundary Instability in Dense Proton-Conducting Oxides

The long-term stability of protonic ceramic electrolysis cell (PCEC) materials under high-steam operating conditions remains a critical barrier to device commercialization. Here, we investigate the fundamental degradation mechanisms of dense BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ (BCZYYb) electrolytes operated at 550 °C, 50% H 2 O in air. Over 1,000 h, the total electrolyte conductivity decreases by 11.1%, driven primarily by a >130% increase in grain-boundary resistivity. Post-mortem analyses reveal that damage is localized to near-surface grain boundaries extending ∼50 μm into the dense electrolyte pellet. This surface localization indicates that degradation is likely to be severe in thin, device-level electrolytes. Degradation is primarily attributed to chemo-mechanical grain-boundary weakening arising from hydration-induced chemical expansion, culminating in the formation of intergranular cracks oriented parallel to the pellet surface. These internal cracks subsequently react with steam and/or CO 2 , leading to the formation of nanoscale insulating phases, including Ba(OH) 2 , nanocrystalline BaCO 3 , and amorphous Ce/Zr/Y/Yb-containing oxides or hydroxycarbonates. After an initial degradation period of approximately 200 h, the overall conductivity stabilizes. Incorporating NiO sintering aids reduces grain-boundary density by an order of magnitude under identical sintering conditions. Although addition of NiO increases the initial resistivity by >160% at 550 °C, it substantially suppresses grain-boundary instability and mitigates chemical degradation. These findings underscore the urgent need for chemical and/or physical stabilization of BCZYYb electrolytes and offer design guidelines to enable durable, high-performance PCECs.

08 HYDROGEN↗
DOE OSTI2020

(Invited) All-Solid-State Batteries Using Li 7 La 3 Zr 2 O 12 Garnet Electrolyte Framework

All-solid-state batteries (ASSB) using LLZO (variants of Li 7 La 3 Zr 2 O 12 ) garnet solid electrolyte with lithium metal anode potentially offer higher energy density and improved safety. Rational design of cell architecture as well as manufacturing scalability are key aspects to consider as the technology readiness level advances. A thick composite cathode layer attached to a thin solid electrolyte layer is desirable to obtain superior energy densities. Furthermore, the architecture within the composite cathode may be engineered to contain directional conduction paths of lithium ions or electrons for enhanced rate capabilities. Here, we demonstrate a functioning bulk-type LLZO based all-solid-state battery with a practical form factor incorporating the above described design concepts. Freeze-tape-casting (FTC), a scalable and environmentally friendly ceramic processing method, is used to construct 3D porous LLZO scaffolds composed of vertical arrays of LLZO walls. The thin solid-electrolyte layer is fabricated by tape-casting (TC). By sintering the stacks of FTC and TC green tapes, porous/dense bilayers and porous/dense/porous trilayers of LLZO frameworks are obtained. An ASSB was constructed using a porous/dense bilayer by infiltrating LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode powder and carbon black into the porous layer and adhering lithium metal foil to the dense side. We find it crucial to introduce a plastic crystal based soft solid electrolyte to the porous layer to electrochemically connect all cathode components, obviating the need for co-sintering to establish contact. The soft nature of the plastic crystal based solid-electrolyte may be able to accommodate the volume change of the cathode material as it cycles. In this device, which contained no liquid component, the initial discharge capacities were similar to those observed in a lithium ion battery configuration using the same cathode powder at C/10 rates.

25 ENERGY STORAGE↗
DOE OSTI2020

X-Ray Diffraction and Electron Microscopy Studies of the Size Effects on Pressure-Induced Phase Transitions in CdS Nanocrystals

In recent years, investigations of the phase transition behavior of semiconducting nanoparticles under high pressure has attracted increasing attention due to their potential applications in sensors, electronics, and optics. However, current understanding of how the size of nanoparticles influences this pressure-dependent property is somewhat lacking. In particular, phase behaviors of semiconducting CdS nanoparticles under high pressure have not been extensively reported. Therefore, in this work, CdS nanoparticles of different sizes are used as a model system to investigate particle size effects on high-pressure-induced phase transition behaviors. In particular, 7.5, 10.6, and 39.7 nm spherical CdS nanoparticles are synthesized and subjected to controlled high pressures up to 15 GPa in a diamond anvil cell. Analysis of all three nanoparticles using in-situ synchrotron wide-angle X-ray scattering (WAXS) data shows that phase transitions from wurtzite to rocksalt occur at higher pressures than for bulk material. Bulk modulus calculations not only show that the wurtzite CdS nanomaterial is more compressible than rocksalt, but also that the compressibility of CdS nanoparticles depends on their particle size. Furthermore, sintering of spherical nanoparticles into nanorods was observed for the 7.5 nm CdS nanoparticles. Our results provide new insights into the fundamental properties of nanoparticles under high pressure that will inform designs of new nanomaterial structures for emerging applications.

Meng, Lingyao↗
DOE OSTI2013

In situ characterization of nanoscale catalysts during anodic redox processes

Controlling the structure and composition of the anode is critical to achieving high efficiency and good long-term performance. In addition to being a mixed electronic and ionic conductor, the ideal anode material should act as an efficient catalyst for oxidizing hydrogen, carbon monoxide and dry hydrocarbons without de-activating through either sintering or coking. It is also important to develop novel anode materials that can operate at lower temperatures to reduce costs and minimized materials failure associated with high temperature cycling. We proposed to synthesize and characterize novel anodecermets materials based on ceria doped with Pr and/or Gd together with either a Ni or Cu metallic components. Ceria is a good oxidation catalyst and is an ionic conductor at room temperature. Doping it with trivalent rare earths such as Pr or Gd retards sintering and makes it a mixed ion conductor (ionic and electronic).

08 HYDROGEN↗
DOE OSTI2013

Uranium Silicide/Nitride Pellet Fabrication Demonstration: Report on Powder Characteristics (Final CRADA Report)

This report details experimental procedures and results of work at the Idaho National Lab to fabricate U 3 Si 2 and UN ceramic powders from their basic elements. The reaction procedure centers on arc melting using a cold, copper hearth. The reacted "buttons" are then ground into powder, and the powder is characterized. The preliminary experiments utilized feeding pieces of metallic U and Si (in the proper ratio) into the arc-melting furnace for melting into "buttons." This melting was repeated several times with the intent of homogenizing the reaction to produce phase pure U 3 Si 2 powder. However, sintering of the pressed-powder at over 1400C showed partial melting and slumping of the pellets. Characterization of the powder using x-ray diffraction (XRD) indicated the crystalline portion of the powder was U 3 Si 2 . However, further investigations indicated a significant portion (12.4%) of the powder was amorphous Si that was transformed into crystalline Si after a period of annealing. Therefore, a greatly improved method of powder fabrication was developed using mixing fine powders of U and Si together, pressing into a pellet, followed by arc melting and grinding into U 3 Si 2 powder. This method was highly successful in producing high phase purity (>98.5% U 3 Si 2 ) powder. One feature of this method is that the fine U powder is made by a hydride/de-hydride cycle. The equipment available at INL only allows for fabrication of relatively small batches, and the method (using INL equipment) is somewhat labor intensive. The powder was used to successfully press and sinter U 3 Si 2 pellets ("Final Report on Pellet Fabrication," INL/LTD-13-29465). A limited attempt was made to fabricate high purity UN powder using the fine U powder made at INL (hydride/de-hydride method) and heating it under flowing nitrogen gas. X-ray diffraction was used to characterize the resulting powder, and a Rietveld refinement was performed on the data. The refinement showed a result of 70.0% UN and 30.0% U 2 N 3 . It is thought that the UN content can be easily increased

Source record↗
DOE OSTI2013

Mechanisms Underpinning Degradation of Protective Oxides and Thermal Barrier Coatings in High Hydrogen Content (HHC) - Fueled Turbines

The overarching goal of this research program has been to evaluate the potential impacts of coal-derived syngas and high-hydrogen content fuels on the degradation of turbine hot-section components through attack of protective oxides and thermal barrier coatings. The primary focus of this research program has been to explore mechanisms underpinning the observed degradation processes, and connections to the combustion environments and characteristic non-combustible constituents. Based on the mechanistic understanding of how these emerging fuel streams affect materials degradation, the ultimate goal of the program is to advance the goals of the Advanced Turbine Program by developing materials design protocols leading to turbine hot-section components with improved resistance to service lifetime degradation under advanced fuels exposures. This research program has been focused on studying how: (1) differing combustion environments – relative to traditional natural gas fired systems – affect both the growth rate of thermally grown oxide (TGO) layers and the stability of these oxides and of protective thermal barrier coatings (TBCs); and (2) how low levels of fuel impurities and characteristic non-combustibles interact with surface oxides, for instance through the development of molten deposits that lead to hot corrosion of protective TBC coatings. The overall program has been comprised of six inter-related themes, each comprising a research thrust over the program period, including: (i) evaluating the role of syngas and high hydrogen content (HHC) combustion environments in modifying component surface temperatures, heat transfer to the TBC coatings, and thermal gradients within these coatings; (ii) understanding the instability of TBC coatings in the syngas and high hydrogen environment with regards to decomposition, phase changes and sintering; (iii) characterizing ash deposition, molten phase development and infiltration, and associated corrosive/thermo-chemical attack mechanisms; (iv) developing a mechanics-based analysis of the driving forces for crack growth and delamination, based on molten phase infiltration, misfit upon cooling, and loss of compliance; (v) understanding changes in TGO growth mechanisms associated with these emerging combustion product streams; and (vi) identifying degradation resistant alternative materials (including new compositions or bi-layer concepts) for use in mitigating the observed degradation modes. To address the materials stability concerns, this program integrated research thrusts aimed at: (1) Conducting tests in simulated syngas and HHC environments to evaluate materials evolution and degradation mechanisms; assessing thermally grown oxide development unique to HHC environmental exposures; carrying out high-resolution imaging and microanalysis to elucidate the evolution of surface deposits (molten phase formation and infiltration); exploring thermo-chemical instabilities; assessing thermo-mechanical drivers and thermal gradient effects on degradation; and quantitatively measuring stress evolution due to enhanced sintering and thermo-chemical instabilities induced in the coating. (2) Executing experiments to study the melting and infiltration of simulated ash deposits, and identifying reaction products and evolving phases associated with molten phase corrosion mechanisms; utilizing thermal spray techniques to fabricate test coupons with controlled microstructures to study mechanisms of instability and degradation; facilitating thermal gradient testing; and developing new materials systems for laboratory testing; (3) Correlating information on the resulting combustion environments to properly assess materials exposure conditions and guide the development of lab-scale simulations of material exposures; specification of representative syngas and high-hydrogen fuels with realistic levels of impurities and contaminants, to explore differences in heat transfer, surface degradation, and deposit formation; and facilitating combustion rig testing of materials test coupons.

Mumm, Daniel↗
DOE OSTI2015

AREVA Team Enhanced Accident Tolerant Fuels Concepts (Phase 1A Final Report)

In response to the Department of Energy (DOE) funded initiative to develop and deploy lead fuel assemblies (LFAs) of Enhanced Accident Tolerant Fuel (EATF) into a US reactor within 10 years, AREVA put together a team to develop promising technologies for improved fuel performance during off normal operations. This team consisted of the University of Florida (UF) and the University of Wisconsin (UW), Savannah River National Laboratory (SRNL), Duke Energy and Tennessee Valley Authority (TVA). This team brought broad experience and expertise to bear on EATF development. AREVA has been designing; manufacturing and testing nuclear fuel for over 50 years and is one of the 3 large international companies supplying fuel to the nuclear industry. The university and National Laboratory team members brought expertise in nuclear fuel concepts and materials development. Duke and TVA brought practical utility operating experience. This report documents the results from the initial “discovery phase” where the team explored options for EATF concepts that provide enhanced accident tolerance for both Design Basis (DB) and Beyond Design Basis Events (BDB). The main driver for the concepts under development were that they could be implemented in a 10 year time frame and be economically viable and acceptable to the nuclear fuel marketplace. The economics of fuel design make this DOE funded project very important to the nuclear industry. Even incremental changes to an existing fuel design can cost in the range of $100M to implement through to LFAs. If this money is invested evenly over 10 years then it can take the fuel vendor several decades after the start of the project to recover their initial investment and reach a breakeven point on the initial investment. Step or radical changes to a fuel assembly design can cost upwards of $500M and will take even longer for the fuel vendor to recover their investment. With the projected lifetimes of the current generation of nuclear power plants large scale investment by the fuel vendors is difficult to justify. Specific EATF enhancements considered by the AREVA team were; Improved performance in DB and BDB conditions; Reduced release to the environment in a catastrophic accident; Improved performance during normal operating conditions; Improved performance if US reactors start to load follow; Equal or improved economics of the fuel; and Improvements to the fuel behavior to support future transportation and storage of the used nuclear fuel (UNF). In pursuit of the above enhancements, EATF technology concepts that our team considered were; Additives to the fuel pellets which included; Chromia doping to increase fission gas retention. Chromia doping has the potential to improve load following characteristics, improve performance of the fuel pellet during clad failure, and potentially lock up cesium into the fuel matrix; Silicon Carbide (SiC) Fibers to improve thermal heat transfer in normal operating conditions which also improves margin in accident conditions and the potential to lock up iodine into the fuel matrix; Nano-diamond particles to enhance thermal conductivity; Coatings on the fuel cladding; and Nine coatings on the existing Zircaloy cladding to increase coping time and reduce clad oxidation and hydrogen generation during accident conditions, as well as reduce hydrogen pickup and mitigate hydride reorientation in the cladding. To facilitate the development process AREVA adopted a formal “Gate Review Process” (GR) that was used to review results and focus resources onto promising technologies to reduce costs and identify the technologies that would potentially be carried forward to LFAs within a 10 year period. During the initial discovery phase of the project AREVA took the decision to be relatively hands off and allow our university and National Laboratory partners to be free thinking and consider options that would not be constrained by preconceived ideas from the fuel vendor. To counter this and to keep the partners focused, the GR process was utilized. During this GR process each of the team members presented their findings to a board made up of technical experts from utilities, fuel manufacturing experts, fuel technical experts, and fuel research and development (R&D) experts. During the initial 2 years of the project there were several major accomplishments. These accomplishments, along with the implications for successfully implementing EATF, are; The experimental spark plasma sintering process (SPS) process was successfully used to produce fuel pellets containing either 10% SiC whiskers or nano-diamond particles. The ability to use this process enables the thermal margin enhancements of the fuel additives to be realized. Without the SPS process, the conventional process cannot support adding pellet additives in the required quantities; Coatings of Ti2AlC were successfully applied to Zircaloy-4 cladding. Testing of Ti2AlC coatings at Loss of Cooling Accident (LOCA) conditions showed reduced cladding oxidation compared to present un-coated Zircaloy-4 cladding. This achievement allows the presently used cladding system to be retained so that the 10 year schedule can be met. Having to implement a new cladding material will extend the development schedule beyond 10 years; Several documents were produced to support future development, testing, and licensing of EATF, including a design requirements traceability matrix, a draft business plan, a draft test plan, a draft regulatory plan, and the acceptance criteria for lead fuel assembly insertion into a commercial reactor. This preparatory work lays the foundation for ensuring the future development plans address all the areas required to test, license, and manufacture the new EATF; and In addition, the high velocity oxy-fuel and electrophoretic deposition (EPD) coating application processes were dropped from further consideration due to their inability to meet manufacturing criteria. This allows the resources to be focused on the most promising EATF concepts identified. Future development opportunities that were identified during this work include; The use of SiC or diamond requires that a new pellet production technique (Spark Plasma Sintering), be developed. This entails investment in developing, proving and implementing a new commercial pellet production process. Development of the process to apply thinner coatings is required; Coatings cannot be too “thick” or they will displace a significant volume of water in the core resulting in reduced thermal hydraulic characteristics; Application of the coating at high temperature can affect the Zircaloy substrate. This will require the development and implementation of a new cladding coating manufacturing process; and Replace the Cold Spray (CS) cladding coating application with the Physical Vapor Deposition (PVD) process to eliminate duplication of work and provide greater control over coating thicknesses. This can result in a reduction in the final cycle economic penalty of coatings.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2015

MST Filterability Tests

The Savannah River Site (SRS) is currently treating radioactive liquid waste with the Actinide Removal Process (ARP) and the Modular Caustic Side Solvent Extraction Unit (MCU). The low filter flux through the ARP has limited the rate at which radioactive liquid waste can be treated. Recent filter flux has averaged approximately 5 gallons per minute (gpm). Salt Batch 6 has had a lower processing rate and required frequent filter cleaning. Savannah River Remediation (SRR) has a desire to understand the causes of the low filter flux and to increase ARP/MCU throughput. In addition, at the time the testing started, SRR was assessing the impact of replacing the 0.1 micron filter with a 0.5 micron filter. This report describes testing of MST filterability to investigate the impact of filter pore size and MST particle size on filter flux and testing of filter enhancers to attempt to increase filter flux. The authors constructed a laboratory-scale crossflow filter apparatus with two crossflow filters operating in parallel. One filter was a 0.1 micron Mott sintered SS filter and the other was a 0.5 micron Mott sintered SS filter. The authors also constructed a dead-end filtration apparatus to conduct screening tests with potential filter aids and body feeds, referred to as filter enhancers. The original baseline for ARP was 5.6 M sodium salt solution with a free hydroxide concentration of approximately 1.7 M.3 ARP has been operating with a sodium concentration of approximately 6.4 M and a free hydroxide concentration of approximately 2.5 M. SRNL conducted tests varying the concentration of sodium and free hydroxide to determine whether those changes had a significant effect on filter flux. The feed slurries for the MST filterability tests were composed of simple salts (NaOH, NaNO 2 , and NaNO 3 ) and MST (0.2 – 4.8 g/L). The feed slurry for the filter enhancer tests contained simulated salt batch 6 supernate, MST, and filter enhancers.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Advanced thermal barrier coatings for operation in high hydrogen content fueled gas turbines

The Center for Thermal Spray Research (CTSR) at Stony Brook University in partnership with its industrial Consortium for Thermal Spray Technology is investigating science and technology related to advanced metallic alloy bond coats and ceramic thermal barrier coatings for applications in the hot section of gasified coal-based high hydrogen turbine power systems. In conjunction with our OEM partners (GE and Siemens) and through strategic partnership with Oak Ridge National Laboratory (ORNL) (materials degradation group and high temperature materials laboratory), a systems approach, considering all components of the TBC (multilayer ceramic top coat, metallic bond coat & superalloy substrate) is being taken during multi-layered coating design, process development and subsequent environmental testing. Recent advances in process science and advanced in situ thermal spray coating property measurement enabled within CTSR has been incorporated for full-field enhancement of coating and process reliability. The development of bond coat processing during this program explored various aspects of processing and microstructure and linked them to performance. The determination of the bond coat material was carried out during the initial stages of the program. Based on tests conducted both at Stony Brook University as well as those carried out at ORNL it was determined that the NiCoCrAlYHfSi (Amdry) bond coats had considerable benefits over NiCoCrAlY bond coats. Since the studies were also conducted at different cycling frequencies, thereby addressing an associated need for performance under different loading conditions, the Amdry bond coat was selected as the material of choice going forward in the program. With initial investigations focused on the fabrication of HVOF bond coats and the performance of TBC under furnace cycle tests , several processing strategies were developed. Two-layered HVOF bond coats were developed to render optimal balance of density and surface roughness and resulted in improved TBC lifetimes. Processing based approaches of identifying optimal processing regimes deploying advanced in-situ coating property measurements and in-flight diagnostic tools were used to develop process maps for bond coats. Having established a framework for the bond coat processing using the HVOF process, effort were channeled towards fabrication of APS and VPS bond coats with the same material composition. Comparative evaluation of the three deposition processes with regard to their microstrcuture , surface profiles and TBC performance were carried out and provided valuable insights into factors that require concurrent consideration for the development of bond coats for advanced TBC systems. Over the course of this program several advancements were made on the development of durable thermal barrier coatings. Process optimization techniques were utilized to identify processing regimes for both conventional YSZ as well as other TBC compositions such as Gadolinium Zirconate and other Co-doped materials. Measurement of critical properties for these formed the initial stages of the program to identify potential challenges in their implementation as part of a TBC system. High temperature thermal conductivity measurements as well as sintering behavior of both YSZ and GDZ coatings were evaluated as part of initial efforts to undersand the influence of processing on coating properties. By effectively linking fundamental coating properties of fracture toughness and elastic modulus to the cyclic performance of coatings, a durability strategy for APS YSZ coatings was developed. In order to meet the goals of fabricating a multimaterial TBC system further research was carried out on the development of a gradient thermal conductivity model and the evaluation of sintering behavior of multimaterial coatings. Layer optimization for desired properties in the multimaterial TBC was achieved by an iterative feedback approach utilizing process maps and in-situ and ex-situ coating property sensors. Addressing the challenges pertaining to the integration of the two materials YSZ and GDZ led to one of most the critical outcomes of this program, the development of durable multimaterial, multifunctional TBC systems.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Determination of Desorbed Species During Heating of AgI-Mordenite Provided by ORNL

This study is focused on describing the desorbed off gases due to heating of the AgIMordenite (MOR) produced at ORNL for iodine (I 2 ) gas capture from nuclear fuel aqueous reprocessing. In particular, the interest is for the incorporation of the AgI-MOR into a waste form, which might be the Sandia developed, low temperature sintering, Bi-Si oxide based, Glass Composite Material (GCM). The GCM has been developed as a waste form for the incorporation any oxide based getter material. In the case where iodine may be released during the sintering process of the GCM, additional Ag flake is added as further insurance in total iodine capture and retention. This has been the case for the incorporated ORNL developed AgIMOR. Thermal analysis studies were carried out to determine off gasing processes of ORNL AgIMOR. Independent of sample size, ~7wt% of total water is desorbed by 225°C. This includes both bulk surface and occluded water, and are monitored as H2O and OH. Of that total, ~5.5wt% is surface water which is removed by 125°C, and 1.5wt% is occluded (in zeolite pore) water. Less than ~1 wt% total water continues to desorb, but is completely removed by 500°C. Above 300°C, the detectable remaining desorbing species observed are iodine containing compounds, including I and I 2 .

09 BIOMASS FUELS↗
DOE OSTI2016

Collaboration for the Advancement of Indirect 3D Printing Technology

Amorphous powders often possess high hardness values and other useful mechanical properties. However, densifying these powders into complex shapes while retaining their unique properties is a challenge with standard processing routes. Pressureless sintering, for example, can densify intricate green parts composed of rapidly-solidified powders. But this process typically involves long exposures to elevated temperatures, during which the non-equilibrium microstructure of the powder can evolve towards lower energy configurations with inferior properties. Pressure-assisted compaction techniques, by contrast, can consolidate green parts with simple shapes while preserving the microstructure and properties of the powder feedstock. But parts made with these processes generally require additional post-processing, including machining, which introduces new challenges due to the high hardness of these materials. One processing route that can potentially avoid these issues is Indirect 3D Printing (I-3DP; aka Binder Jetting) followed by melt infiltration. In I-3DP, an organic binder is used to join powder feedstock, layer-by-layer, into a green part. In melt infiltration, this green preform is densified by placing it in contact with a molten alloy that wets the preform and wicks into the pores as a result of capillary forces. When these processes are paired together, they offer two key advantages for the densification of rapidly-solidified powders. The first advantage is that the timescale associated with melt infiltration is on the order of seconds for parts with cm-scale dimensions. So in many instances, infiltration requires only a brief thermal excursion that does not degrade the feedstock’s microstructure. The second advantage is that the combination of binder-jet 3D printing and melt infiltration gives fully-dense net shape objects, minimizing the need for subsequent post-processing. In this work, fully-dense, net shape objects have been fabricated from an amorphous powder using I-3DP and molten bronze infiltration while maintaining the amorphous microstructure. X-ray diffraction, scanning electron microscopy, and differential thermal analysis were used to characterize the structural evolution of the powder feedstock during an infiltration heating cycle. Microindentation and bend tests were performed on the infiltrated material to evaluate its mechanical properties. It was found that infiltration improved both the ductility and strength of the sintered preforms by eliminating the stress concentration at the interparticle necks. The infiltrated material had an 11 GPa Vickers hardness and moderate damage tolerance, making it well-suited for applications requiring hard, net shape parts.

42 ENGINEERING↗
DOE OSTI2016

Investigation of the Deposition and Densification Parameters on the Mechanical Properties of Pressurized Spray Deposited (PSD) 3-D Printed Ceramic Components

Oak Ridge National Laboratory (ORNL) and HotEnd Works teamed to investigate the use of pressurized spray deposition (PSD) technology for the production of ceramic parts via additive manufacturing. Scanning electron microscopy of sintered parts provided by HotEnd Works revealed voids large enough to compromise the mechanical properties of PSD manufactured parts. Scanning electron microscopy and particle size analysis of the alumina oxide powder feedstocks indicated that the powders contained some large particles and some agglomerations in the powder. Further classification of the powder feedstocks and removal of the agglomerates by sonication in the liquid used for the PSD process are recommended. Analysis of sintered parts indicated that the sonic modulus for the alumina part is consistent with other known values for alumina. The density for this part was determined by standard Archimedes immersion density methods and was found to be > 99.7 % of the theoretical density for pure alumina.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Radiochemical purity of Mo and Tc solution obtained after irradiation and dissolution of Mo-100-enriched and ultra-high-purity natural Mo disks

Four irradiations of ultra-high-purity natural Mo targets and one irradiation using 97.4% Mo-100-enriched material were performed. The purpose of these irradiations was to determine whether the presence of Sn stabilizer in the H 2 O 2 used for the dissolution of sintered Mo disks can affect the radiochemical purity of the final K 2 MoO 4 in 5M KOH solution. Results from radiochemical purity tests performed using thin-layer paper chromatography show that even 2– 3× excess of Sn-stabilized H 2 O 2 typically used for dissolution of sintered Mo disks did not affect the radiochemical purity of the final product.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2016

Gel Fabrication of Molybdenum “Beads”

Spherical molybdenum particles or “beads” of various diameters are of interest as feedstock materials for the additive manufacture of targets and assemblies used in the production of 99 Mo medical isotopes using accelerator technology. Small metallic beads or ball bearings are typically fabricated from wire; however, small molybdenum spheres cannot readily be produced in this manner. Sol-gel processes are often employed to produce small dense microspheres of metal oxides across a broad diameter range that in the case of molybdenum could be reduced and sintered to produce metallic spheres. These Sol-gel type processes were examined for forming molybdenum oxide beads; however, the molybdenum trioxide was chemically incompatible with commonly used gelation materials. As an alternative, an aqueous alginate process being assessed for the fabrication of oxide spheres for catalyst applications was employed to form molybdenum trioxide beads that were successfully reduced and sintered to produce small molybdenum spheres.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Printed Nano Cu and NiSi Contacts and Metallization for Solar Cell Modules

There has long been a desire to replace the front-side silver contacts in silicon solar cells. There are two driving forces to do this. First, silver is an expensive precious metal. Secondly, the process to use silver requires that it be formulated into screen print pastes that need a lead-containing glass frit, and the use of lead is forbidden in many parts of the world. Because of the difficulty in replacing these pastes and the attendant processes, lead exemptions have granted to solar cells. Copper has been the replacement metal of choice because it is significantly cheaper than silver and is very close to silver in electrical conductivity. Using processes which do not use lead, obviates it as an environmental contaminant. However, copper cannot be in contact with the silicon of the cell since it migrates through the silicon and causes defects which severely damage the efficiency of the cell. Hence, a conductive barrier must be placed between the copper and silicon and nickel, and especially nickel silicide, have been shown to be materials of choice. However, nickel must be sputtered and annealed to create the nickel silicide barrier, and copper has either been sputtered or plated. All of these processes require expensive, specialized equipment and plating uses environmentally unfriendly chemicals. Therefore, Intrinsiq proposed using printed nano nickel silicide ink (which we had previously invented) and printed nano copper ink to create these electrodes and barriers. We found that nano copper ink could be readily printed and sintered under a reducing atmosphere to give highly conductive grids. We further showed that nano nickel silicide ink could be readily jetted into grids on top of the silicon cell. It could then be annealed to create a barrier. However, it was found that the combination of printed NiSi and printed Cu did not give contact resistivity good enough to produce efficient cells. Only plated copper on top of the printed NiSi gave useful contact resistivity, and that proved to five to ten times less conductive than the commercial silver grids. Even so, the NiSi layer was a very good barrier to copper migration, even under harsh environmental conditions. Additionally, both plated copper and printed copper could be soldered to. While it may be possible to produce an all printed copper/nickel silicide top electrode for silicon cells, it was not easily demonstrated within the time and monetary constraints of the present project. Additionally, potential customers have told us that having to laser ablate the anti-reflection coating of cells to create a connection for NiSi, and the addition of two printing and annealing (sintering for copper) steps, adds too much expense to compensate for any potential cost savings from using copper. The cost benefits of copper have been further eroded by the facts that over the lifetime of this project, the cost of silver electrodes decreased due to manufacturers finding ways to use less and less silver, and inventing pastes which use less costly silver materials to begin with. All of these factors were considered and led to the decision to stop the program before actual manufacturing scale was attempted.

14 SOLAR ENERGY↗
DOE OSTI2017

Ceramic Proppant Design for In-situ Microbially Enhanced Methane Recovery

This project designed a new type of multi-functional lightweight proppant. The proppant is utilized as the conventional lightweight proppant but also transports microorganisms to coalbed reservoirs. The proppant is coated with a polymer which protects the methanogenic microorganisms and serves as a time-release delivery for methane generation. To produce the multifunctional proppant, we assigned five tasks: 1) culturing methanogenic microbes from natural carbon sources; 2) identifying optimized growth and methanogenesis conditions for the microbial consortia; 3) synthesizing the lightweight ceramic proppant; 4) encapsulating the consortia and proppant; and 5) demonstrating lab scale simulated performance by monitoring in-situ methane generation and hydraulic conductivity. Task 1) To evaluate the feasibility of ex-situ cultivation, natural microbial populations were collected from various hydrocarbon-rich environments and locations characterized by natural methanogenesis. Different rank coals, complex hydrocarbon sources, hydrocarbon seeps, and natural biogenic environments were incorporated in the sampling. Three levels of screening allowed selection of microbial populations, favorable nutrient amendments, sources of the microbial community, and quantification of methane produced from various coal types. Incubation periods of up to 24 weeks were evaluated at 23°C. Headspace concentrations of CH 4 and CO 2 were analyzed by gas chromatography. After a two-week incubation period of the most promising microbes, generated headspace gas concentrations reached 873,400 ppm for methane and 176,370 ppm for carbon dioxide. Task 2) A central composite design (CCD) was used to explore a broad range of operational conditions, examine the effects of the important environmental factors, such as temperature, pH and salt concentration, and query a feasible region of operation to maximize methane production from coal. Coal biogasification was optimal for this consortium at an initial pH value of 5.5, at 30 °C, and at a NaCl concentration 3.7 mg/cm 3 (i.e., 145,165 ppm). Task 3) To create the lightweight ceramic proppant, the kaolinite and iron oxide (Fe 2 O 3 ) mixture were sintered under reducing atmosphere varying partial pressures of oxygen from 1.7×10 -13 atm to 1.8×10-11 atm. The Fe 2 O 3 reduces to FeO and reacts with kaolinite decomposed to mullite to form Fe 2 SiO 4 , FeSiO 3 , and FeAl 2 O 4 . As a result the proppant develops large pores (~100 µm), giving it a low bulk density (1.43 g/cm 3 ), and high porosity (45.2 vol%) at P_(O_2 )of 1.8×10 -11 atm. The proppant sintered at P_(O_2 )of 1.7×10 -13 atm is characterized by smaller pores (26 µm), higher density (1.72 g/cm3) and lower porosity (37.5 vol%). Crush resistance testing at 9,000 psi yields 6.8 wt% fine particles increasing to 17.7 wt% in porous samples. Acid solubility varies from 5.5 wt% loss increasing to 12.9 wt% in porous samples. Task 4 and 5) The microbial consortia obtained from the optimized condition and lightweight proppant were encapsulated by calcium-alginate polymer. The encapsulation system, including microbes and a proppant, was stored at 20°C and 36°C. The sample stored at 36°C generated 7.1×[10] 3 ppm of methane at 670 h, whereas the sample incubated at 20°C generated 1.1×[10] 3 ppm of methane. Benchtop lab-scale bioreactors were constructed and showed with real-time measurements that, as the microbes produced methane, the pH decreased, and hydrogen and carbon dioxide gases were consumed. A calcium ion-selective sensor revealed the release mechanism of the microbes from encapsulation. The calcium ions interconnecting the alginate monomers were disassociated by counter cations such as protons and potassium ions. The counter cations bound to the carboxyl group on the alginate monomer, which thus lost its ionic interactions with the calcium ions, resulting in decomposition of the hydrogel structure. Furthermore, the conductivity was increased to ~700 mD-ft from ~530 mD-ft once the encapsulated sample was applied to the coal pack. The particle size of coal was reduced when the encapsulated sample was added to the coal. The reduced coal size implied that the microbes would consume the hydrocarbon in coal.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2018

Computational and Experimental Studies of Microstructure-Scale Porosity in Metallic Fuels for Improved Gas Swelling Behavior

This proposal will investigate the stability of bimodal pore size distributions in metallic uranium and uranium-zirconium alloys during sintering and re-sintering annealing treatments. The project will utilize both computational and experimental approaches. The computational approach includes both Molecular Dynamics simulations to determine the self-diffusion coefficients in pure U and U-Zr alloys in single crystals, grain boundaries, and free surfaces, as well as calculations of grain boundary and free surface interfacial energies. Phase-field simulations using MOOSE will be conducted to study pore and grain structure evolution in microstructures with bimodal pore size distributions. Experiments will also be performed to validate the simulations, and measure the time-dependent densification of bimodal porous compacts.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Mechanical Behavior of UO 2 at Sub-grain Length Scales: Quantification of Elastic, Plastic and Creep Properties via Microscale Testing

Techniques were developed to measure properties at sub-grain scales using depleted Uranium Oxide (d-UO2) samples heat-treated to obtain different grain sizes and oxygen stoichiometries, through three main tasks: 1) sample processing and characterization, 2) microscale and conventional testing and 3) modeling. Grain size and crystallography were characterized using Scanning Electron Microscopy (SEM), in conjunction with Electron Backscattering Diffraction (EBSD) and Electron Channeling Contrast Imaging (ECCI). Grains were then carefully selected based on their crystallographic orientations to perform ex-situ micromechanical tests with samples machined via Focused Ion Beam (FIB), with emphasis on micro-cantilever bending. These experiments were performed under controlled atmospheres, to insure stoichiometry control, at temperatures up to 700 °C and allowed measurements involving elastic (effective Young’s modulus), plastic (critical resolved shear stresses) and creep (creep strain rates) behavior. Conventional compression experiments were performed simultaneously to compare with the ex-situ measurements and study potential size effects. Modeling was implemented using anisotropic elasticity and inelastic constitutive relations for plasticity and creep based on kinematics and kinetics of dislocation glide that account for the effects of crystal orientation, and stress. The models will be calibrated and validated using the experimental data. This project provided insight on correlations among stoichiometry, crystallography and mechanical behavior in advanced oxide fuels, provided valuable experimental data to validate and calibrate mesoscale fuel performance codes and also a framework to measure sub-grain scale mechanical properties that should be suitable for use with irradiated samples due to small volumes required. The goals and metrics of the ongoing study of thermo-mechanical behavior in depleted uranium dioxide (d-UO 2 ) outlined in this project have been concluded successfully, resulting in: 1) the successful fabrication, processing, and characterization of large-grained samples with various orientations (up to and including single crystals) having stoichiometric and hyper-stoichiometric O/U ratios; 2) formulation, calibration, and validation of a crystal plasticity constitutive model to describe the creep deformation of UO 2 at the sub-grain length scale (single crystal level) at intermediate temperatures; 3) the successful calibration of a crystal plasticity constitutive model to describe the elasto-plastic deformation of microcantilever beams, also at moderate temperatures. Samples were prepared from natural uranium oxide powder of production-quality provided by Areva. The powder was pressed in a die to a pressure of 100 MPa to produce green pellets with no sintering aids, lubricants, or any other additives. The green pellets were then heated up to 1700 °C under ultra-high purity argon atmosphere (~1 ppm O2). The atmosphere was then changed to 79% Argon, 21% O 2 and the temperature was held at 1700 °C for 2 hours to sinter the pellets under oxidative conditions [1] that are known to increase grain growth kinetics in UO 2 [2]. Samples were then cooled down under Ar-4%H2 atmosphere to reduce the samples back to stoichiometric UO 2 . For macro-scale procedures, testing of UO 2 samples with large grains was performed at 1200 °C using a modified load frame capable of applying dead-weight loads to ensure constant stress conditions, while displacement of the sample produced by the applied load was measured with high precision micrometers to obtain strains. Stress steps were used during testing and the strains were monitored to measured creep strain rates under steady state for each level of stress used, so that stress exponents could be obtained. The results of the mechanical testing, along with sample geometry and crystal orientation of the grains in the samples, as well as post-test sample characterization were used to formulate a viscoplastic model to account for steady state (stage II) creep behavior, along with basic assumptions from crystal plasticity and kinematic constraints due to testing fixtures. In the micro-scale, testing of microcantilever beams at temperatures ranging from 25 to 570 °C was performed in-situ with a scanning electron microscope with a special attachment to apply load and measure displacement while the samples were at temperature. The load-displacement curves obtained showed linear behavior before fracture for all temperatures attempted except 570 °C, where clear deviations from non-linearity were observed before fracture. These deviations were consistently observed for all samples tested for a given orientation. A viscoplastic model was used to account for the presence of inelastic strain, along with basic assumptions from crystal plasticity and beam theory. These models were kept as simple as possible, and results from tests performed in a set of samples with a given crystal orientation were used to calibrate the material constants for the model, while results from a different sample set were then used for validation, thus satisfying the conditions of all main tasks within the parameters of this project. Details of these efforts are outlined in this report.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗