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At least 1,207 records · Page 67

Development, fabrication and test of a high purity silica heat shield

A highly reflective hyperpure ( 25 ppm ion impurities) slip cast fused silica heat shield material developed for planetary entry probes was successfully scaled up. Process development activities for slip casting large parts included green strength improvements, casting slip preparation, aggregate casting, strength, reflectance, and subscale fabrication. Successful fabrication of a one-half scale Saturn probe (shape and size) heat shield was accomplished while maintaining the silica high purity and reflectance through the scale-up process. However, stress analysis of this original aggregate slip cast material indicated a small margin of safety (MS. = +4%) using a factor of safety of 1.25. An alternate hyperpure material formulation to increase the strength and toughness for a greater safety margin was evaluated. The alternate material incorporates short hyperpure silica fibers into the casting slip. The best formulation evaluated has a 50% by weight fiber addition resulting in an 80% increase in flexural strength and a 170% increase in toughness over the original aggregate slip cast materials with comparable reflectance.

Rusert, E. L.↗

Method of forming a relatively stable slip of silicon metal particles and yttrium containing particles

The method concerns forming a relatively stable slip of silicon metal particles and yttrium containing particles. In one embodiment, a casting slip of silicon metal particles is formed in water. Particles of a yttrium containing sintering aid are added to the casting slip. The yttrium containing sintering aid is a compound which has at least some solubility in water to form Y.sup.+3 ions which have a high potential for totally flocculating the silicon metal particles into a semiporous solid. A small amount of a fluoride salt is added to the casting slip which contains the yttrium containing sintering aid. The fluoride salt is one which will produce fluoride anions when dissolved in water. The small amount of the fluoride anions produced are effective to suppress the flocculation of the silicon metal particles by the Y.sup.+3 ions so that all particles remain in suspension in the casting slip and the casting slip has both an increased shelf life and can be used to cast articles having a relatively thick cross-section. The pH of the casting slip is maintained in a range from 7.5 to 9. Preferably, the fluoride salt used is one which is based on a monovalent cation such as sodium or ammonia. The steps of adding the yttrium containing sintering aid and the fluoride salt may be interchanged if desired, and the salt may be added to a solution containing the sintering aid prior to addition of the silicon metal particles.

Dickie, Ray A.↗

Development of Metallic Fuels for Actinide Transmutation

Research and development activities on metallic fuels are focused on their potential use for actinide transmutation in future sodium fast reactors. As part of this application, there is also a need for a near zero-loss fabrication process and a desire to demonstrate a multifold increase in burnup potential. The incorporation of Am and Np into the traditional U-20Pu-10Zr metallic fuel alloy was demonstrated in the US during the Integral Fast Reactor Program of the 1980’s and early 1990’s. However, the conventional counter gravity injection casting method performed under vacuum, previously used to fabricate these metallic fuel alloys, was not optimized for mitigating loss of the volatile Am constituent in the casting charge; as a result, approximately 40% of the Am casting charge failed to be incorporated into the as-cast fuel alloys. Fabrication development efforts of the past few years have pursued an optimized bottom-pour casting method to increase utilization of the melted charge to near 100%, and a differential pressure casting approach, performed under an argon overpressure, has been demonstrated to result in essentially no loss of Am due to volatilization during fabrication. In short, a path toward zero-loss fabrication of metallic fuels including minor actinides has been shown to be feasible. Irradiation testing of advanced metallic fuel alloys in the Advanced Test Reactor (ATR) has been underway since 2003. Testing in the ATR is performed inside of cadmium-shrouded positions to remove >99% of the thermal flux incident on the test fuels, resulting in an epi-thermal driven fuel test that is free from gross flux depression and producing an essentially prototypic radial temperature profile inside the fuel rodlets. To date, three irradiation test series (AFC-1,2,3) have been completed. Over 20 different metallic fuel alloys have been tested to burnups as high as 30% with constituent compositions of Pu up to 30%, Am up to 12%, Np up to 10%, and Zr between 10 and 60%. In general, the performance of all of these substantially disparate metallic fuel alloys has been observed to be excellent, and their irradiation behaviors are generally consistent with historic norms for metallic fuels without minor actinide additions and having lower Pu or Zr contents. Future work is being undertaken with a view toward increasing the burnup potential of metallic fuels even more. Design innovations under investigation include: 1) lowering the fuel smear density in order to accommodate more swelling, 2) annular fuel geometry to eliminate the need for a sodium bond, 3) minor alloy additions to stabilize lanthanide fission products inside the fuel and prevent their transport to the cladding where they can participate in fuel-cladding chemical interaction (FCCI), and 4) coatings/liners on the cladding inner surface to mitigate FCCI and enable higher temperature operation. This paper will present the current state of development of metallic fuels for actinide transmutation in the US. Highlights will include recent results from metallic fuel casting experiments, experiments to identify alloy additions to immobilize lanthanide fission products, and postirradiation examinations of annular metallic fuels at low burnup.

actinide transmutation↗

Experience of Graphite Crucibles during the Pyrometallurgical Processing of Uranium

Throughout the history of processing molten uranium, various materials have been investigated and utilized for the containment of uranium at temperatures greater than 1135oC. Of these, graphite is the most prevalent material due to its ease of fabrication, expense, compatibility with induction systems, and robust characteristics. Graphite in contact with molten uranium will react to form uranium carbide species, thus a coating or mold is needed to prevent reaction of the uranium and the subsequent adherence of the solidified metal. During the pyrometallurgical treatment of used nuclear fuel for uranium recovery at the Idaho National Laboratory, two operational steps utilize graphite crucibles for containment of molten uranium. The cathode processor step separates molten salt from the uranium while the casting step blends uranium for de-enrichment and allows molten sampling of the uranium. Zirconia and yttria based materials on graphite are employed for the cathode processor and casting steps, respectively. For the cathode processor, zirconia coatings were applied initially to graphite crucibles but more recently a zirconia castable material has been molded into the graphite. Although not perfect, zirconia has been found to be compatible with both molten salt and uranium whereas yttria will react with molten salts if carried over to the casting operation. With development, the uranium losses associated with the reaction of uranium and zirconia have been reduced to approximately 1 wt. % of the total uranium throughput. Losses from yttria coating reaction during casting are typically an order of magnitude less than zirconia. The real benefit of these materials is their cost effectiveness given the multiple number of times the graphite crucibles can be reused and/or recoated. Nearly thirty uses have been recorded for graphite crucibles at both the cathode processor and casting operations. The amount of impurity pickup to the uranium products from the graphite crucibles has been minimal (<300 ppm) in terms of carbon, oxygen, zirconium, and yttrium content. Based on the promising results with the zirconia castable at the cathode processor, zirconia material has been cast into a graphite casting crucible and will be tested for comparison in the absence of salt.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The Effect of Environmental Relative Humidity on Carbonation and Oxidation in a Cementitious Waste Form - 18448

Cementitious material has been developed and used for the nuclear waste disposal. Cast Stone, a type of cementitious waste form, is considered for solidification and immobilization of part of low activity radioactive waste (LAW) at DOE Hanford Site in Richland, WA. During its life cycle, the waste form, which is produced from Portland cement, fly ash, blast furnace slag and liquid waste, is subject to reaction with carbon dioxide and oxygen, both in gaseous and dissolved form. The reactions may alter the physical and chemical properties of the waste form and thus change its retention ability for the radionuclides. Therefore, understanding the rate and the impact of oxidation and carbonation in the material is important for projecting the long-term performance of Cast Stone. However, the rate of carbonation and oxidation in Cast Stone closely depends on the moisture content in the material, which varies largely with the environmental relative humidity (RH). In this study, experiments are carried out to study the effect of environmental relative humidity on the carbonation and oxidation rate as well as the leaching of the constituents from Cast Stone. Cast Stone samples doped with Cr as a reaction indicator are aged for 16 to 32 weeks under N{sub 2}, air, and 2% CO{sub 2} (in nitrogen) environments with various relative humidities (15%, 40%, 68%, 100%). After aging, samples were tested for the pH-dependent leaching (EPA Method 1313) and mass transfer rate under diffusion-controlled leaching (EPA Method 1315) of constituents. The progress of the carbonation was measured for each condition to determine the rate of carbonation front ingress. The results show that environmental relative humidity strongly influences carbonation and oxidation in Cast Stone; however, the impact is different for the rate of reaction and for the extent of reactions. The former refers to the rate at which the reaction front ingresses, while the latter refers to the fraction of the material reacted. For both carbonation and oxidation, the largest impact of the reactions at the exposure surface is observed at intermediate relative humidity (68%). However, for carbonation, the reaction front evolves more rapidly under drier conditions, with the highest rate observed at 15% RH. As a result, carbonation and oxidation have different degree of impact on the leaching behavior of Cast Stone samples aged under various relative humidities. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Transmutation Fuel Fabrication-Fiscal Year 2016

ABSTRACT Nearly all of the metallic fuel that has been irradiated and characterized by the Advanced Fuel Campaign, and its earlier predecessors, has been arc cast. Arc casting is a very flexible method of casting lab scale quantities of materials. Although the method offers flexibility, it is an operator dependent process. Small changes in parameter space or alloy composition may affect how the material is cast. This report provides a historical insight in how the casting process has been modified over the history of the advanced fuels campaign as well as the physical parameters of the fuels cast in fiscal year 2016.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Co-Design: Fabrication of Unalloyed Plutonium

The successful induction casting of plutonium is a challenge which requires technical expertise in areas including physical metallurgy, surface and corrosion chemistry, materials science, electromagnetic engineering and a host of other technologies all which must be applied in concert. Here at LANL, we are employing a combined experimental and computational approach to design molds and develop process parameters needed to produce desired temperature profiles and improved castings. Computer simulations are performed using the commercial code FLOW-3D and the LANL ASC computer code TRUCHAS to reproduce the entire casting process starting with electromagnetic or radiative heating of the mold and metal and continuing through pouring with coupled fluid flow, heat transfer and non-isothermal solidification. This approach greatly reduces the time required to develop a new casting designs and also increases our understanding of the casting process, leading to a more homogeneous, consistent product and better process control. We will discuss recent casting development results in support of unalloyed plutonium rods for mechanical testing.

CASTING↗

Corrosion Behavior of B and Ti Grain-Refined Sr-Modified A356

Corrosion behavior of A356 aluminum alloy with different grain refiners was evaluated. For this purpose, the Sr-modified A356 alloy was grain refined with Al5Ti1B and Al3B, and then, the corrosion characteristics were determined. For the mechanical properties, impact and Vickers hardness tests were carried out. To determine the corrosion behavior, both the electrochemical impedance spectroscopy technique and by potentiodynamic polarization plots were carried out in a 3.5 wt.% NaCl solution at 25 °C. The corrosion resistance of A356 alloy was dramatically improved in sequence with the following modifications compared to the unmodified castings: Sr, Ti and B additions. This situation applies to both different cooling rates, namely die and sand casting. The increase in corrosion rate was more than 80% for all alterations of the microstructure. Additionally, charge transfer resistance was increased ten times in die cast samples, while this value was 2.5 for sand cast samples compared to the unmodified alloy. It is important to note that sand casting of the unmodified alloy was improved four times with regard to the die cast unmodified A356.

36 MATERIALS SCIENCE↗

Additively Manufactured Single-Use Molds and Reusable Patterns for Large Automotive and Hydroelectric Components

Additive manufacturing (AM) has the potential to reduce costs in the casting industry, particularly for large parts (i.e., components with any dimension > 12 in.). In this study, pilot-scale production case studies of hydroelectric and automotive parts were used to evaluate two AM-enabled casting methods: the direct printing of sand molds by binder jet and printing of reusable cope and drag patterns for sand casting. An additional benefit was found when additively manufactured patterns were used in combination with heat-treat free aluminum alloys, to produce castings of complex hydrodynamic surfaces. These parts previously required production via subtractive machining due to part distortion induced by the quench step of heat treatments. The machine types used for the three case studies are sand-binder jet, high-resolution polymer fused deposition modeling (FDM), and big area additive manufacturing (BAAM) FDM in combination with CNC machining. Each method demonstrated distinct advantages over traditional casting practices in particular use cases. Single-use molds show great reductions in start-up cost to produce one-off or legacy parts, and additively manufactured impression patterns show promise for innovating the tooling design process for complex geometry and large castings.

36 MATERIALS SCIENCE↗

Chrysler Upset Protrusion Joining Techniques for Joining Dissimilar Metals

The project goal was to develop and demonstrate a robust, cost effective, and versatile joining technique, known as Upset Protrusion Joining (UPJ), for joining challenging dissimilar metal com-binations, especially those where one of the metals is a die cast magnesium (Mg) component. Since two of the key obstacles preventing more widespread use of light metals (especially in high volume automotive applications) are 1) a lack of robust joining techniques and 2) susceptibility to galvanic corrosion, and since the majority of the joint combinations evaluated in this project include die cast Mg (the lightest structural metal) as one of the two materials being joined, and since die casting is the most common and cost effective process for producing Mg components, then successful project completion provides a key enabler to high volume application of lightweight materials, thus potentially leading to reduced costs, and encouraging implementation of lightweight multi-material vehicles for significant reductions in energy consumption and reduced greenhouse gas emissions. Eco-nomic benefits to end-use consumers are achieved primarily via the reduction in fuel consumption. Unlike currently available commercial processes, the UPJ process relies on a very robust mechanical joint rather than intermetallic bonding, so the more cathodic material can be coated prior to joining, thus creating a robust isolation against galvanic attack on the more anodic material. Additionally, since the UPJ protrusion is going through a hole that can be pre-drilled or pre-punched prior to coating, the UPJ process is less likely to damage the coating when the joint is being made. Further-more, since there is no additional cathodic material (such as a steel fastener) used to create the joint, there is no joining induced galvanic activity beyond that of the two parent materials. In accordance with its originally proposed plan, this project has successfully developed process variants of UPJ to enable joining of Mg die castings to aluminum (Al) and steel sheet components of various thicknesses, strengths and coating configurations. While most development focused on the simpler round boss version of the process, an additional phase of the work focused on devel-opment of an oval boss version to support applications with narrow flanges, while yet another vari-ant of the process, known as Upset Cast Riveting (UCR), was developed and evaluated for joining mixed metals that may not necessarily include Mg or Al die cast components. Although each varia-tion posed unique challenges described later in the report, all variations were successfully produced and evaluated, and each could be further developed for specific types of commercial applications. In this project, UPJ performed favorably against the benchmark self-pierce riveting (SPR) process in Mg AM60B to Al 6013 combinations although significant corrosion challenges were observed in both processes, especially for the bare Mg to bare Al configurations. Additional challenges were observed in joining Mg to steel with the UPJ process (SPR was not evaluated for this combination as it was not considered viable). To pass FCA’s specified corrosion tests with Mg/steel combina-tions, new steel treatments were evaluated, as well as adhesives and sealed edges. These showed significant improvement. In general, UPJ performed very well in Mg to Al 6016 combinations, even in corrosion evaluation of the bare Mg to bare Al configuration (again, SPR was not evaluated for this material combination as the 1.1 mm thick Al6016 sheet thickness was considered too thin for the SPR process). The improvement in corrosion performance of the Mg to Al 6016 combina-tion over the Mg to Al 6013 combination was thought to be a result of the lower copper content in the Al 6016 alloy. Oval boss joints showed substantial improvement in all joint strength criteria compared to 8.0-mm diameter round boss joints but were not evaluated for corrosion performance. The improved joint strength is likely a result of larger shear area. Cosmetic corrosion performance of all test assemblies (UPJ, UCR and SPR) was a challenge due to exposed edges and crevices al-lowing undercutting of the coatings. In real world component applications, the exposed edges, so prevalent on the joining test coupons, would be less prevalent and easier to protect.

36 MATERIALS SCIENCE↗

Positron annihilation lifetime spectroscopy study of polyvinylpyrrolidone‐added polyvinylidene fluoride membranes: Investigation of free volume and permeation relationships

ABSTRACT Polyvinylidene fluoride (PVDF) membranes were prepared via the phase inversion method from casting solutions containing PVDF, dimethylformamide (DMF), and polyvinylpyrrolidone (PVP) as pore former. PVP was used in the casting solution in a range of 0–5 wt % and extracted. The effect on membranes of using PVP in the casting process was analyzed by X‐ray diffraction, differential scanning calorimetry, scanning electron microscopy, viscosity, and water permeability techniques. With an increase of PVP from 0 to 5 wt %, the PVDF casting solution viscosities increased from 858 to 1148 cP; the resulting PVDF membrane thickness increased; and the crystallinity of PVDF membranes decreased from 40.0 to 33.3%, which indicates that the addition of PVP inhibits the degree of crystallization in the PVDF membranes. SEM results revealed the shape and size of macropores in the membranes; these macropores changed after PVP addition to the casting solutions. The impact of structural changes on free‐volume properties was evaluated using positron annihilation lifetime spectroscopy (PALS) studies. PALS analysis indicated no effect on the average radius (~3.4 Å) of membrane free‐volume holes from the addition of PVP to the casting solution. However, the percentage of o ‐Ps pick‐off annihilation intensity, I 3 , increased from 1.7 to 5.1% with increased PVP content. Further, increasing the PVP content from 0.5 to 5% resulted in an increased final pure water permeability flux. For instance, the 210 min flux for a 14% PVDF + 0.5% PVP membrane was found to be 3.3 times greater than a control membrane having the same PVDF concentration. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58 , 589–598

Eren, Bilge↗

Processing of High-Entropy AlCoCr{sub 0.75}Cu{sub 0.5}FeNi Alloy by Spray Forming

Compositionally complex AlCoCrCuFeNi alloy system is one of the extensively studied high-entropy alloys (HEA). Most of these studies have been carried out on as-cast materials that witness slow cooling rate during solidification. In the present investigation, HEA based on AlCoCrCuFeNi system was processed employing spray forming so as to realize its inherent rapid solidification effect and unique microstructural evolution mechanism. The spray formed as well as the as-cast alloys were compared in terms of their microstructural features, phase constitution and hardness. These microstructural features were also compared with that of the overspray powders (< 250 µm) obtained as a by-product of spray forming. Both the as-cast and spray formed alloys showed a mixture of mainly two phases, i.e., face-centered and body-centered cubic (BCC) phases, in contrast to a single BCC phase in overspray powders. However, the spray formed alloy revealed unidentified phases, as against the as-cast material, which disappeared after heat treatment at 1473 K for 3 h. The grain size of the as-cast alloy was around 600-1000 μm compared to a highly refined grain size of 25-30 μm in the as-spray formed alloy. It was found that the hardness of the regions dominated by the constituent phases as well as the bulk of the spray formed material was higher than that of the as-cast alloy. The results validate the efficacy of the process in achieving drastic refinement in grain size, in a single step of large-scale spray forming. The characteristic microstructural features and the phase constitutions have been discussed in light of the prevailing mechanisms of structural evolution and possible solidification phenomena during spray atomization and deposition. This study gives a new direction in processing of these alloys and understanding their solidification behavior under the conditions of layer-by-layer deposition of semi-solid/liquid droplets.

36 MATERIALS SCIENCE↗

Preparation of defect-free asymmetric gas separation membranes with dihydrolevoglucosenone (Cyrene TM ) as a greener polar aprotic solvent

Nonsolvent-induced phase separation (NIPS) is widely used to prepare asymmetric gas separation membranes. Most industrial NIPS casting solution formulations are limited to a small group of glassy polymers and, importantly, require toxic polar aprotic solvents such as N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), or N-methyl-2-pyrrolidone (NMP). Growing restrictions on the use of such solvents are spurring the search for more benign casting solution formulations that do not compromise membrane performance. Herein this study reports high-flux, defect-free asymmetric polysulfone (PSf) gas separation membranes prepared using dihydrolevoglucosenone (Cyrene TM ), a polar aprotic solvent that is believed to be safer than DMAc, DMF, and NMP, as the majority casting solution component. Optimized formulations and casting conditions produce membranes with hydrogen permeances exceeding 100 gas permeance units (GPU) and selectivities at or above those of dense PSf films. Dry/wet NIPS membrane performance improved with shorter dry step times and increased Cyrene TM loadings relative to the volatile solvent, tetrahydrofuran (THF), in the casting solution. The high water-Cyrene TM Flory-Huggins interaction parameter, $\mathcal{X}12$ , and high casting solution viscosities help suppress the formation of skin layer defects and sublayer macrovoids. In some cases, membrane selectivities were influenced by substructure resistance, providing insight into the relationship between sublayer morphology and membrane performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Repurposing the θ (Al 2 Cu) phase to simultaneously increase the strength and ductility of an additively manufactured Al–Cu alloy

The Al–Cu–Mn–Zr (ACMZ) cast family of alloys offers unique properties and value propositions for higher strength, higher temperature lightweight components of future vehicles. Earlier research has demonstrated trade-offs in the selection of the alloy chemistry in which an increase in Cu content from 6 up to 9 wt% improves hot tear resistance but lowers ductility. However, a recent study has demonstrated that higher-Cu (9Cu) ACMZ fabricated with laser powder bed fusion additive manufacturing (AM) results in an increase in both ductility and strength when compared to as-aged microstructure of cast 9Cu alloys. The mechanisms of differing mechanical performance of the cast and AM ACMZ alloys are elucidated in the current paper through the utilization of in situ high energy x-ray diffraction (HEXRD) tensile testing wherein lattice strains of different phases are calculated and correlated to their stresses. The ACMZ alloys consisted of theta (θ) and theta prime (θ') phases (both Al 2 Cu in nominal composition) within an aluminum matrix. The larger micron-size θ phase which decorated the grain boundaries in 9Cu ACMZ cast alloys recorded small lattice strains, while the submicron, homogeneously distributed θ phase in the 9Cu ACMZ AM alloy recorded considerably higher lattice strains. The maximum stress reached in the θ phase for the cast 9Cu alloy was found to be ~280 MPa, which was lower than the AM 9Cu alloy which registered a maximum stress of ~1.4 GPa. These measurements indicate that delayed fracture of the finer intermetallic phases simultaneously improves the ductility and strength of AM 9Cu alloy relative to the cast 9Cu alloy, which exhibits early fracture of the larger intermetallic particles.

36 MATERIALS SCIENCE↗

Solvent-Free Melt-Processed Cathode Mitigates Li Anode Instability in Polymer-Based Solid-State Batteries

Solvent-free manufacturing of battery components is a promising alternative to traditional slurry processing for reducing the cost and environmental impact. In this work, we used twin-screw melt extrusion to fabricate a polymer-based high voltage composite cathode. The melt-processed cathode is dense (near zero porosity) and thick (65 μm) and has high active material loading (80 wt %). The active particles are distributed uniformly throughout the melt-processed cathode, unlike the traditional slurry-cast cathode, which exhibits inhomogeneous particle distribution. In the melt-processed cathode, polymer and carbon form separate phases, whereas in the slurry-cast cathode they blend into a single phase. Due to these structural differences, the melt-processed cathode shows smooth charge–discharge profiles, while the slurry-cast cathode shows noisy charging and soft-shorting behavior. In conclusion, this work highlights that twin-screw extrusion as a scalable, solvent-free manufacturing method is advantageous in producing uniform cathodes, which mitigates anode instability.

25 ENERGY STORAGE↗

Studies on magnetocaloric effect of Tb 2 Ni 0.90 Si 2.94 compound

A comparative study has been carried out on the magnetocaloric properties of as-cast and annealed Tb 2 Ni 0.90 Si 2.94 intermetallic compound. While the as-cast material exhibits ferromagnetic cluster-glass behaviour below 9.9 K coexisting with antiferromagnetic (AFM) interaction, the annealed system shows AFM ordering below 13.5 K and spin freezing occurs below 4 K. The compound exhibits moderate magnetocaloric performance with maximum isothermal entropy changes (–ΔS M ) 8.8 and 10.9 J kg –1 K –1 , relative cooling power (RCP) 306 and 365 J kg –1 , along with adiabatic temperature change (ΔT ad ) 5.5 and 8.15 K for 70 kOe magnetic field change in as-cast and annealed forms, respectively. The estimated magnetic entropy change is found to be larger for annealed sample in comparison to that of as-cast analogue. However, the full width at half maxima (FWHM) of –ΔS M (T) behaviour is larger in as-cast compound due to the presence of inherent structural disorder which reduces with thermal annealing. A positive isothermal entropy change (–ΔS M ) and adiabatic temperature change (ΔT ad ) is observed for the as-cast compound in the measured field and temperature region. In contrast, the annealed system exhibits inverse magnetocaloric effect in the low field and temperature region where AFM interactions dominate. Magnetocaloric effect (MCE) is used as a tool to establish a subtle correlation between the observed magnetocaloric effect and the reported magnetic properties of the system.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Radiation behavior of high-entropy alloys for advanced reactors. Final report

In the first task, we have demonstrated the radiation damage and the recrystallization behaviors in multicomponent alloys through molecular-dynamics simulations. It is found that by alloying with atoms of different sizes, the atomic-level strain increases, and the propensity of the radiation-induced crystalline to amorphous transition increases as the defects cluster in the cascade body. Recrystallization of the radiation induced supercooled or glass regions show that by tuning the composition and the equilibrium temperature, the multicomponent alloys can be healed. The crystalline-amorphous-crystalline transitions predict the potential high radiation resistance in multicomponent alloys. In the second task, three types of high-entropy alloys (HEAs) were fabricated from AlCoCrFeNi and AlCuCrFeNi quinary alloys. Hardness and reduced contact modulus were measured using nanoindentation tests. Heavy ion irradiation were performed using 10 MeV gold and 5 MeV nickel to study radiation effects. Al 0.5 CrCuFeNi 2 shows phase separation upon the presence of copper. Both hardness and contact modulus exhibit the same trend as increasing the applied load, and it indicates that excessive free volume may alter the growth rate of the plastic zone. The as-cast Al 0.1 CoCrFeNi specimen undergone the hot isostatic pressing (HIP) process and steady cooling rate which mitigate the quenching effect. The swelling behavior was characterized by the atomic force microscopy (AFM), and the swelling rate is approximately 0.02% dpa. Selected area diffraction (SAD) patters show irradiation-induced amorphization throughout the ion projected range. Within the peak damage region, an amorpous ring is observed, and a mixture of amorphous/ crystalline structure at deeper depth is found. The Al 0.3 CoCrFeNi HEAs shows good radiation resistance up to 60 peak dpa. No voids or dislocations are observed. The crystal structures remain face-centered-cubic (FCC) before and after 5 MeV Ni irradiation. Higher dpa might be required to study defects formation mechanisms. In the third task, all the constituent binary and ternary systems of the Al-Co-Cr-Fe-Ni system were thermodynamically modeled within the whole composition range. Comparisons between the calculated phase diagrams and literature data are in good agreement. The multi-component thermodynamic database of the Al-Co-Cr-Fe-Ni system was then obtained via extrapolation. The current Al-Co-Cr-Fe-Ni thermodynamic database enables us to carry out the calculations of phase diagrams, which can be used as useful guidelines to identify the Al-Co-Cr-Fe-Ni HEAs with desirable microstructures. In the fourth task, we discuss how as-cast and homogenized phases can be identified, what phases are usually found in the as-cast and homogenized conditions, and what the thermodynamics and kinetics of phase transformations are in the AlCoCrFeNi HEA. The microstructure and phase composition were studied in as-cast and homogenized conditions. It showed the dendritrical structure in the as-cast condition consisting primarily of a nano-lamellar mixture of A2 [disorder body-centered-cubic (BCC)] and B2 (ordered BCC) phases, in addition to a very small amount of A1 [disorder face-centered-cubic (FCC)] phases. The homogenization heat treatment resulted in an increase in the volume fraction of the A1 phase and formation of a Sigma phase. Tensile properties in as-cast and homogenized conditions are reported at 700 °C. Thermodynamic modeling of non-equilibrium and equilibrium phase diagrams for the AlCoCrFeNi HEA gave good agreement with the experimental observations of the phase contents. The reasons for the improvement of ductility after the heat treatment are discussed.

36 MATERIALS SCIENCE↗

Development of Novel Ferritic-Martensitic Steels with Superior Creep Properties for Power Plant Applications

A creep resistant martensitic steel, CPJ-7, was developed with an operating temperature approaching 650°C. Subsequently, another creep resistant martensitic steel, JMP, was designed with the potential to operate at, or slightly above, 650°C. This report describes the development of these alloys from early iterations of CPJ steels to the final CPJ-7 formulation as well as the more heat resistant JMP steel formulation. The design originated from computational modeling for phase stability and precipitate strengthening using fifteen constituent elements. Approximately forty heats of CPJ and ten of JMP, each weighing ~7 kg, were vacuum induction melted. A computationally optimized heat treatment schedule was developed to homogenize the ingots prior to hot forging and rolling prior to final normalization and tempering. Overall, wrought and cast versions of CPJ-7 present superior creep properties when compared to wrought and cast versions of COST alloys for steam turbine and wrought and cast versions of P91/92 for boiler applications. For instance, the Larson Miller Parameter curve for CPJ-7 at 650°C almost coincides with that of COST E at 620°C. The prolonged creep life was attributed to slowing down the process of the destabilization of the MX and M 23 C 6 precipitates at 650°C. On the other hand, the cast version of CPJ-7 also revealed superior mechanical performance, well above commercially available cast 9% Cr martensitic steel or derivatives, especially for creep life at 650°C. The casting process employed slow cooling to simulate the conditions of a thick wall full-size steam turbine casing but utilized a separate homogenization step prior to final normalization and tempering. To advance the development of CPJ-7 for commercial applications, a process was used to scale up the production of the alloy using vacuum induction melting (VIM) and electroslag remelting (ESR), which underlined the importance of melt processing control of intentionally designed minor and trace elements in these advanced alloys. Following the work on CPJ-7, the JMP steels were designed with higher Co for increased solid solution strengthening, Si for oxidation resistance and increased W (with low Mo content) for matrix strength and stability as well as solid solution strengthening. The JMP steels showed increases in creep life compared to CPJ-7 between 118 to 150% at 650°C for testing at various stresses between 138 MPa and 207 MPa. On a Larson-Miller plot, the performance of the JMP steels surpasses that of state-of-the-art MARBN and other MARBN-type steels. The influence of various elements within the composition of the alloys on the microstructure and mechanical properties are discussed. This report presents approximately 420,000 h of in-house creep testing, the equivalent of almost 50 years of cumulative creep tests.

36 MATERIALS SCIENCE↗