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Abstract The oxidation of chromium in air at 700 °C was investigated with a focus on point defect behavior and transport during oxide layer growth. A comprehensive set of characterization techniques targeted characteristics of chromium oxide microstructure and chemical composition analysis. TEM showed that the oxide was thicker with longer oxidation times and that, for the thicker oxides, voids formed at the metal/oxide interface. PAS revealed that the longer the oxidation time, there was an overall reduction in vacancy-type defects, though chromium monovacancies were not found in either case. EIS found that the longer oxidized material was more electrochemically stable and that, while all oxides displayed p-type character, the thicker oxide had an overall lower charge carrier density. Together, the results suggest anion oxygen interstitials and chromium vacancy cluster complexes drive transport in an oxidizing environment at this temperature, providing invaluable insight into the mechanisms that regulate corrosion.

The grade 91 ferritic/martensitic steel is considered a promising structural or cladding material for various nuclear reactor applications. Here, grade 91 was fabricated via the Directed Energy Deposition Laser technique. This alternative manufacturing process potentially enables tailoring of the mechanical properties through increased control of the product’s microstructure.Aimed at linking fabrication to performance via defining the process-structure–property relationships, the current research includes macro and up to nano-scale mechanical testing using microhardness, tensile, and in-situ nanoindentation hardness, coupled with electron diffraction-based microstructure characterization. Mapping of the product structure and properties was conducted by testing miniature-sized samples, parallel to the built direction (‘Z’ direction) and perpendicular (‘X’ direction) at constant distances.We found the majority of the microstructure consists of fine and coarsened-size lath-type martensite grains, with up to 15% δ-phase, preferentially observed at the melt pool boundaries. Most intriguing was the gradual decrease found in observed metallurgical pores alongside softening at farthest distances from the cold build platform. Here, these changes were successfully explained in terms of phase composition, ‘grain-like’ size effects of the lath-type martensite, and geometry necessary dislocation density. In finalizing this work, several competing strengthening mechanisms were addressed, and their activity was considered owing to fabrication-related mechanisms.

Nickel-based alloys are extensively used in a wide range of extreme environments because of their exceptional mechanical properties. The excellent strength of these alloys is derived from the addition of long-range ordered precipitates, introduced by thermal aging. The interactions between the dislocations and LRO precipitates dictate the deformation modes and plastic response in these alloys. While the majority of studies have focused on L12-structured precipitate-strengthened Ni-based alloys, less work has considered the Ni-based alloys containing Pt2Mo-structured, Ni2(Cr,Mo)-typed precipitates. In these alloys, Pt2Mo-structured precipitates enable room-temperature deformation twinning in addition to slip, which increases strain hardenability measured from bulk mechanical testing. Although previous geometric-based model suggested that deformation twinning is favored over slip, the factors that influence the activation between twinning versus slip have not been thoroughly explored in this class of Ni-based alloys. In this work, molecular dynamics examined the possible types of dislocation and Pt2Mo-structured precipitate interactions at low temperature. Combined with in situ micromechanical testing, the role of resolved shear stresses on dislocation partials were shown to directly influence the activation of slip versus twinning. Additionally, using an energy-based approach, molecular dynamics results demonstrated a novel twin formation process, caused by the dislocation interaction with the Pt2Mo-structured precipitates.

The quest for better nutritious foods has encouraged novel scientific investigations to find trans-fat reduction methods. This research proposes an innovative approach for the production of healthier trans-fat-free margarine from palm oil by the use of dielectric barrier discharge (DBD) plasma technology with glycerol serving as the principal source of hydrogen. The effectiveness of DBD plasma in hydrogenating palm olein was investigated. By employing a methodical series of experiments and thorough analytical approaches, examination of the saturated fatty acid conversion experienced its iodine value (IV) reduction from 67.16 ± 0.70 to 31.61 ± 1.10 under the optimal process parameters of 1 L min-1 He flow rate, 35 W plasma discharge power, 10 mm gap size, ambient initial temperature, and 12 h reaction time with solid texture. According to the method for producing trans-fat-free margarine in the absence of a catalyst and H2 gas, the hydrogenation rate of the prepared mixture of palm olein-glycerol was remarkably improved; the trans-fat content in the produced product was zero; the efficacy of incorporating cis- and trans-isomerization was lowered, and the method has a promising industrial application prospect.

The dealloying corrosion behavior of the FCC Ni20Cr (wt%) in molten LiF-NaF-KF (FLiNaK) salts at 600 °C under varying applied potentials was investigated. Using in-operando electrochemical techniques and a multi-modal suite of characterization methods, we connect electrochemical potential, thermodynamic stability, and electro-dissolution kinetics to the corrosion morphologies. Notably, under certain potential regimes, a micron-scale bicontinuous structure, characterized by a network of interconnected pores and ligaments riched with the composition of the more noble (MN) element, becomes prominent. At other potentials both MN and less noble (LN) elements dealloy but at different rates. The dealloying process consists of lattice and grain boundary diffusion of Cr to the metal/salt interface, interphase Cr oxidation, accompanied by surface diffusion of Ni to form interconnected ligaments. At higher potentials, the bicontinuous porous structure undergoes further surface coarsening. Concurrently, Cr(II), Cr(III), and Ni(II) begin to dissolve, with the dissolution of Ni occurring at a significantly slower rate. When solid-state transport of Cr is exceeded by the interfacial rates, dealloying depths are limited.

Joining of dissimilar metals is required for numerous applications in industries such as chemical, energy and automotive. It is challenging due to differences in melting point, density, and thermal expansion of the metals being joined. Common welding techniques involve limiting melting and solidification to a narrow area leading to high thermal stresses and potentially brittle intermetallic phases. Furthermore, the geometric complexity of these welded joints can be rather limited. Additive Manufacturing (AM) presents new techniques for joining of dissimilar metals. One of the emerging methods is the building of functionally graded parts using Directed Energy Deposition (DED) to spatially vary composition. In this paper, a SS316 L and C300 maraging steel couple were joined by DED and heat treated. 13 discrete composition layers were selected using metallurgical considerations, in order to ensure a smooth transition in properties and microstructure. The mechanical properties of the as-built joints were found to be similar to the SS part and no intermetallic phases were found in the interface.

Lead-bismuth eutectic (LBE) is a promising heat transfer fluid candidate for fast-neutron nuclear reactors and for concentrating solar power systems, due to its low melting point and advantageous thermophysical properties, but suffers from causing liquid-metal corrosion in many solids used as structural materials. Adding a suitable element to LBE to form a ternary alloy, along with proper oxygen concentration in LBE at desired temperature, might provide a formation of the protective intermetallic layers besides the formation of protective oxides on the solid surface. In this study, novel Pb-Bi-X alloys, as improvement LBE, have been designed for a broad temperature range, with X additions selected based on thermodynamic considerations and modeling, and experimentally evaluated at 700 °C. Thermodynamic calculations indicated Pb-Bi-Sb and Pb-Bi-Ge as the best candidates, and experiments provided some evidence of possible intermetallic formation of Sb with Fe-Cr-Al alloy constituents. The work pointed to the need for further research into the compatibility with structural materials at high temperatures. Keywords: Solar energy, Heat transfer, Liquid metal, Oxygen control, Fe-Cr-Al alloy

Ion irradiation is often used to simulate the effects of neutron irradiation due to reduced activation of materials and vastly increased dose rates. However, the low penetration depth of ions requires the development of small-scale mechanical testing techniques, such as nanoindentation and microcompression, in order to measure mechanical properties of the irradiated material. In this study, several candidate structural alloys for Gen-IV reactors (800H, T91, nanocrystalline T91 and 14YWT) were irradiated with 70 MeV Fe9+ ions at 452 °C to an average damage of 20.68 dpa. Both the nanoindentation and microcompression techniques revealed significant irradiation hardening and an increase in yield stress after irradiation in austenitic 800H and ferritic-martensitic T91 alloys. Ion irradiation was observed to have minimal effect on the mechanical properties of nanocrystalline T91 and oxide dispersion strengthened 14YWT. These observations are further supported by line broadening analysis of X-ray diffraction measurements, which show a significantly smaller increase in dislocation density in the 14YWT and nanocrystalline T91 alloys after irradiation. In addition, good agreement was observed between cross-sectional nanoindentation and the damage profile from SRIM calculations.

Focused ion beam (FIB) milling techniques have been used for more than a decade to prepare organic-rich shale samples for electron microscopy. Nano- and micro-scale imaging of organic pores is used to assess pore volumes and hence estimate gas-in-place. Ion milling natural composites is particularly challenging due to drastic extremes in the physical properties of individual phases such as minerals and organics. Damage to the organic-rich phases occurs due to the large differences in thermal conductivities of minerals and organics that could reach an order of magnitude and the resulting buildup of heat in the organics. Furthermore, radiation damage via ion implantation may also alter the structural characteristics of the shale. Herein, the damage associated with preparing electron-transparent kerogen specimen using low kV FIB, cryo-FIB, and cryomicrotome, a new technique for shale kerogen, is quantified using experimental and modeling techniques. The degree of gallium implantation is quantified using scanning transmission electron microscopy (STEM), selected area electron diffraction (SAED), and energy dispersive X-ray spectroscopy (EDX) along with the stopping range of ions in matter (SRIM) model. Interestingly, although the use of cryogenic temperature removes the thermal effect, Ga+ ion implantation is observed in the specimen prepared by cryo-FIB. Furthermore, the magnitude of the thermal damage at a highly localized level was determined using nano-beam electron diffraction (NBED) performed at −196 °C. Time-resolved diffraction patterns indicate that despite the fact kerogen is among the most stable geopolymers, the aromatic components still degraded due to the local temperature increases. On the other hand, the cryomicrotome technique operating at liquid nitrogen temperature is demonstrated as a suitable method to prepare thin kerogen specimen while minimizing structural damage and preserving its native porosity and chemical composition.

Lithium phosphorus oxynitride (LiPON) is an amorphous solid electrolyte that has been extensively studied over the last three decades. Despite the promise of pairing it with various electrode materials, LiPON's rigidity and air sensitivity set limitations to understanding its intrinsic properties. Here we report a methodology to synthesize LiPON in a free-standing form that manifests remarkable flexibility and a Young's modulus of ∼33 GPa. We use solid-state nuclear magnetic resonance and differential scanning calorimetry to quantitatively reveal the chemistry of the Li/LiPON interface and the presence of a well-defined LiPON glass-transition temperature of 207 °C. Combining interfacial stress and a gold seeding layer, our free-standing LiPON shows a uniformly dense deposition of lithium metal without the aid of external pressure. This free-standing LiPON film offers opportunities to study fundamental properties of LiPON for interface engineering for solid-state batteries.

Adsorption is regarded as an efficient method to eliminate per- and polyfluoroalkyl substances from an aqueous solution. In the present investigation, an adsorbent based on rice husks (RHs) was successfully prepared by phosphoric acid (PA) activation and dielectric barrier discharge (DBD) plasma treatment, and it was used to adsorb perfluorooctanoic acid (PFOA) from water. The electrodes employed in the experiment were planar type. This research investigated RH surface properties and adsorption capacity before and after modification using DBD plasma. The results revealed that the He-O2 plasma modification introduced oxygen-containing functional groups and increased the PFOA removal efficiency. Increasing the oxygen content and total gas flow rate to 30 vol.% and 1.5 L/min, respectively, with 10 min of RH plasma treatment time at 100 W plasma discharge power enhanced the PFOA removal efficiency to 92.0%, while non-treated RH showed the removal efficiency of only 46.4%. The removal efficiency of the solution increased to 96.7% upon adjusting the pH to 4. The adsorption equilibrium isotherms fitted the Langmuir model, and the adsorption kinetic followed the pseudo-second-order model. The maximum adsorption capacity was 565 mg/g when the Langmuir isotherm model was applied.

Ion beam implantations are widely performed to understand the effects of irradiation-induced displacement damage on nuclear structural materials. However, the volume of material that can be investigated is often limited by the maximum energies of accelerator facilitates, leading to a limitation in the thickness of samples whose mechanical properties can be evaluated. The Lawrence Berkeley National Laboratory's 88-Inch Cyclotron offers a wide range of ions and energies, allowing for material ion implantations at larger scales than typical. Four HT-9 SS-J-geometry tensile specimens were polished and then irradiated with deuterons at the 88-Inch Cyclotron to doses of approximately 0.2 dpa prior to small scale tensile testing. The results from this study show irradiation hardening characterized by the tensile test results and black dot irradiation defects. Additionally, a comprehensive look at low temperature irradiations of high-Cr F/M steels is presented and our results show agreement with the available data.

The Advanced Fuels Campaign performed a series of irradiation tests of minor actinide-bearing mixed oxide fuel (MA-MOX), the so-called AFC-2C&D experiments, to investigate the transmutation of long-lived transuranic actinide isotopes contained in spent nuclear fuel via fast reactor technology at burnups exceeding 10 % fission of initial metallic atoms. This manuscript reports the test results derived from one of the five MA-MOX rodlets taken to higher burnup in the AFC-2D irradiation. This includes both non-destructive investigations, such as gamma and neutron spectrometry, and destructive investigations, such as fission gas release, ceramography, and chemical burnup analysis. In addition, the microstructure of the fuel was investigated using advanced electron microscopy techniques including electron backscatter diffraction (EBSD) and transmission electron microscopy (TEM). It was observed with EBSD that the pellet had subdivision of the grains and the TEM observed migration of cladding material into the 5 metal precipitates in the fuel which could have been from the higher than desired oxygen/metal ratio. The TEM also showed an enrichment of Cr in fuel clad chemical interaction (FCCI) layer.

SPT-3G is the third survey receiver operating on the South Pole Telescope dedicated to high-resolution observations of the cosmic microwave background (CMB). Sensitive measurements of the temperature and polarization anisotropies of the CMB provide a powerful data set for constraining cosmology. Additionally, CMB surveys with arcminute-scale resolution are capable of detecting galaxy clusters, millimeter-wave bright galaxies, and a variety of transient phenomena. The SPT-3G instrument provides a significant improvement in mapping speed over its predecessors, SPT-SZ and SPTpol. The broadband optics design of the instrument achieves a 430 mm diameter image plane across observing bands of 95, 150, and 220 GHz, with 1.2′ FWHM beam response at 150 GHz. In the receiver, this image plane is populated with 2690 dual-polarization, trichroic pixels ( 1/416,000 detectors) read out using a 68× digital frequency-domain multiplexing readout system. In 2018, SPT-3G began a multiyear survey of 1500 deg2 of the southern sky. We summarize the unique optical, cryogenic, detector, and readout technologies employed in SPT-3G, and we report on the integrated performance of the instrument.

The oxidation of chromium in air at 700 °C was investigated with a focus on point defect behavior and transport during oxide layer growth. A comprehensive set of characterization techniques targeted characteristics of chromium oxide microstructure and chemical composition analysis. TEM showed that the oxide was thicker with longer oxidation times and that, for the thicker oxides, voids formed at the metal/oxide interface. PAS revealed that the longer the oxidation time, there was an overall reduction in vacancy-type defects, though chromium monovacancies were not found in either case. EIS found that the longer oxidized material was more electrochemically stable and that, while all oxides displayed p-type character, the thicker oxide had an overall lower charge carrier density. Together, the results suggest anion oxygen interstitials and chromium vacancy cluster complexes drive transport in an oxidizing environment at this temperature, providing invaluable insight into the mechanisms that regulate corrosion.

Understanding the impact of microstructure on the thermo-mechanical behavior of oxide nuclear fuels is vital to predicting their performance through multiscale models. Evaluating the mechanical properties at the sub-grain length scale is key to developing these multiscale models. In this work, 3D finite element (FE) models were constructed to simulate the micrometer-scale bending of micro-cantilever beams fabricated using porous polycrystalline uranium dioxide (UO2) and tested at room temperature. The results showed that the porosity and elastic anisotropy of individual grains can play a significant role in determining the effective mechanical properties of the material deduced from the tests. Specifically, the porosity had a non-negligible effect, given that the pore size was of the same order of magnitude as the dimensions of the micro-beams. Correlations between load-deflection data, pore location, and elastic properties (effective Young's modulus) were investigated using UO2 micro-beam FE models, where pore clusters were included and placed at different locations along the length of the beam. Results indicated that the presence of pore clusters near the substrate, i.e., the clamp of the micro-cantilever beam, has the strongest effect on the load-deflection behavior, with the porosity leading to a reduction of stiffness that is the largest for any location of the pore clusters. Furthermore, it was also found that pore clusters located towards the middle of the span and close to the end of the beam have a comparatively small effect on the load-deflection behavior. Therefore, it is concluded that accurate estimates of Young's modulus can be obtained from micro-cantilever experiments after accounting for porosity on the one third of the beam length close to the clamp. This, in turn, provides an avenue to improve microscale experiments and their analysis in porous, anisotropic elastic materials.

We present constraints on extensions to the ΛCDM cosmological model from measurements of the E-mode polarization autopower spectrum and the temperature-E-mode cross-power spectrum of the cosmic microwave background (CMB) made using 2018 SPT-3G data. The extensions considered vary the primordial helium abundance, the effective number of relativistic degrees of freedom, the sum of neutrino masses, the relativistic energy density and mass of a sterile neutrino, and the mean spatial curvature. We do not find clear evidence for any of these extensions, from either the SPT-3G 2018 dataset alone or in combination with baryon acoustic oscillation and Planck data. None of these model extensions significantly relax the tension between Hubble-constant, H0, constraints from the CMB and from distance-ladder measurements using Cepheids and supernovae. The addition of the SPT-3G 2018 data to Planck reduces the square-root of the determinants of the parameter covariance matrices by factors of 1.3-2.0 across these models, signaling a substantial reduction in the allowed parameter volume. We also explore CMB-based constraints on H0 from combined SPT, Planck, and ACT DR4 datasets. While individual experiments see some indications of different H0 values between the TT, TE, and EE spectra, the combined H0 constraints are consistent between the three spectra. For the full combined datasets, we report H0=67.49±0.53 km s-1 Mpc-1, which is the tightest constraint on H0 from CMB power spectra to date and in 4.1σ tension with the most precise distance-ladder-based measurement of H0. The SPT-3G survey is planned to continue through at least 2023, with existing maps of combined 2019 and 2020 data already having ∼3.5×lower noise than the maps used in this analysis.

Above-ground nuclear explosions that interact with the surface of the earth entrain materials from the surrounding environment, influencing the resulting physical and chemical evolution of the fireball, which can affect the final chemical phase and mobility of hazardous radionuclides that are dispersed in the environment as fallout particles. The interaction of iron with a nuclear explosion is of specific interest due to the potential for iron to act as a redox buffer and because of the likelihood of significant masses of metals to be present in urban environments. We investigated fallout from a historic surface interacting nuclear explosion conducted on a steel tower and report the discovery of widespread and diverse iron-rich micro-structures preserved within the samples, including crystalline dendrites and micron-scale iron-rich spheres with liquid immiscibility textures. We assert these micro-structures reflect local redox conditions and cooling rates and can inform interpretation of high temperature events, enabling new insights into fireball condensation physics and chemistry when metals from the local environment (i.e. structural steel) are vaporized or entrained. These observations also significantly expand the availability of silicate immiscibility datasets applicable to rapidly quenched systems such as meteorite impact melt glass.

Fatty acid methyl esters (FAMEs) are sustainable biofuel that can alleviate high oil costs and environmental impacts of petroleum-based fuel. A modified 1200 W high-efficiency food blender was employed for continuous transesterification of various refined vegetable oils and waste cooking oil (WCO) using sodium hydroxide as a homogeneous catalyst. The following factors have been investigated on their effects on FAME yield: baffles, reaction volume, total reactant flow rate, methanol-oil molar ratio, catalyst concentration and reaction temperature. Results indicated that the optimal conditions were: 2000 mL reaction volume, 50 mL/min total flow rate, 1% and 1.25% catalyst concentration for refined palm oil and WCO, respectively, 6:1 methanol-to-oil molar ratio and 62-63 °C, obtaining yield efficiency over 96.5% FAME yield of 21.14 × 10-4 g/J (for palm oil) and 19.39 × 10-4 g/J (for WCO). All the properties of produced FAMEs meet the EN 14214 and ASTM D6751 standards. The modified household food blender could be a practical and low-cost alternative biodiesel production apparatus for continuous biodiesel production for small communities in remote areas.

The T91 grade and similar 9Cr tempered-martensitic steels (also known as ferritic-martensitic) are leading candidate structural alloys for fast fission nuclear and fusion power reactors. At low temperatures (300–400 °C) neutron irradiation hardens and embrittles these steels, therefore it is important to investigate the origin of this mode of life limiting property degradation. T91 steel specimens were separately neutron irradiated to 2.14 dpa at 327 °C and 8.82 dpa at 377 °C in the Idaho National Laboratory Advanced Test Reactor. Atom probe tomography was used to investigate the segregation driven formation of Mn–Ni–Si-rich (MNSPs) and Cu-rich (CRP) co-precipitates. The precipitates increase in size and, slightly, in volume fraction at the higher irradiation temperature and dose, while their corresponding compositions were very similar, falling near the Si(Mn,Ni) phase field in the Mn–Ni–Si projection of the Fe-based quaternary phase diagram. While the structure of the precipitates has not been characterised, this composition range is distinctly different than that of the typically cited G-phase. The precipitates are composed of CRP with MNSP appendages. Such features are often observed in neutron irradiated reactor pressure vessel (RPV) steels. However, the Si, Ni, Mn, P and Cu solutes concentrations are lower in the T91 than in typical RPV steels. Thus, in T91 precipitation primarily takes place in solute segregated regions of line and loop dislocations. These results are consistent with the model for radiation induced segregation driven precipitation of MNSPs proposed by Ke et al. Cr-rich alpha prime (α’) phase formation was not observed.

The impedance behavior of pre-oxidized iron in liquid lead-bismuth eutectic (LBE) at 200 °C is studied using electrochemical impedance spectroscopy. The structures and resistance of oxide grown on iron oxidized in air at different temperatures and durations are compared. The results show that the resistance of the oxide film increases with increasing oxidizing temperature, due to the formation of a thicker scale and fewer defects. At the same temperature (600 °C), increasing the oxidation time can also reduce the defect concentration in the oxide film and improve the impedance of the oxide scale in LBE.

The nondestructive investigation of single vacancies and vacancy clusters in ion-irradiated samples requires a depth-resolved probe with atomic sensitivity to defects. The recent development of short-pulsed positron beams provides such a probe. Here, we combine depth-resolved Doppler broadening and positron annihilation lifetime spectroscopies to identify vacancy clusters in ion-irradiated Fe and measure their density as a function of depth. Despite large concentrations of dislocations and voids in the pristine samples, positron annihilation measurements uncovered the structure of vacancy clusters and the change in their size and density with irradiation dose. When combined with transmission electron microscopy measurements, the study demonstrates an association between the increase in the density of small vacancy clusters with irradiation and a remarkable reduction in the size of large voids. This, previously unknown, mechanism for the interaction of cascade damage with voids in ion-irradiated materials is a consequence of the high porosity of the initial microstructure.