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At least 1,423 records · Page 79

Scanning tunneling microscope tip-induced formation of Bi bilayers on Bi 2 Te 3

We report the formation of Bi(111) bilayer islands and crater structures on Bi 2 Te 3 (111) surfaces induced by voltage pulses from a scanning tunneling microscope tip. Pulses above a threshold voltage (+3 V) produce craters ∼0.5μm in diameter, similar to the size of the tip. Redeposited material self-assembles into a network of atomically ordered islands with a lattice constant identical to the underlying Bi2Te3 surface. The island size monotonically decreases over several micrometers from the pulse site, until the pristine Bi 2 Te 3 surface is recovered. We assign these islands to Bi bilayer based on atomic resolution images, analysis of step heights, and tunneling spectroscopy. Here, the dependence of bilayer formation on bias polarity and the evidence for defect diffusion together suggest a mechanism driven by the interplay of field evaporation and tunneling-current-induced Joule heating.

Bi bilayer↗

Roles of Mn and Co in Ni-rich layered oxide cathodes synthesized utilizing a Taylor Vortex Reactor

It is reported that layered oxides, composed of nickel, manganese, and cobalt (NMC), are sought after as cathode materials which provide improved energy density, cycle life, and safety in commercial lithium ion batteries (LIBs). Increasing Ni contents higher than 80% can provide even higher practical discharge capacities >200 mAh/g and similar to ~4 V discharge potential vs Li/Li + , making them promising cathodes for next generation LIBs. However, rapid capacity fade during cycling and heat-related safety concerns are delaying their successful transition to industry. We report systematic performance optimization of LiNiO 2 , LiNi 0.9 Mn 0.1 O 2 , and LiNi 0.9 Co 0.1 O 2 high Ni layered oxide cathodes synthesized by utilizing a Taylor Vortex Reactor. Co-free LiNi 0.9 Mn 0.1 O 2 cathode showed 200 mAh/g highest discharge capacity at 0.1 C rate with 84% retention after 103 cycles at 0.3C rate while LiNi 0.9 Co 0.1 O 2 cathode showed higher initial but poor cycle life (225 mAh/g highest discharge capacity at 0.1C rate with only 56% capacity retention after 103 cycles at 0.3 C rate. Synchrotron based X-ray diffraction (SXRD), X-ray absorption spectroscopy (XAS) and focused ion beam (FIB) imaging of pristine and cycled cathodes after 103 cycles provided important information on degradation mechanism. The roles of Mn and Co on layered structure formation, charge balance, cationic mixing, and electrochemical performance were elucidated using the crystallographic information from XRD refinement and electronic state analysis from XAS providing valuable information to design future Ni-rich layered oxide cathodes.

25 ENERGY STORAGE↗

Microstructure and fission products in the UCO kernel of an AGR-1 TRISO fuel particle after post irradiation safety testing

Tristructural isotropic (TRISO) coated particle fuel as a key fuel concept for the High Temperature Gas-cooled Reactors (HTGRs) and a candidate accident tolerant fuel (ATF) has been currently investigated under the US-DOE Advanced Gas Reactor (AGR) fuel development and qualification program. Over the past decades, extensive studies have been conducted to evaluate the fission product release, diffusion on Ag, Pd and Cd in the SiC layer and the TRISO coating system, and post-safety-test performance. However, to date, there are limited reported results on the fuel kernels’ response to irradiation with or without post irradiation high temperature annealing. To incrementally fulfill this knowledge gap extensive studies using transmission electron microscopes (TEM) and atom probe tomography (APT) were conducted on a TRISO fuel particle kernel with a 19.74% 235U enrichment, irradiated to 18.63% FIMA and subsequently subjected to post-safety testing at 1600ºC for 300 hours.. Microstructure characterizations, elemental analysis, and phase identification were conducted using conventional TEM and scanning TEM (STEM) imaging, energy-dispersive X-ray spectroscopy (EDS), selected-area electron diffraction (SAED) and atom probe tomography (APT). The following findings were made: (1) significant reconstructions and phase evolutions occurred in the irradiated and post-safety annealed fuel kernel, and its microstructure consists of two primary phases, namely a “high-Z (atomic mass)” UC phase and a “low-Z” UO phase, (2) no fission gas bubbles are identified within the fuel kernel, that can be attributed to the high temperature post safety annealing, (3) fission products Zr, Nb, Mo, Ru, Tc and Rh were found to preferentially segregate into UC phase or to form metallic precipitates, while the lanthanide fission products tend to stay in the solution of UO phase, (4) Pd was detected in the rod-shaped precipitates, (5) APT data reveals segregation of Te, Pd, and Ag at the UO and UC phase boundary, and (6) Pd is detected in both the UO and UC phases but with an enrichment in the former one.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Enhanced detection of volatile organic compounds (VOCs) by caffeine modified carbon nanotube junctions

Detection of vapor phase analytes and gas molecules is primarily essential for numerous applications including medical diagnostic, environmental monitoring, chemical threat detection, food quality control, and chemical warfare agents. Here, we developed Caffeine functionalized carbon nanotubes (CNTs) random network based vapor quantum resistive sensors (vQRSs) for volatile organic compounds (VOCs) detection. The localized transmission electron microscopy (TEM) image and energy dispersive X-ray spectroscopy (EDS) confirm migration of caffeine to CNT–CNT junction (CNTj). We have recorded more than one order of magnitude higher sensitivity and unique selectivity towards selective VOCs (e.g., acetone, toluene, ethanol, methanol, etc.) with short response time (few seconds) for caffeine modified CNT junction (Caf-CNTj) vQRSs. Molecular dynamics (MD) calculations suggest that the sensitivity of the sensor is diffusion limited, with an advective contribution for ethanol. Furthermore, the designed Caf-CNTj sensors can potentially be important candidate to be a part of electronic nose used for various application such as breath analysis and food quality monitoring.

36 MATERIALS SCIENCE↗

Fe Oxidation and Species Distribution at the Rock–Fluid Interface of Marcellus Shale Reacted with Hydraulic Fracturing Fluid

Hydraulic fracturing of shale reservoirs resulted in significant opportunity for increased oil and gas production in the United States. Rock-fluid interactions can cause mineral dissolution and precipitation reactions that lead to permeability changes in the shale matrix, which ultimately may affect transport pathways and hydrocarbon production. Understanding the distribution of secondary precipitates, such as barite and Fe(III) (hydro)oxides, and cation leaching at the rock-fluid interface is an important step to further investigate how these geochemical processes can change permeability and transport pathways. In this study, thin sections of the fracture-matrix interface were made from reacted Marcellus shale cores. The thin sections were characterized using synchrotron X-ray fluorescence imaging and synchrotron X-ray absorption spectroscopy. Fe species with different oxidation states were identified in the maps, together with barite and Ca distribution. The results show that ferrihydrite, as newly formed Fe(III)-bearing precipitates, aligned well with the border of the Ca (e.g., calcite) leaching region in the reaction front. Some Fe-containing clay also dissolved, but the dissolution region for the clay was not as deep as the calcite. Further, the reaction front is about three times deeper in the direction parallel to the shale bedding than that perpendicular to the bedding. The Ca leaching region can be an index for reaction front detection for Marcellus shale. Reactive transport modeling was conducted and the predicted Ca leaching boarder align well with ferrihydrite precipitation, consistent with the experimental observation. The carbonate mineral dissolution can be crucial to promote fluid access into the shale matrix. Together with our previous study on the shale reactive surface, this follow-up study showed similar Ca leaching region and Fe(III) precipitates distribution in the reaction front regardless of barite precipitation on the surface, indicating that the barite coatings on the surface may not pose a significant impact on reactive transport at the shale-fluid interface.

04 OIL SHALES AND TAR SANDS↗

Thicknesses of Chemically Altered Zones in Shale Matrices Resulting from Interactions with Hydraulic Fracturing Fluid

Hydraulic fracturing of unconventional shale reservoirs increases the fracture network surface area to access hydrocarbons from the low permeability rock matrix. Porosity and permeability of the matrix, through which hydrocarbons migrate to fractures, are important for determining production efficiency and can be altered by chemical interactions between shale and hydraulic fracturing fluids (HFFs). Here, we present results from an experimental study that characterizes the thickness of the alteration zone in the shale matrix after shale–HFF interactions. Experiments were conducted with whole cores submerged in HFF both with and without added barium and sulfate to promote barite scale formation. After 3 weeks of reaction at 77 bar and 80°C, the cores were characterized using X-ray microtomography, synchrotron X-ray fluorescence microprobe imaging, and synchrotron X-ray absorption spectroscopy. Our results show that the thickness of the altered zone depends on shale mineralogical composition and varies for different chemical reactions. Reactions between the low-carbonate Marcellus shale and HFF, pyrite (FeS 2 ) oxidation manifests as both a thick zone of sulfur oxidation (>0.5 cm) and a thinner zone of iron oxidation (100–150 $μ$m). Carbonate dissolution extended 100–200 μm into the matrix, with the resulting observable secondary porosity localized at the shale–fluid interface where mineral grains were removed by either dissolution or mechanical erosion. In solutions oversaturated with respect to barite, barite precipitates were observed in the reaction fluid and at the shal–HFF interface. In contrast, the carbonate dissolution zone in the high-carbonate Eagle Ford was only 30–40 μm thick, within which a uniform texture of increased porosity was observed. Pyrite oxidation in the Eagle Ford was evident from an iron oxidation zone (150–200 μm thick), while sulfur oxidation was minor and hard to observe. Barite precipitation extended 1–2 mm into the matrix when the initial HFF was oversaturated with respect to barite, filling shale microcracks down to the submicrometer length scale. Our findings provide a scientific basis to predict the extent of chemical alteration in shale reservoirs during hydraulic fracturing and its impacts on hydrocarbon production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Anisotropic Raman Scattering and Lattice Orientation Identification of 2M-WS 2

Anisotropic materials with low symmetries hold significant promise for next-generation electronic and quantum devices. 2M-WS 2 , which is a candidate for topological superconductivity, has garnered considerable interest. However, a comprehensive understanding of how its anisotropic features contribute to unconventional superconductivity, along with a simple, reliable method to identify its crystal orientation, remains elusive. Here, we combine theoretical and experimental approaches to investigate angle- and polarization-dependent anisotropic Raman modes of 2M-WS 2 . Through first-principles calculations, we predict and analyze the phonon dispersion and lattice vibrations of all Raman modes in 2M-WS 2 . We establish a direct correlation between their anisotropic Raman spectra and high-resolution transmission electron microscopy images. Finally, we demonstrate that anisotropic Raman spectroscopy can accurately determine the crystal orientation and twist angle between two stacked 2M-WS 2 layers. Furthermore, our findings provide insights into the electron–phonon coupling and anisotropic properties of 2M-WS 2 , paving the way for the use of anisotropic materials in advanced electronic and quantum devices.

2M-WS2↗

Tonian Carbonates Record Phosphate-Rich Shallow Seas

The early-middle Neoproterozoic is thought to have witnessed significant perturbations to marine P cycling, in turn facilitating the rise of eukaryote-dominated primary production. However, with few robust constraints on aqueous P concentrations, current understanding of Neoproterozoic P cycling is generally model-dependent. To provide new geochemical constraints, we combined microanalytical data sets with solid-state Nuclear Magnetic Resonance, synchrotron-based X-ray Absorption Near Edge Structure spectroscopy, and micro-X-ray Fluorescence imaging to characterize the speciation and distribution of P in Tonian shallow-water carbonate rocks. These data reflect shallow water phosphate concentrations 10–100× higher than modern systems, supporting the hypothesis that tectonically-driven influxes in P periodically initiated kinetically-controlled CaCO 3 deposition, in turn destabilizing marine carbonate chemistry, climate, and nutrient inventories. Alongside these observations, a new compilation and statistical analysis of mudstone geochemistry data indicates that, in parallel, C org and P burial increased across later Tonian continental margins until becoming decoupled at the close of the Tonian, implicating widespread N-limitation triggered by increasing atmospheric O 2 .

58 GEOSCIENCES↗

Distilling nanoscale heterogeneity of amorphous silicon using tip-enhanced Raman spectroscopy (TERS) via multiresolution manifold learning

Abstract Accurately identifying the local structural heterogeneity of complex, disordered amorphous materials such as amorphous silicon is crucial for accelerating technology development. However, short-range atomic ordering quantification and nanoscale spatial resolution over a large area on a-Si have remained major challenges and practically unexplored. We resolve phonon vibrational modes of a-Si at a lateral resolution of <60 nm by tip-enhanced Raman spectroscopy. To project the high dimensional TERS imaging to a two-dimensional manifold space and categorize amorphous silicon structure, we developed a multiresolution manifold learning algorithm. It allows for quantifying average Si-Si distortion angle and the strain free energy at nanoscale without a human-specified physical threshold. The multiresolution feature of the multiresolution manifold learning allows for distilling local defects of ultra-low abundance (< 0.3%), presenting a new Raman mode at finer resolution grids. This work promises a general paradigm of resolving nanoscale structural heterogeneity and updating domain knowledge for highly disordered materials.

36 MATERIALS SCIENCE↗

Mapping the pathways of photo-induced ion migration in organic-inorganic hybrid halide perovskites

Abstract Organic-inorganic hybrid perovskites exhibiting exceptional photovoltaic and optoelectronic properties are of fundamental and practical interest, owing to their tunability and low manufacturing cost. For practical applications, however, challenges such as material instability and the photocurrent hysteresis occurring in perovskite solar cells under light exposure need to be understood and addressed. While extensive investigations have suggested that ion migration is a plausible origin of these detrimental effects, detailed understanding of the ion migration pathways remains elusive. Here, we report the characterization of photo-induced ion migration in perovskites using in situ laser illumination inside a scanning electron microscope, coupled with secondary electron imaging, energy-dispersive X-ray spectroscopy and cathodoluminescence with varying primary electron energies. Using methylammonium lead iodide and formamidinium lead iodide as model systems, we observed photo-induced long-range migration of halide ions over hundreds of micrometers and elucidated the transport pathways of various ions both near the surface and inside the bulk of the samples, including a surprising finding of the vertical migration of lead ions. Our study provides insights into ion migration processes in perovskites that can aid perovskite material design and processing in future applications.

14 SOLAR ENERGY↗

Neutral rhenium( i ) tricarbonyl complexes with sulfur-donor ligands: anti-proliferative activity and cellular localization

Rhenium(I) tricarbonyl complexes are widely studied for their cell imaging properties and anti-cancer and anti-microbial activities, but the complexes with S-donor ligands remain relatively unexplored. A series of six fac-[Re(NN)(CO) 3 (SR)] complexes, where (NN) is 2,2'-bipyridyl (bipy) or 1,10-phenanthroline (phen), and RSH is a series of thiocarboxylic acid methyl esters, have been synthesized and characterized. Cellular uptake and anti-proliferative activities of these complexes in human breast cancer cell lines (MDA-MB-231 and MCF-7) were generally lower than those of the previously described fac-[Re(NN)(CO) 3 (OH 2 )]+ complexes; however, one of the complexes, fac-[Re(CO) 3 (phen)(SC(Ph)CH 2 C(O)OMe)] (3b), was active (IC 50 ~ 10 μM at 72 h treatment) in thiol-depleted MDA-MB-231 cells. Moreover, unlike fac-[Re(CO) 3 (phen)(OH 2 )]+, this complex did not lose activity in the presence of extracellular glutathione. Taken together these properties show promise for further development of 3b and its analogues as potential anti-cancer drugs for co-treatment with thiol-depleting agents. Conversely, the stable and non-toxic complex, fac-[Re(bipy)(CO) 3 (SC(Me)C(O)OMe)] (1a), predominantly localized in the lysosomes of MDA-MB-231 cells, as shown by live cell confocal microscopy (λ ex = 405 nm, λ em = 470–570 nm). It is strongly localized in a subset of lysosomes (25 μM Re, 4 h treatment), as shown by co-localization with a Lysotracker dye. Longer treatment times with 1a (25 μM Re for 48 h) resulted in partial migration of the probe into the mitochondria, as shown by co-localization with a Mitotracker dye. These properties make complex 1a an attractive target for further development as an organelle probe for multimodal imaging, including phosphorescence, carbonyl tag for vibrational spectroscopy, and Re tag for X-ray fluorescence microscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural transition and recovery of Ge implanted β -Ga 2 O 3

Ion implantation-induced effects were studied in Ge implanted β-Ga 2 O 3 with the fluence and energy of 3 × 10 13 cm -2 /60 keV, 5 × 10 13 cm -2 /100 keV, and 7 × 10 13 cm -2 /200 keV using analytical electron microscopy via scanning/transmission electron microscopy, electron energy loss spectroscopy, and precession electron diffraction via TopSpin. Imaging shows an isolated band of damage after Ge implantation, which extends ~130 nm from the sample surface and corresponds to the projected range of the ions. Electron diffraction demonstrates that the entirety of the damage band is the κ phase, indicating an implantation-induced phase transition from β to κ-Ga 2 O 3 . Post-implantation annealing at 1150 °C for 60 s under the O 2 atmosphere led to a back transformation of κ to β; however, an ~17 nm damage zone remained at the sample surface. Despite the back transformation from κ to β with annealing, O K-edge spectra show changes in the fine structure between the pristine, implanted, and implanted-annealed samples, and topspin strain analysis shows a change in strain between the two samples. These data indicate differences in the electronic/chemical structure, where the change of the oxygen environment extended beyond the implantation zone (~130 nm) due to the diffusion of Ge into the bulk material, which, in turn, causes a tensile strain of 0.5%. This work provides a foundation for understanding of the effects of ion implantation on defect/phase evolution in β-Ga 2 O 3 and the related recovery mechanism, opening a window toward building a reliable device for targeted applications.

36 MATERIALS SCIENCE↗

Disorder and diffuse scattering in single-chirality (TaSe 4 ) 2 ⁢I crystals

The quasi-one-dimensional chiral compound (TaSe 4 ) 2 I has been extensively studied as a prime example of a topological Weyl semimetal. Upon crossing its phase transition temperature $T$ CDW ≈263K, (TaSe 4 ) 2 I exhibits incommensurate charge density wave (CDW) modulations described by the well-defined propagation vector ∼(0.05,0.05,0.11), oblique to the TaSe 4 chains. Although optical and transport properties greatly depend on chirality, there is no systematic report about chiral domain size for (TaSe 4 ) 2 I. In this study, our single-crystal scattering refinements reveal a bulk iodine deficiency, and Flack parameter measurements on multiple crystals demonstrate that separate (TaSe 4 ) 2 I crystals have uniform handedness, supported by direct imaging and helicity-dependent terahertz emission spectroscopy. Our single-crystal x-ray scattering and calculated diffraction patterns identify multiple diffuse features and create a real-space picture of the temperature-dependent (TaSe 4 ) 2 I crystal structure. Further, the short-range diffuse features are present at room temperature and decrease in intensity as the CDW modulation develops. These transverse displacements, along with electron pinning from the iodine deficiency, help explain why (TaSe 4 ) 2 I behaves as an electronic semiconductor at temperatures above and below $T$ CDW , despite a metallic band structure calculated from density functional theory of the ideal structure.

36 MATERIALS SCIENCE↗

In situ coherent x-ray scattering reveals polycrystalline structure and discrete annealing events in strongly coupled nanocrystal superlattices

Solution-phase bottom up self-assembly of nanocrystals into superstructures such as ordered superlattices is an attractive strategy to generate functional materials of increasing complexity, including very recent advances that incorporate strong interparticle electronic coupling. While the self-assembly kinetics in these systems have been elucidated and related to the product characteristics, the weak interparticle bonding interactions suggest the superstructures formed could continue to order within the solution long after the primary nucleation and growth have occurred, even though the mechanism of annealing remains to be elucidated. Here, we use a combination of Bragg coherent diffractive imaging and x-ray photon correlation spectroscopy to create real-space maps of supercrystalline order along with a real-time view of the strain fluctuations in aging strongly coupled nanocrystal superlattices while they remain suspended and immobilized in solution. By combining the results, we deduce that the self-assembled superstructures are polycrystalline, initially comprising multiple nucleation sites, and that shear avalanches at grain boundaries continue to increase crystallinity long after growth has substantially slowed. This multimodal approach should be generalizable to characterize a breadth of materials in their native chemical environments, thus extending the reach of high-resolution coherent x-ray characterization to the benefit of a much wider range of physical systems. Published by the American Physical Society 2024

36 MATERIALS SCIENCE↗

Reliability Implications of Solder in Multiwire Modules under Dynamic Mechanical Loading

Two generations of multiwire modules were studied under dynamic mechanical loading (DML) with in-situ differential conductance (dG) and electroluminescence (EL) imaging. Energy-dispersive x-ray spectroscopy (EDS) was used to identity the solder alloys. The earlier generation module was found to use an In-based solder alloy, and the current generation a Bi-based alloy. The earlier generation module degraded significantly under DML with increasing resistance, while the current generation module did not demonstrate degradation under DML. Atomic force microscopy scratch testing was used to probe the wear resistance of each solder alloy. These results indicate that current multiwire designs may have higher mechanical durability than earlier generations.

atomic force microscopy↗

Biomineralization of Cu 2 S Nanoparticles by Geobacter sulfurreducens

Biomineralization of Cu has been shown to control contaminant dynamics and transport in soils. However, very little is known about the role that subsurface microorganisms may play in the biogeochemical cycling of Cu. In this study, we investigate the bioreduction of Cu(II) by the subsurface metal-reducing bacterium Geobacter sulfurreducens. Rapid removal of Cu from solution was observed in cell suspensions of G. sulfurreducens when Cu(II) was supplied, while transmission electron microscopy (TEM) analyses showed the formation of electron-dense nanoparticles associated with the cell surface. Energy-dispersive X-ray spectroscopy (EDX) point analysis and EDX spectrum image maps revealed that the nanoparticles are rich in both Cu and S. This finding was confirmed by X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses, which identified the nanoparticles as Cu 2 S. Biomineralization of Cu x S nanoparticles in soils has been reported to enhance the colloidal transport of a number of contaminants, including Pb, Cd, and Hg. However, formation of these Cu x S nanoparticles has only been observed under sulfate-reducing conditions and could not be repeated using isolates of implicated organisms. As G. sulfurreducens is unable to respire sulfate, and no reducible sulfur was supplied to the cells, these data suggest a novel mechanism for the biomineralization of Cu 2 S under anoxic conditions. The implications of these findings for the biogeochemical cycling of Cu and other metals as well as the green production of Cu catalysts are discussed.

59 BASIC BIOLOGICAL SCIENCES↗

SpecTel: A 10-12 meter class Spectroscopic Survey Telescope

We recommend a conceptual design study for a spectroscopic facility in the southern hemisphere comprising a large diameter telescope, fiber system, and spectrographs collectively optimized for massively-multiplexed spectroscopy. As a baseline, we propose an 11.4-meter aperture, optical spectroscopic survey telescope with a five square degree field of view. Using current technologies, the facility could be equipped with 15,000 robotically-controlled fibers feeding spectrographs over 360<λ<1330 nm with options for fiber-fed spectrographs at high resolution and a panoramic IFU at a separate focus. This would enable transformational progress via its ability to access a larger fraction of objects from Gaia, LSST, Euclid, and WFIRST than any currently funded or planned spectroscopic facility. An ESO-sponsored study (arXiv:1701.01976) discussed the scientific potential in ambitious new spectroscopic surveys in Galactic astronomy, extragalactic astronomy, and cosmology. The US community should establish links with European and other international communities to plan for such a powerful facility and maximize the potential of large aperture multi-object spectroscopy given the considerable investment in deep imaging surveys.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Deformation Mechanism of Age Hardened Alloy 709 Materials

This report provides an in-depth study of the microstructures of creep-deformed Alloy 790 materials. Five specimens, all creep-tested at 600°C under 330 MPa to failure, were investigated. The creep specimens were machined from plates fabricated by different melt practices, Argon Oxygen Decarburization (AOD), or AOD followed by Electroslag remelting (ESR), and different heat treatments: 1100 or 1150°C Solution Anneal (SA), and some with additional Precipitation Treatment (PT) of 775°C for 10 hours. TEM samples were made from the gauge and the grip sections of each creep-deformed specimen. Bright-field (BF) imaging, high-angle annular dark field (HAADF) imaging, and energy dispersive x-ray spectroscopy (EDS) using a scanning transmission electron microscope (STEM) were carried out on all the samples.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗