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Method and apparatus for holding two separate metal pieces together for welding

A method of holding two separate metal pieces together for welding is described including the steps of overlapping a portion of one of the metal pieces on a portion of the other metal piece, encasing the overlapping metal piece in a compressible device, drawing the compressible device into an enclosure, and compressing a portion of the compressible device around the overlapping portions of the metal pieces for holding the metal pieces under constant and equal pressure during welding. The preferred apparatus for performing the method utilizes a support mechanism to support the two separate metal pieces in an overlapping configuration; a compressible device surrounding the support mechanism and at least one of the metal pieces, and a compressing device surrounding the compressible device for compressing the compressible device around the overlapping portions of the metal pieces, thus providing constant and equal pressure at all points on the overlapping portions of the metal pieces.

Mcclure, S. R.↗

Alkali metal for ultraviolet band-pass filter

An alkali metal filter having a layer of metallic bismuth deposited onto the alkali metal is provided. The metallic bismuth acts to stabilize the surface of the alkali metal to prevent substantial surface migration from occurring on the alkali metal, which may degrade optical characteristics of the filter. To this end, a layer of metallic bismuth is deposited by vapor deposition over the alkali metal to a depth of approximately 5 to 10 A. A complete alkali metal filter is described along with a method for fabricating the alkali metal filter.

Mardesich, Nick↗

Elevated initial Sr-87/Sr-86 in ordinary chondrite metal

The metal phase of ordinary chondrites has been found to contain a complex assemblage of non-metal phases, evidently formed when elements such as Si, Cr and P, originally dissolved in the metal, were subsequently oxidized and exsolved. We have investigated the Rb-Sr isotopic system in samples of H-chondrite metal, finding small but nontrivial amounts of Sr, apparently concentrated toward the surface of metal grains, and characterized by pronounced excesses of Sr-87/Sr-86 in chondritic metal can plausibly account for the characteristically elevated initial Sr-87/Sr-86 found in ordinary chondrite phosphates, but it remains unclear when and where the metal experienced the high Rb/Sr environment needed to account for such high Sr-87/Sr-86. We have previously reported Rb-Sr data for separated metal from Dhajala (H3), Forest Vale (H4) and Estacado (H6). Here we report data for two size fractions (80-160 and 280-450 microns) of separated metal from the H4 chondrite Ste. Marguerite. These samples were etched twice (.5N HCl for one hour) before dissolution (6N HCl). Aliquots of the solutions were spiked for Fe, Ca and Rb + Sr. The results for Ste. Marguerite metal are presented; errors are two-sigma and elemental concentrations are stated in terms of total sample weight.

Podosek, F. A.↗

Ultraviolet to near-infrared spectral distributions of star-forming galaxies: Metallicity and age effects

Spectral distributions from the UV to the near-IR of a sample of 44 star-forming galaxies are used to calculate the metallicity (O/H), star-formation rate (SFR) and age of the starbursts. The oxygen abundance covers the range 8.3 less than O/H less than 9.4 and nitrogen (N) is found to be mostly a product of secondary nucleosynthesis for O/H greater than 8.4. Due to its secondary origin, N/O ratios up to approximately equals 4 times the solar value can be obtained for metal-rich starbursts. The SFR ranges 0.01 to 100 solar mass/year. The lower metallicity galaxies seem to be experiencing an instantaneous burst of star formation, with ages ranging from under 5 x 10(exp 6) to 10(exp 7) yr. The highest metallicity galaxies are most probably experiencing a continuous burst. Correlations between the calculated quantities and several spectral features are investigated. We found a highly significant correlation between the equivalent width W(C IV lambda 1550)-a stellar (absorption) feature- and the oxygen abundance of the emitting gas (O/H). Thus we show for the first time that the stellar metallicity is well correlated with the gas metallicity in star-bursting galaxies. The equivalent width W(Si IV lambda 1400) and the emission line ratio (N II) lambda lambda 6548.84/H(sub alpha) also correlate well with O/H, and all three features can be used as metallicity indicators for star-forming galaxies. The continuum color between lambda 1400 and lambda 3500 (C(14 - 35)) is shown to correlate with O/H, although it is better correlated with E(B - V). It was not possible to disentangle the metallicity from the reddening effect in C(14- 35). We estimate that the reddening affecting the UV continuum is about half the one derived from the Balmer decrement of the emitting gas. The SFR correlates well with the galaxy luminosity and there is no dependence of the continuum color on the SFR. The higher metallicities are only found in the more luminous galaxies, while low metallicities are found over the whole luminosity interval (-16 less than M(sub B) less than -23, H(sub 0) = 50 km/sec/Mpc) covered by the sample.

Storchi-Bergmann, Thaisa↗

The Formation of Carbonaceous Material in the Early Solar Nebula: The Role of Metal Dusting

For many years it has been suggested that the carbonaceous material found in association with Fe/Ni metal and metal carbides in primitive bodies is linked to the Fischer–Tropsch reaction. This is especially true with chondritic-porous interplanetary dust particles, which are considered to have a cometary origin and are among some of the most primitive and least processed materials available for study. Another phenomenon which occurs under the same carburizing conditions as the Fischer–Tropsch reaction is called metal dusting and could be a possible pathway to forming some of the carbonaceous material found in primitive bodies. Metal dusting is a catastrophic corrosion of metal under these carburizing conditions that results in a porous mixture of carbonaceous material, metal, and metal carbides. In the case of pure iron, type I metal dusting results in the formation of a metastable iron carbide, typically cementite, Fe3C. While metal dusting has been studied industrially for over 50 years, it does not appear to have been applied to the formation of carbonaceous material in astrophysical settings. In this work, the general mechanism of metal dusting on iron is described and a thermodynamic analysis of the dusting phenomena applied to solar nebula conditions. Rate measurements are made with pure iron samples over the temperature range from 400°C to 950°C. In addition, the products from experimental runs at 500°C and 600°C are studied by transmission electron microscopy. Results show that iron carbide particles are formed with carbonaceous material consisting of poorly graphitized carbon.

Interplanetary dust↗

A Transmission Electron Microscopy Study of a Refractory Metal Grain from a Calcium-Aluminum-Rich Inclusion in the Leoville CV3 Chondrite

Introduction: Calcium-aluminum-rich inclusions (CAIs) are an important component of chondritic meteorites. They can contain materials that are thermodynamically predicted and isotopically age dated to be among the first-formed solids in our solar system [1-5]. Observed in some CAIs are micron to sub-micron sized inclusions rich in Fe, Ni, and high-Z elements such as Pt, Os, Ir and W, in the form of refractory metal nuggets (RMNs), fremdlinges, and ‘nugget like objects’ (NLOs) [1,6]. Refractory siderophile elements such as Os, Ir and Ru are thermodynamically predicted to condense at temperatures well in excess of the major CAI phases such as melilite, perovskite, spinel and hibonite [2,7-9]. These refractory metal inclusions in CAIs can therefore serve as probes into the thermodynamic landscape of the early solar protoplanetary disk. Here we report on a refractory grain identified in a CAI of the Leoville CV3 chondrite. This work is part of an ongoing effort to gain insight into the thermochemistry of the early solar system through systematic analyses of the structure and chemistry of various components in CAIs [10-13]. Sample and Analytical Techniques: A fluffy type A CAI (Fig. 1A) was identified in a section of the Leoville, CV3 chondrite (Center for Meteorite Studies, Arizona State University collection, #821_C_3) using a JOEL-JXA 8530F electron microprobe at Arizona State University. Backscattered electron (BSE) imaging and energy-dispersive X-ray spectroscopy (EDS) were used to identify refractory metal grains in the CAI using a Thermo Fisher (formerly FEI) Helios NanoLab 660 G3 focused-ion-beam scanning-electron microscope (FIBSEM) located at the Kuiper Materials Imaging and Characterization Facility (KMICF) at the Lunar and Planetary Laboratory, University of Arizona. The FIB is equipped with an EDAX EDS system. We selected one of the larger (micron-sized) refractory metal grains, designated as ‘Spud’ (Fig. 1B) for further analysis. ‘Spud’ was extracted and thinned to electron transparency (<100 nm) using the FIB-SEM located in KMICF, following methods described by [14- 15]. The FIB section was analyzed using a 200 keV Hitachi HF5000 scanning transmission electron microscope (S/TEM) located at KMICF. The HF5000 is equipped with cold-field emission gun, 3rd-order spherical aberration corrector for STEM imaging, and an Oxford Instruments X-Max N 100 TLE energydispersive spectroscopy (EDS) system with dual 100 mm2 windowless silicon-drift detectors (Ω = 2.0 sr). Selected-area electron-diffraction (SAED) patterns were acquired to aid in determination of crystallinity and phase. Results: The mineralogy, texture, and morphology of the CAI are consistent with that of a fluffy type A (FTA) CAI [16]. BSE imaging at high magnifications revealed grains with high contrast, indicative of compositions rich in elements of higher atomic number relative to surrounding material. These high-Z grains have sizes that range from ∼250 nm to 4 µm. EDS analyses confirm that the bright grains are metal-rich inclusions. A minor fraction of the grains are composed of only Fe and Ni, but the majority (∼60%) of the identified inclusions also contained various refractory siderophiles including Os, Ru, Zr, Ir and Mo. EDS analysis on the FIB-SEM of Spud shows that it contains Fe, Ni, Mo and Ru. High-angle annular dark-field (HAAFD) imaging and EDS mapping in the TEM (Fig. 2) show that Spud occurs in melilite (Ca1.9Al1.99Si1.06O7). Spud contains a subhedral to anhedral morphology and is compositionally heterogenous (polyphasic, Fig. 2). Local spatial correlation occurs among Fe, Ni, and Pt, and also among Os, Ru, and Mo. SAED patterns show that the Fe-Ni-Pt, Fe-Os-Mo-Ru and Fe-Pt regions are crystalline. Discussion: CAIs can contain various types of inclusions rich in Fe, Ni and refractory siderophiles such as Os, Ru, W and Pt [1]. RMNs are micron-sized, single phase alloy grains and can contain Os, Ir, Ru and Rh [1,7,17]. NLOs are also micron-sized inclusions, but contain two phases, a refractory metal, and an oxide [6]. Fremdlinge are the largest of such inclusions (tens of microns in size) and are complex aggregates of Fe-Ni alloy, silicates, oxides, and sulfides [1,17]. While the size of Spud matches previous descriptions of RMNs and NLOs, Spud is neither a single-phase alloy like RMNs, nor does it contain one metal phase and one oxide like NLOs. Spud does not match the above described categories of refractory metal inclusions. The presence of refractory siderophiles such as Mo, Os, Ru, and Pt suggests a high-temperature origin. Thermodynamic modelling by [7] indicates condensation temperatures of 1917 K, 1693 K, 1613 K and 1415 K for Os, Mo, Ru and Pt respectively. These models also show that following the initial condensation of a refractory metal, alloying of solutes such as Fe, Ni and W, occurs in levels proportional to their partial pressures in the surrounding gas. Such alloying occurs at temperatures above the condensation temperatures of common CAI phases such as melilite (1529 K), perovskite (1441 K), spinel (197 K) and forsterite (1354 K) [2]. The polyphasic nature of Spud could be the result of such high-temperature alloying, possibly shortly after the condensation of Mo and Ru at 1693 K and 1613 K respectively. That Spud occurs as an inclusion is consistent with it having formed prior to and at temperature above that of its host melilite in this FTA CAI, which is qualitatively consistent with such prior thermodynamic modeling. Further, the polyphasic nature of Spud is similar to refractory grains from a FTA CAI in the Northwest Africa (NWA) 8323, CV3 chondrite [11-13]. These data suggest that such refractory metal grains could have been widespread in the inner and early solar protoplanetary disk and represent some of the earliest formed solids to have condensed. Acknowledgments: Research and instrumentation supported by NASA grants #NNX12AL47G, #NNX15AJ22G and #80NSSC19K0509, and NSF grants #1531243 and #0619599. Fig 2. STEM data on ‘Spud’. HAADF Image (Top) False-color EDS Maps (Bottom) References: [1] MacPherson G. J. (2014) T. of Geochem. Vol I: Met. And Cosmochem. Processes, 139-179. [2] Lodders K. (2003) ApJ, 591, 1220-1247. [3] Ebel D. S. (2006) Met. & the Early S. Sys. II., 253- 277. [4] Amelin Y. (2002) Science, 297, 1678-1683. [5] Connelly J.N. et.al. (2012) Science, 338, 651-655. [6] Schwander D. et al. (2015) GCA, 18, 70-87. [7] Palme H. and Wlotzka F. (1976) EPSL, 33, 45-60. [8] Berg T. et al. (2009) ApJ, 702, 172-176. [9] Liffman K. et al. (2021) Icarus, 221, 89-105. [10] Zega T.J. et al. (2021) PSJ, 2, 115. [11] Ramprasad T. et al. (2020) LPSC LI, Abstract #2472. [12] Ramprasad T. et al. (2021) Microscopy & Microanalysis, S1, 2792-2794. [13] Ramprasad T. et al. (2021) 84th MetSoc, Abstract #6123. [14] Zega T.J. et al. (2007) MAPS, 42, 1373-1386. [15] Ramprasad T. et al. (2022) MAPS, in revision. [16] Grossman L. (1975), GCA, 39, 433-454. [17] El Goresy A. et al. (1978) LPSC IX, Abstract#1100

T. Ramprasad↗

Overcoming Universal Restrictions on Metal Selectivity by Protein Design

Selective metal coordination is central to the functions of metalloproteins:1,2 each metalloprotein must pair with its cognate metallocofactor to fulfl its biological role3 . However, achieving metal selectivity solely through a three-dimensional protein structure is a great challenge, because there is a limited set of metal-coordinating amino acid functionalities and proteins are inherently fexible, which impedes steric selection of metals3,4 . Metal-binding afnities of natural proteins are primarily dictated by the electronic properties of metal ions and follow the Irving–Williams series5 (Mn2+ < Fe2+ < Co2+ < Ni2+ Zn2+) with few exceptions6,7 . Accordingly, metalloproteins overwhelmingly bind Cu2+ and Zn2+ in isolation, regardless of the nature of their active sites and their cognate metal ions1,3,8 . This led organisms to evolve complex homeostatic machinery and non-equilibrium strategies to achieve correct metal speciation1,3,8–10. Here we report an artifcial dimeric protein, (AB)2, that thermodynamically overcomes the Irving–Williams restrictions in vitro and in cells, favouring the binding of lower-Irving–Williams transition metals over Cu2+, the most dominant ion in the Irving–Williams series. Counter to the convention in molecular design of achieving specifcity through structural preorganization, (AB)2 was deliberately designed to be fexible. This fexibility enabled (AB)2 to adopt mutually exclusive, metal-dependent conformational states, which led to the discovery of structurally coupled coordination sites that disfavour Cu2+ ions by enforcing an unfavourable coordination geometry. Aside from highlighting fexibility as a valuable element in protein design, our results illustrate design principles for constructing selective metal sequestration agents.

Tae Su Choi↗

Assessing Metal Ion Assignment Accuracy in Protein Data Bank Models via Elemental Spectroscopy

Accurate representation of metal ions in macromolecular structures is critical for chemical interpretation, computational modeling, and machine-learning methods that rely on Protein Data Bank (PDB) entries. However, the elemental identity of metals modeled in crystallographic structures is often inferred indirectly and rarely validated experimentally. Here, we combine Particle Induced X-ray Emission (PIXE) and X-ray Fluorescence Spectroscopy (XRFS) to determine the elemental composition of protein samples used to generate 70 deposited metalloprotein crystal structures. By analyzing the original protein material employed for crystallization, but before the addition of crystallization buffer solutions, we assess whether the modeled metal ions in deposited structures are consistent with experimentally detectable elemental content. We find that in a majority of cases, the metals modeled in the corresponding PDB entries are inconsistent with the metals present in the protein samples before crystallization, or that additional metals are present but not represented in the structural models. Spectroscopic results were integrated with automated crystallographic validation metrics, including real-space Z-difference (RSZD) analysis and systematic rerefinement, to evaluate atomic-number mismatch at metal sites. PIXE and XRFS show strong agreement for dominant elemental signals and provide complementary, scalable approaches for identifying suspect metal assignments. This work does not address physiological or functional metalation but instead highlights a widespread data integrity issue in deposited macromolecular structures, PDB-wide. These results establish an experimentally corroborated link between elemental identity and crystallographic validation metrics, enabling the large-scale detection of chemically inconsistent annotations in structural databases used for computational modeling and machine learning.

Crystallization↗

Predicting metal-binding proteins and structures through integration of evolutionary-scale and physics-based modeling

Metals are essential elements in all living organisms, binding to approximately 50% of proteins. They serve to stabilize proteins, catalyze reactions, regulate activities, and fulfill various physiological and pathological functions. While there have been many advancements in determining the structures of protein-metal complexes, numerous metal-binding proteins still need to be identified through computational methods and validated through experiments. Here, to address this need, we have developed the ESMBind workflow, which combines evolutionary scale modeling (ESM) for metal-binding prediction and physics-based protein-metal modeling. Our approach utilizes the ESM-2 and ESM-IF models to predict metal-binding probability at the residue level. In addition, we have designed a metal-placement method and energy minimization technique to generate detailed 3D structures of protein-metal complexes. Our workflow outperforms other models in terms of residue and 3D-level predictions. To demonstrate its effectiveness, we applied the workflow to 142 uncharacterized fungal pathogen proteins and predicted metal-binding proteins involved in fungal infection and virulence.

59 BASIC BIOLOGICAL SCIENCES↗

Humic Acid Complexation of Th, Hf and Zr in Ligand Competition Experiments: Metal Loading and Ph Effects

The mobility of metals in soils and subsurface aquifers is strongly affected by sorption and complexation with dissolved organic matter, oxyhydroxides, clay minerals, and inorganic ligands. Humic substances (HS) are organic macromolecules with functional groups that have a strong affinity for binding metals, such as actinides. Thorium, often studied as an analog for tetravalent actinides, has also been shown to strongly associate with dissolved and colloidal HS in natural waters. The effects of HS on the mobilization dynamics of actinides are of particular interest in risk assessment of nuclear waste repositories. Here, we present conditional equilibrium binding constants (Kc, MHA) of thorium, hafnium, and zirconium-humic acid complexes from ligand competition experiments using capillary electrophoresis coupled with ICP-MS (CE- ICP-MS). Equilibrium dialysis ligand exchange (EDLE) experiments using size exclusion via a 1000 Damembrane were also performed to validate the CE-ICP-MS analysis. Experiments were performed at pH 3.5-7 with solutions containing one tetravalent metal (Th, Hf, or Zr), Elliot soil humic acid (EHA) or Pahokee peat humic acid (PHA), and EDTA. CE-ICP-MS and EDLE experiments yielded nearly identical binding constants for the metal- humic acid complexes, indicating that both methods are appropriate for examining metal speciation at conditions lower than neutral pH. We find that tetravalent metals form strong complexes with humic acids, with Kc, MHA several orders of magnitude above REE-humic complexes. Experiments were conducted at a range of dissolved HA concentrations to examine the effect of [HA]/[Th] molar ratio on Kc, MHA. At low metal loading conditions (i.e. elevated [HA]/[Th] ratios) the ThHA binding constant reached values that were not affected by the relative abundance of humic acid and thorium. The importance of [HA]/[Th] molar ratios on constraining the equilibrium of MHA complexation is apparent when our estimated Kc, MHA values attained at very low metal loading conditions are compared to existing literature data. Overall, experimental data suggest that the tetravalent transition metal/-actinide-humic acid complexation is important over a wide range of pH values, including mildly acidic conditions, and thus, these complexes should be included in speciation models.

humic acid↗

Screen-Printed Complex Ag Inks for Si HJT Metallization

Metallization using reactive metal inks has recently attracted significant research interest due to its advantages in cost of materials and manufacturing, while still achieving performance comparable to traditional fire-through particle pastes. Here, we present for the first time the use of reactive silver (Ag) inks via industrial screen-printing and inkjet printing methods for the metallization of different Si surfaces used in tunneling oxide passivating contacts (TOPCon) and Silicon heterojunction (SHJ) solar cells. Printed Ag lines exhibit a conductivity of ~5 Mu O·cm, which is approximately 3 times that of bulk Ag (1.59 µO·cm). The printed metal has a thickness of ~0.5-1.5 Mu m, an order of magnitude smaller than the current fire-through metal finger thickness (~15 Mu m). Contact resistivity measurements of the screen-printed and inkjet-printed samples on a transparent conducting oxide (TCO) surface show a very low value of ~0.2-12 mO·cm 2. Photoluminescence images of the metallized samples demonstrate minimal surface passivation degradation compared to the non-metallized areas (?iVoc <3.5 mV). Scanning electron microscopy images (SEM) reveal the structure of the printed metals on the Si surfaces as porous but much denser than fire-through Ag by nanoparticle paste. In the final presentation, we will showcase our results of printing these reactive Ag inks on high-efficiency heterojunction and TOPCon solar cells with full-area M6 wafers. Additionally, the adhesion of these reactive Ag inks on different Si surfaces according to ASTM D3359-17, as well as the performance of solar cells after standard IEC 61215 freeze/thaw and damp heat tests, will be presented. These new metal inks show promising potential as an alternative to the currently dominant particle-based pastes, offering lower Ag consumption and lower processing temperatures without compromising performance.

heterojunction solar cells↗

Metal ion dopant-induced famatinite to chalcostibite phase transformation of copper antimony sulphide colloidal nanostructures: effect on photophysical and pseudocapacitance properties

Here, the strategic doping of transition metal ions into copper antimony sulphide (CAS) semiconducting nanostructures can significantly influence their photophysical and pseudocapacitive properties, for which there are few reports and therefore is the focus of this study. Accordingly, highly crystalline metal ion (Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ and Zn 2+ ) doped off-stoichiometric copper rich/poor, antimony-rich/poor, and sulphur-poor CAS nanostructures (10–23 nm) were grown via colloidal (hot-injection) synthesis using metal diethyldithiocarbamate precursors. Importantly, metal ion doping significantly influences the structure and composition of the off-stoichiometric CAS nanostructures. Data from powder X-ray diffraction, Raman spectroscopy, high-resolution scanning/transmission electron microscopy, and energy dispersive X-ray spectroscopy confirm that the heavier metal ion dopants induce a novel phase transformation from famatinite (fCAS) to chalcostibite (cCAS) nanostructures. The influence of the metal ion dopants is also observed in the optical properties of as-synthesized nanostructures. This involves blue-shifted ultraviolet-visible absorption, reduced Urbach tailing, and tunable bandgaps between 2.17 and 2.38 eV. Also, the doped nanostructures display broad visible-near infrared photoluminescence via a triple radiative pathway with relatively short decay lifetimes between 0.2 and 6.1 ns. This is mediated by electronic transitions involving intrinsic (copper/antimony/sulphur interstitial) and extrinsic (metal ion interstitial) defect states. Additionally, electrodes prepared from Mn 2+ -doped fCAS nanostructures show enhanced pseudocapacitance via Na+ surface adsorption and intercalation relative to undoped fCAS electrodes, while Zn 2+ -doped cCAS electrodes exhibit pseudocapacitance via a combination of Na+ surface adsorption, intercalation, and redox reactions. These electrodes exhibit reduced charge transfer resistance, improved electronic conductivity and notably enhanced specific capacitance (∼222 F g −1 ), and charge transport, as measured in 1 M Na 2 SO 4 electrolyte via cyclic voltammetry and electrochemical impedance spectroscopy. To this end, the discovery of the metal ion-induced phase transformation presents a new avenue for optimizing the functional properties of fCAS and cCAS nanostructures, highlighting the critical role of metal ion-related defects in controlling the optical and electrochemical properties, towards potential solar absorption and energy storage applications.

25 ENERGY STORAGE↗

Influence of Surfactants on Noble Metal Liquid-Gas Interface Mass Transfer in Molten Salt Reactors

Noble metals, a group of insoluble fission products (FPs), can accumulate in molten salt reactors (MSRs) and influence system performance and safety through deposition. Upon generation in fission, noble metals are transported by circulating salt and may either deposit on structural surfaces or enter the circulating gas bubble interfaces. While sparging was primarily designed for xenon and krypton removal, the mass transfer of noble metals into bubble interfaces highlights a potential pathway for their transport and partial extraction. The properties of the liquid-gas interface therefore play an important role in noble metal deposition and removal behaviors. Observations from earlier studies suggest that noble metals accumulated at the bubble interface can act as surfactants, making the bubble interface partially immobile. This behavior reduces the mass transfer capacity of circulating bubbles and affects both the overall distribution of noble metals in the loop and their removal efficiency. To investigate the influence of surfactants on noble metal transport, deposition, and extraction behaviors in MSRs, a previously developed and validated species transport model incorporating noble metal interphase mass transfer was used to simulate these behaviors. Two designed cases were studied to predict the distribution of 132Te along the Molten Salt Reactor Experiment (MSRE) loop under different bubble interface conditions. The results show that the mass transfer coefficients at the liquid-gas interface, determined by bubble interface characteristics, significantly influence noble metal distribution within the reactor loop. These findings emphasize the importance of continuously introducing fresh circulating bubbles into the molten salt to improve the removal efficiency of insoluble FPs from the MSR primary loop.

MSR↗

Catalytic Activation of Pyran Ethers in Self-Solvating Saccharides with Alkaline Earth Metals (Final Report)

Catalytic activation of cellulose ethers occurs via hydroxyl-stabilized cleavage of inter-monomer glycosidic bonds. Cooperativity between two hydroxyl groups lowers the ether cleavage transition state necessary to break apart long carbohydrate chains to initiate small molecule formation as fuel precursors. Metals existing with lignocellulosic materials including alkaline earth metals (Ca 2+ , Mg 2+ ) or alkali (Na + , K + ) also can catalyze ether scission cooperatively. By bonding with carbohydrate hydroxyl groups, a metal cation disrupt the hydrogen bonding network and free carbohydrate functional groups to react; a second metal cation stabilizes the carbohydrate ether transition state and enhances the rate of polymer scission. In this work, we expanded our initial understanding of metal-catalyzed glycoside ether scission. Within polysaccharides such as cellulose, two ether groups exist: one between monomers (glycosidic linkages) and one within a pyran ring. The hydroxyl-group hydrogen bonding network and bound metal ions form low energy binding states that interact with both ether oxygens simultaneously. Based on this interaction, our primary hypothesis was that the competition between stabilizing the two ether scission transition states determines the extent of the major pathways. Metals that disrupt the hydrogen bonding network of the C6 of sugars and stabilize the glycosidic ether promote transglycosylation to levoglucosan; in contrast, metals that stabilize the pyran ether oxygen promote sugar ring fragmentation to furans such as furfural. Varying characteristics of metal cation catalysts and configurations of bound polysaccharide chains dictate the relative rates of ether scission.

09 BIOMASS FUELS↗

Technical Considerations on MURR Control Blade Design Change and Testing using a New Metal Matrix Composite

The University of Missouri Research Reactor (MURR) is one of six research reactors, including a critical facility, that are pursuing conversion as part of a collaboration with the U.S. Department of Energy National Nuclear Security Administration Material Management and Minimization Office of Reactor Conversion and Uranium Supply, under the U.S. High Performance Research Reactors (USHPRR) conversion project. Five of the six USHPRR are planned to convert from highly enriched uranium (HEU) fuel using a low-enriched uranium (LEU) high assay monolithic alloy of uranium-10 wt% molybdenum (U-10Mo). As part of the conversion safety analysis, it is necessary to demonstrate the safety performance of the proposed core fueled with LEU as compared to the current HEU cores. The MURR reactor is planning to switch to a new control blade design that uses a metal matrix composite of boron carbide (B 4 C) and aluminum as the absorber in place of Boral®. Since MURR is expected to adopt the new metal matrix composite control blade design prior to conversion, the impact of the new blade design on the neutronics characteristics of the MURR cores for conversion are analyzed in this work through updates to incorporate the changes to the blade design in conversion models as they directly impact the LEU conversion safety analysis. The quantitative comparison shows that the neutronics and thermal hydraulic behavior of one metal matrix composite blade replacing a Boral blade is comparable for the two example MURR LEU and HEU cores states considered. Geometrical changes in the metal matrix composite blade design, combined with a 4% increase in areal boron density, showed local heating effects up to 20% higher than the Boral design. As expected, the metal matrix composite showed slightly lower heat depositions and absorber region temperatures for the LEU cases compared to HEU. Although this analysis was comparative for a single blade, maximum control blade temperatures for both Boral, metal matrix composite, and HEU/LEU remained below 100 °C, though additional analysis at a core level could differ. A qualitative irradiation behavior assessment concludes that the mechanisms that may drive swelling and blistering in the current Boral design are eased by the adoption of the metal matrix composite design. The work concludes that the two blade designs are essentially equivalent with regards to neutronics, thermal hydraulics, and expected material behavior under irradiation. However, due to the geometrical changes to the blades including redesigned and thinner cladding, new testing and increased surveillance for distortion and swelling are recommended to confirm the performance of the metal matrix composite control blade design. Where testing is completed prior to conversion, the only anticipated impacts on conversion to LEU U-10Mo fuel would be the need for models and safety analysis incorporating the metal matrix composite control blades.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Observing one-divalent-metal-ion-dependent and histidine-promoted His-Me family I-PpoI nuclease catalysis in crystallo

Metal-ion-dependent nucleases play crucial roles in cellular defense and biotechnological applications. Time-resolved crystallography has resolved catalytic details of metal-ion-dependent DNA hydrolysis and synthesis, uncovering the essential roles of multiple metal ions during catalysis. The histidine-metal (His-Me) superfamily nucleases are renowned for binding one divalent metal ion and requiring a conserved histidine to promote catalysis. Many His-Me family nucleases, including homing endonucleases and Cas9 nuclease, have been adapted for biotechnological and biomedical applications. However, it remains unclear how the single metal ion in His-Me nucleases, together with the histidine, promotes water deprotonation, nucleophilic attack, and phosphodiester bond breakage. By observing DNA hydrolysis in crystallo with His-Me I-PpoI nuclease as a model system, we proved that only one divalent metal ion is required during its catalysis. Moreover, we uncovered several possible deprotonation pathways for the nucleophilic water. Interestingly, binding of the single metal ion and water deprotonation are concerted during catalysis. Our results reveal catalytic details of His-Me nucleases, which is distinct from multi-metal-ion-dependent DNA polymerases and nucleases.

59 BASIC BIOLOGICAL SCIENCES↗

Shear strength of metal-sapphire contacts

The shear strength of polycrystalline Ag, Cu, Ni, and Fe contacts on clean (0001) sapphire has been studied in ultrahigh vacuum. Both clean metal surfaces and surfaces exposed to O2, Cl2, and C2H4 were used. The results indicate that there are two sources of strength of Al2O3-metal contacts: an intrinsic one that depends on the particular clean metal in contact with Al2O3 and an additional one due to intermediate films. The shear strength of the clean metal contacts correlated directly with the free energy of oxide formation for the lowest metal oxide, in accord with the hypothesis that a chemical bond is formed between metal cations and oxygen anions in the sapphire surface. Contacts formed by metals exposed to chlorine exhibited uniformly low shear strength indicative of van der Waals bonding between chlorinated metal surfaces and sapphire. Contacts formed by metals exposed to oxygen exhibited enhanced shear strength, in accord with the hypothesis that an intermediate oxide layer increases interfacial strength.

Pepper, S. V.↗

Friction and transfer behavior of pyrolytic boron nitride in contact with various metals

Sliding friction experiments were conducted with pyrolytic boron nitride in sliding contact with itself and various metals. Auger emission spectroscopy was used to monitor transfer of pyrolytic boron nitride to metals and metals to pyrolytic boron nitride. Results indicate that the friction coefficient for pyrolytic boron nitride in contact with metals can be related to the chemical activity of the metals and more particularly to the d valence bond character of the metal. Transfer was found to occur to all metals except silver and gold and the amount of transfer was less in the presence than in the absence of metal oxide. Friction was less for pyrolytic boron nitride in contact with a metal in air than in vacuum.

Buckley, D. H.↗