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The Mobility of Mo during Microbially Mediated Ferrihydrite Phase Transformation

Molybdenum (Mo) is an essential nutrient for almost all organisms. However, at high concentrations, it can be toxic to animals and plants. This study investigated the interactions of Mo(VI) with iron oxyhydroxides during ferrihydrite bioreduction in the presence of the Fe(III)- reducing Geobacter sulfurreducens. Here, in this study, we showed that Mo concentration controlled ferrihydrite phase transformation, leading to Mo release. With the biotic reduction of ferrihydrite and Fe(II) production, Mo(VI) reduction and Mo(IV)O 2 formation were observed for the first time, which further immobilised Mo after surface adsorption of Mo(VI). At low Mo levels (Mo/Fe molar ratios of 1-2 %), sufficient Fe(II) adsorption onto ferrihydrite resulted in its transformation into magnetite nanoparticles (>80%, ~25 nm) which catalysed the reduction of Mo(VI) to form Mo(IV)O 2 and immobilised Mo. Contrastingly, at high Mo concentrations (Mo/Fe molar ratios of 5-10%), Mo(VI)O 4 2- adsorption onto ferrihydrite limited Fe(II) adsorption, subsequently less magnetite (<8-12%) formed while more goethite (~30- 50%, width & length > 15 & 100 nm, respectively) and siderite (~20-30%, width & length > 100 & 200 nm, respectively) with larger particle sizes formed instead, causing Mo(VI) release due to lower Mo adsorption. This study provides a comprehensive understanding of the interaction mechanisms among Geobacter sulfurreducens, Mo(VI), and iron oxyhydroxides, enabling predictions and controls of long-term Mo mobility and Fe mineral transformation under a variety of biogeochemical scenarios.

Geobacter sulfurreducens↗

Endemic Mo Isotopic Anomalies in Iron and Carbonaceous Meteorites

Mo in refractory interstellar grains shows large isotope anomalies. Recent Mo studies showed isotope effects in Allende and Murchison, and in iron meteorites, mesosiderites, and pallasites. Excesses of p- and r-process isotopes (or depletion of sprocess isotopes) of up to 3.5 epsilon units (epsilon u=parts in 10(exp 4)) were reported. We have reported on endemic isotope anomalies in Ru. Other workers have resolved no isotope anomalies for Mo or Ru and have claimed that the work by others is incorrect. Because Ru isotopes can interfere at Mo-96, Mo-98, Mo-100, we improved the chemical separations and eliminated interferences. For Mo work, we used the same solutions from which we separated and analyzed Ru. Three of the iron meteorites (Coahuila, Cape York, and Cape of Good Hope) were chosen for their large Mo isotopic effects. Mo was loaded on outgassed Re filaments, and then reduced; we used Ba(OH)2-NaOH as emitter, and measured Mo in static mode, as MoO3(-). We used Mo-98/Mo-96 for the mass fractionation correction (exponential law). No interferences from Ru or Zr isotopes were detected using the electron multiplier and no corrections were needed. For results on Mo standards we show 2 sigma(not 2 sigma mean) external precision better than: 0.7 epsilon u for Mo-94/Mo-96 and Mo-95/Mo-96; 1.0 epsilon u for Mo-92/Mo-96 and Mo-97/Mo-96; 1.4 epsilon u for Mo-100/Mo-96. Reproducibility for Mo standards is shown as contours (blue lines).

Chen, J. H.↗

Expression of V-nitrogenase and Fe-nitrogenase in Methanosarcina acetivorans is controlled by molybdenum, fixed nitrogen, and the expression of Mo-nitrogenase

ABSTRACT All nitrogen-fixing bacteria and archaea (diazotrophs) use molybdenum (Mo) nitrogenase to reduce dinitrogen (N 2 ) to ammonia, with some also containing vanadium (V) and iron-only (Fe) nitrogenases that lack Mo. Among diazotrophs, the regulation and usage of the alternative V-nitrogenase and Fe-nitrogenase in methanogens are largely unknown. Methanosarcina acetivorans contains nif , vnf , and anf gene clusters encoding putative Mo-nitrogenase, V-nitrogenase, and Fe-nitrogenase, respectively. This study investigated nitrogenase expression and growth by M. acetivorans in response to fixed nitrogen, Mo/V availability, and CRISPRi repression of the nif , vnf , and/or anf gene clusters. The availability of Mo and V significantly affected growth of M. acetivorans with N 2 but not with NH 4 Cl. M. acetivorans exhibited the fastest growth rate and highest cell yield during growth with N 2 in medium containing Mo, and the slowest growth in medium lacking Mo and V. qPCR analysis revealed the transcription of the nif operon is only moderately affected by depletion of fixed nitrogen and Mo, whereas vnf and anf transcription increased significantly when fixed nitrogen and Mo were depleted, with removal of Mo being key. Immunoblot analysis revealed Mo-nitrogenase is detected when fixed nitrogen is depleted regardless of Mo availability, while V-nitrogenase and Fe-nitrogenase are detected only in the absence of fixed nitrogen and Mo. CRISPRi repression studies revealed that V-nitrogenase and/or Fe-nitrogenase are required for Mo-independent diazotrophy, and unexpectedly that the expression of Mo-nitrogenase is also required. These results reveal that alternative nitrogenase production in M. acetivorans is tightly controlled and dependent on Mo-nitrogenase expression. IMPORTANCE Methanogens and closely related methanotrophs are the only archaea known or predicted to possess nitrogenase. Methanogens play critical roles in both the global biological nitrogen and carbon cycles. Moreover, methanogens are an ancient microbial lineage and nitrogenase likely originated in methanogens. An understanding of the usage and properties of nitrogenases in methanogens can provide new insight into the evolution of nitrogen fixation and aid in the development nitrogenase-based biotechnology. This study provides the first evidence that a methanogen can produce all three forms of nitrogenases, including simultaneously. The results reveal components of Mo-nitrogenase regulate or are needed to produce V-nitrogenase and Fe-nitrogenase in methanogens, a result not seen in bacteria. Overall, this study provides a foundation to understand the assembly, regulation, and activity of the alternative nitrogenases in methanogens.

Biotechnology & Applied Microbiology↗

Impact of Solution Chemistry on Growth and Structural Features of Mo-Substituted Spinel Iron Oxides

The effect of crystallizing solution chemistry on the chemistry of subsequently as-grown materials was investigated for Mo-substituted iron oxides prepared by thermally activated co-precipitation. In the presence of Mo ions, we find that varying the oxidation state of the iron precursor from Fe(II) to Fe(III) causes a progressive loss of atomic long-range order with the stabilization of 2-4 nm particles for the sample prepared with Fe(III). The oxidation state of the Fe precursor also affects the distribution of Fe and Mo cations within the spinel structure. Increasing the Fe precursor oxidation state gives decreased Fe-ion occupation and increased Mo-ion occupation of tetrahedral sites, as revealed by the extended X-ray absorption fine structure. The stabilization of Mo within tetrahedral sites appears to be unexpected, considering the octahedral preferred coordination number of Mo(VI). The analysis of the atomic structure of the sample prepared with Fe(III) indicates a local ordering of vacancies and that the occupation of tetrahedral sites by Mo induces a contraction of the interatomic distances within the polyhedra as compared to Fe atoms. Moreover, the occupancy of Mo into the thermodynamic site preference of a Mo dopant in Fe 2 O 3 assessed by density functional theory calculations points to a stronger preference for Mo substitution at octahedral sites. Hence, we suggest that the synthetized compound is thermodynamically metastable, that is, kinetically trapped. Such a state is suggested to be a consequence of the tetrahedral site occupation by Mo ions. The population of these sites, known to be reactive sites enabling particle growth, is concomitant with the stabilization of very small particles. Furthermore, we confirmed our hypothesis by using a blank experiment without Mo ions, further supporting the impact of tetrahedral Mo ions on the growth of iron oxide nanoparticles. Our findings provide new insights into the relationships between the Fechemistry of the crystallizing solution and the structural features of the as-grown Mo-substituted Fe-oxide materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantifying the Impact of Metal Population Distribution in MFI-Supported Mo Catalysts for Methane Dehydroaromatization

Precise evaluation of intrinsic kinetic behavior in Mo/MFI catalysts for methane dehydroaromatization (MDA) is confounded by variations in Mo dispersion and speciation, which are influenced by metal loading and zeolite acidity. This work advances the utility of H 2 -temperature programmed reduction (H 2 -TPR) for characterizing Mo/MFI catalysts by enabling quantitative comparison of MoO x populations distinguished by reduction behavior and linked to initial catalytic performance. A comprehensive H 2 reduction pathway is established through systematic H 2 - TPR studies varying catalyst composition (1–10 wt % Mo, Si/Al = 15, 40, ∞), supplemented by UV-Raman spectroscopy, X-ray powder diffraction, N 2 physisorption, NH 3 -TPD, and advanced spectroscopic analysis (in situ XAS with principal component analysis/multivariate curve resolution—alternating least squares). Two low-temperature H 2 -TPR regions capture distinct Mo populations undergoing initial Mo(VI)→Mo(IV) reduction: a lower-temperature population (Mo-RI) associated primarily with highly dispersed, anchored MoO x species expected to predominantly reside within MFI channels, and a higher-temperature population (Mo-RII) corresponding to a broader set of MoO x species that becomes increasingly bulk-like/extrazeolitic at higher Mo loading. Quantification of these populations provides practical, kinetically relevant descriptors for comparing initial MDA rates across catalysts with varying Mo loading, Si/Al ratio, and MoO x heterogeneity. Application of lower-temperature Mo-RI estimates to kinetic measurements reveals a minimum threshold of ∼0.12 × 10 –3 mol Mo-RI/g cat , above which initial forward benzene rates normalized to this population converge despite differences in metal loading and zeolite Brønsted acidity. This threshold coincides with a transition toward a common C 2 -mediated benzene-forming regime, as indicated by approach-to-equilibrium analysis of methane-to-ethane, ethane-to-ethylene, and ethylene-to-benzene reaction steps. Above this threshold, normalized initial benzene rates are nearly invariant with increasing Mo-RII/Mo-RI population ratio, indicating that excess Mo-RII populations, including bulk-like/extrazeolitic MoO x domains present at higher loading, do not measurably suppress benzene formation associated with anchored and mostly channel-confined Mo population under the initial-rate conditions examined.

Mo/MFI↗

Heat transfer optimization of uo 2 -mo fuel using genetic algorithms

Two genetic algorithm (GA) methods were applied to thermal finite element models to optimize the heat transfer efficacy of a UO 2 -Mo composite fuel pellet with typical pressurized water reactor fuel geometry. Mo additions to UO 2 have been shown to increase the thermal conductivity, thus reducing centerline temperatures and temperature gradients. Previous studies evaluated uniformly dispersed Mo or continuous Mo internal geometries (e.g., fins, plates, discs) that were selected using engineering intuition. The current study uses two different implementations of the same GA to optimize Mo placement and minimize the fuel temperature with the only constraint being a maximum 10% Mo volume fraction. One approach superimposed Mo line elements onto the monolithic UO 2 pellet model, and the other converted entire UO 2 volume elements to Mo. The former method generated 1D heat transfer connections between nodes, whereas the latter method allowed for the formation of 3D structures. Features of the optimal fuel design produced by the GAs included dispersed Mo near the centerline that shifted the peak fuel temperature outward by 0.6 mm, Mo chains in the high-heat-flux region in the mid-to-outer radial zone, and a large continuous structure that spanned the full radius and height of the pellet and accounted for 87.7 % of the total Mo in the pellet. Analysis of this design indicates that the optimal Mo configuration is a balance between creating continuous heat transfer pathways and optimally dispersing Mo to minimize the heat transfer distance through UO 2 . This architecture ultimately produced an effective thermal conductivity of 11.3 W/m·K under the assumed boundary conditions. This result is higher than any previous values from the literature. In conclusion, potential fabrication methods and challenges are discussed in addition to the implications on fuel performance.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Molybdenum Recovery from Filters Used in Large-scale Dissolution of Sintered Mo-disks

99 Mo production with linear accelerators can be achieved via the bremsstrahlung photonuclear reaction 100 Mo(γ,n) 99 Mo or the neutron capture reaction 98 Mo(n,γ) 99 Mo. For commercial producers, maximum recovery of enriched 98 Mo and 100 Mo target material is critical for sustaining an economic production cycle. During the peroxide dissolution of Mo metal disks and subsequent conversion to K 2 MoO 4 , several grams of Mo can be lost during filtration from solution when several hundred grams of sintered Mo disks are processed. This investigation shows that 5–8 g Mo is routinely retained on the filter units, but it can be almost fully recovered using aqueous washes. Washing can be done immediately and incorporated into the dissolution procedure, or it can occur several months after the initial filtration process to decrease processing time.

07 ISOTOPE AND RADIATION SOURCES↗

Carbidic Mo is the sole kinetically-relevant active site for catalytic methane dehydroaromatization on Mo/H-ZSM-5

Systematic variation of Mo/Al = {0.10, 0.25, 0.35} in Mo/H-ZSM-5 catalysts effects ~20× change of Mo-to-H + ratio during methane dehydroaromatization (DHA) reactions at steady state and on deactivating catalysts. Mo and Brønsted-acid site count, respectively enumerated by ethane hydrogenolysis probe reaction and dimethyl ether chemical titration, evolve disparately during DHA catalysis, indicating the two sites reduce in number by distinct mechanisms. Here, the deactivation of Mo/H-ZSM-5 catalytic activity is uniquely attributed to the loss of active, or accessible, Mo sites, evinced by (i) the non-selective nature of deactivation (i.e. that deactivation occurs without modification of residual active sites), (ii) invariance in product distribution from Mo/H + = 0.10–2.1, and (iii) linear correspondence between Mo-catalyzed ethane hydrogenolysis rate and active site count during DHA on deactivating samples. DHA forward rate – the intrinsic kinetic descriptor of catalyst activity – normalizes by Mo content at steady state and on deactivating catalysts with Mo/Al = 0.10–0.35 for Mo-based contact times in the range τ Mo = 0.79–44 mol Mo s mol –1 C , unequivocally establishing Mo aggregates as the sole kinetically-relevant active site on Mo/H-ZSM-5. Brønsted-acid site content over a ~40× range in τ H+ = 1.4–54 mol H+ s mol –1 C has no discernable correlation with or effect on DHA rate, methane conversion, or product distribution – demonstrating H + does not catalyze any rate- or selectivity-determining steps in the benzene formation pathway and suggesting that the benefits of zeolitic acid sites are only to disperse Mo during catalyst synthesis and, conceivably, to catalyze equilibrated reaction steps.

02 PETROLEUM↗

Redox effects on the structure and properties of Na-Mo-Fe-phosphate glasses

Na-Mo-Fe-phosphate glasses were prepared with reducing and oxidizing raw materials and the effects of the different Fe 2+ /Fe 3+ and Mo 5+ /Mo 6+ ratios on glass structure and properties were determined. Mssbauer spectroscopy confirms significantly greater concentrations of Fe 2+ ions in the reduced glasses and distorted Fe 3+ O 4 sites preferred over the Fe 3+ O 6 sites in the oxidized glasses. Raman spectroscopy reveals the presence of isolated Mo 6+ O 6 sites in the oxidized glasses, and highly distorted Mo 5+ O 5 sites in reduced Mo-rich glasses. The presence of specific Fe- and Mo-polyhedra is correlated with the average phosphate anion length, as characterized by high-pressure liquid chromatography. Generally, for the similar compositions, oxidized glasses have greater molar volumes than the reduced glasses, associated with the formation of isolated Mo 6+ O 6 octahedra and the absence of highly crosslinked Mo 5+ OPO 4 units. Tg increases with increasing Fe 3+ fractions in the Fe-rich glasses, whereas for the Mo-rich glasses, T g increases with greater Mo 5+ fractions.

36 MATERIALS SCIENCE↗

One-Step Synthesis and Operando Electrochemical Impedance Spectroscopic Characterization of Heterostructured MoP–Mo 2 N Electrocatalysts for Stable Hydrogen Evolution Reaction

Here this study presents a novel synthesis of self-standing MoP and Mo 2 N heterostructured electrocatalysts with enhanced stability and catalytic performance. Facilitated by the controlled phase and interfacial microstructure, the seamless structures of these catalysts minimize internal resistivity and prevent local corrosion, contributing to increased stability. The chemical synthesis proceeds with etching step to activate the surface, followed by phosphor-nitriding in a chemical vapor deposition chamber to produce MoP-Mo 2 N@Mo heterostructured electrocatalysts. X-ray diffraction analyses confirm the presence of MoP, Mo 2 N, and Mo phases in the electrocatalyst. Morphology studies using scanning electron microscopy characterizes the hierarchical growth of structures, indicating successful formation of the heterostructure. X-ray photoelectron spectroscopy (XPS) analyses of the as-synthesized and post-catalytic activity samples reveal the chemical shift in terms of binding energy (BE) of Mo 3d XPS peak, especially after catalytic activity. The XPS BE shifts attributed to changes in oxidation state, electron transfer, and surface reconstruction during catalysis. Electrochemical evaluation of the catalysts demonstrates the superior performance of the MoP-Mo 2 N@Mo heterostructured catalyst in hydrogen evolution reactions (HER), with lower overpotentials and enhanced Tafel slopes. Stability tests reveal changes in double layer capacitance over time, suggesting surface reconstruction and increased active surface area during catalysis. Operando electrochemical impedance spectroscopy (EIS) further elucidates the dynamic changes in resistance and charge transfer during HER. Overall, comprehensive understanding of the synthesis, characterization, and electrochemical behavior of the developed MoP-Mo 2 N@Mo heterostructured electrocatalyst as presented in this paper highlights their potential utilization in sustainable energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Irradiation of Mo-100 Targets and Testing Fe(ll)CI 2 Precipitation for Tc-99 Removal

The production of molybdenum-99 (Mo-99) is a critical step in the generation of technetium-99m (Tc-99m), a radioisotope widely used in medical imaging. NorthStar Medical Radioisotopes, LLC is planning to produce the important medical radioisotope Mo-99 through a photonuclear reaction on molybdenum-100 (Mo-100). Accelerator production of Mo-99 using enriched Mo-100 targets yields undesirable isotopes, such as niobium-95 (Nb-95) and zirconium-95 (Zr-95). Previous studies reported that Nb and Zr isotopes can be effectively removed from Mo-99 products through coprecipitation with Fe(III). To enable the potential utilization of the first milking of Tc-99m from a Mo-99/Tc-99m generator, it is desirable to remove long-lived Tc-99. This can be accomplished by substituting Fe(III) with Fe(II) during the precipitation step, without affecting the removal of Zr and Nb isotopes. Previous experiments demonstrated up to 99+% removal of Tc using this method. It was also observed that the presence of hydrogen peroxide significantly impacts Tc removal. This was evident in the processing of enriched Mo-100 targets, where only 25% of Tc was removed. To further investigate this, another irradiation of enriched Mo-100 disks was conducted, followed by Tc-99 removal using Fe(II). Prior to irradiation, experimental conditions for Tc removal were optimized through several test runs using Mo-100 disks spiked with Tc-99. The results of these tests are discussed in this report.

07 ISOTOPE AND RADIATION SOURCES↗

Impact of uranium oxide (UO 2 ) fuel with molybdenum (Mo) inserts on pressurized water reactor performance and safety

This work investigates nuclear reactor performance and safety characteristics of UO 2 with high thermal conductivity Mo insert structures by using multiphysics modeling techniques. Additionally, the purpose of this study is to use scoping analyses to quantify the impact of using Mo inserts from neutronic and heat transfer standpoints. Attention is given to reactor performance parameters, such as cycle length, maximum fuel temperature, temperature gradients in the fuel, and stored energy in the fuel. The finite-element code BISON and the Monte Carlo particle transport code Serpent were used to perform sensitivity analyses on the Mo insert geometry to optimize the insert design and inform larger scale modeling that required the homogenization of the UO 2 and Mo. Although BISON is often used as a fuel performance analysis tool, it is used in this context for heat transfer analysis only. Fuel performance optimization is outside the scope of the current study, but would be important for future work focused on this concept. The results showed that the insert had little impact on neutronic performance and that homogenizing the UO 2 and Mo was acceptable for reactor physics calculations. Reactivity temperature coefficients calculated using homogeneous UO 2 -Mo were shown to be relatively similar to UO 2 , but higher Mo content and 235 U enrichment can reduce the worth of soluble boron and control rods. The effect of insert geometry on heat transfer was much greater, and an approximately 15–20% difference in maximum fuel temperature was predicted between the best and worst performing heat transfer geometries. Furthermore, thermal conductivity calibration based on the finite element analysis results was performed to improve the accuracy of temperature predictions in reactor analysis models that homogenized the UO 2 -Mo fuel. Compared with UO 2 in a pressurized water reactor (PWR), the optimized UO 2 -Mo design increased the margin to fuel melt by 13–32% across the fuel cycle, but it requires the 235U enrichment to exceed 5% to match the cycle length of conventional UO 2 .

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Semiconducting Zn x Mo 3 S 13 -GO Chalcocarbogel: A High-Capacity and Stable Sulfur-Equivalent Conversion-Based Electrode for Lithium-Ion Batteries

Lithium–sulfur batteries with a sulfur electrode offer a theoretical capacity of ∼1672 mAh g –1 , but rapid capacity loss mainly constrains their practical application. This work introduces a semiconducting and amorphous Zn x Mo 3 S 13 -GO (x = 0.5) chalcocarbogel sulfur-equivalent electrode with superior capacity and stability for lithium-ion batteries (LIBs). The Zn x Mo 3 S 13 -GO is synthesized in solution under ambient conditions, and its local structure contains S–S, M-Q (M = Mo, Zn; Q = S, O), C–S, and Mo–Mo bonding motifs with Mo coordination environment closely related to Mo 3 S 13 anions, as determined by X-ray photoelectron spectroscopy, synchrotron X-ray scattering, X-ray absorption spectroscopy, and ab initio molecular dynamics simulations. The Li/Zn x Mo 3 S 13 -GO cell offers an initial discharge capacity of 1019 mAh g –1 at a rate of C/3. After the activation cycles, the Li/Zn x Mo 3 S 13 -GO cell demonstrates good cycling stability, retaining a discharge capacity of 519.4 mAh g –1 after 250 cycles with ∼99.98% Coulombic efficiency and excellent rate capabilities. Moreover, it provides an initial discharge capacity of ∼574 mAh g –1 and maintains a retention capacity of 279 mAh g –1 at 1C after 625 cycles. The Lewis acidic Zn 2+ ion enhances the Lewis basic polysulfide anchoring ability and reduces the dissolution of polysulfides produced during the redox process through Zn–S covalent interaction, while the semiconducting and amorphous structure of the chalcocarbogel increases the electrical and ionic conductivity. Furthermore, this work highlights chalcocarbogels’ potential for developing high-capacity and stable electrodes for LIBs.

25 ENERGY STORAGE↗

Modulation of the coordination environment enhances the electrocatalytic efficiency of Mo single atoms toward water splitting

Here, enhancing the catalytic efficiency through engineering active site environments is expected to work pronouncedly for single atom catalysts (SACs) because of intense atomic scale interactions involved between SAs and their coordination environments. Taking Mo SACs for catalyzation of the hydrogen evolution reaction (HER) as an example, three SACs of different coordination environments, namely Mo-O 2 N 2 , Mo-O 2 N 1 C 1 , and Mo-O 2 C 2 , were successfully created for demonstration. The HER performances are in an increasing order of Mo-O 2 N 2 , Mo-O 2 N 1 C 1 , and Mo-O 2 C 2 , exhibiting η 10 of 98, 71, and 61 mV, η 500 of 340, 248, and 200 mV, Tafel slopes of 95.8, 39.6, and 33.8 mV dec -1 , and current density decays of 9, 6, and 6% after a 50 hour operation at an initial current density of 100 mA cm -2 , respectively. Substituting C with N in the coordination environment results in inferior HER catalytic efficiency and stability. Density functional theory calculations reveal that replacing carbon with nitrogen for coordination with the Mo SA on a carbon substrate of a higher N-doping level shifts the d-band center of Mo more negatively from the Fermi level, thereby increasing the hydrogen adsorption energy and thus decelerating the hydrogen desorption kinetics, giving consequent inferior HER activities.

25 ENERGY STORAGE↗

Window Cooling Studies and Disk Vibration Testing on a Subset of Mo-100 Disks

Production of metastable Technetium-99 (Tc-99m), a radioactive tracer that emits gamma rays, is vital to the medical imaging community. Tc-99m is extracted from the decay of Molybdenum-99 (Mo-99) which has a half-life of about 2-3 days. The work presented in this report is part of the NNSA’s mission to produce Mo-99 commercially, within the US, without the use of highly enriched uranium (HEU) in support of nonproliferation and global security. Los Alamos National Laboratory (LANL) is working with NorthStar Medical Radioisotopes (NMR) on their efforts to produce Mo-99 through the irradiation of Mo-100 targets using an electron beam. The NMR target comprises a stack of approximately 60-70 Mo-100 disks with diameter 24 mm and thickness 0.74 mm held in stainless steel laminations, each separated using 0.25 mm thick stainless-steel spacers. The symmetric target stack is housed in an Inconel vessel with two Inconel windows on either side. Two electron accelerators are used to produce 40 MeV, 3.16 µA electron beams each that penetrate the Inconel windows and irradiate the Mo-100 disks. Approximately 90% of the total 250 kW beam power is deposited in the NMR target during the irradiation process, with a smaller percentage adding up to 2.2 kW of heat deposited on the Inconel window. During irradiation, pressurized helium gas flows through thin gaps between the disks cooling the beam window, target disks, disk laminations and spacers. Both NMR and LANL have found during cold testing of the target system (no heat deposition) that the Mo 100 disks undergo significant mass loss and disk breakage due to vibrations induced by the flowing helium gas. The mass loss is not only undesirable due to monetary loss from reduced final quantities of Mo-99, but also due to the hazards associated with radioactive material trapped in the cooling lines and particle filters. The effect of flow rate and target geometry on the flow induced vibrations need to be quantified, and recommendations provided to minimize this mass loss. LANL has previously also tested NMR’s Inconel beam window by heating the window, while flowing pressurized helium, using the average heat deposited on the window. However, the NMR beam is pulsed with a duty cycle of 12.5%, which introduces oscillation in temperature around the nominal 600 °C steady state value with each pulse. Available fatigue curves for Inconel are few, established for room temperature, and they are based on mechanical strain cycles not thermally induced strain as in the NMR target. The effect of pulsed beam heating on the Inconel window therefore needs to be quantified. This report details the experiments conducted to assess the factors that lead to mass loss in the NMR target disks as well as to understand the effect of a pulsed beam on NMR’s Inconel window. This work describes LANL’s experimental characterization of the flow induced vibrations and disk mass loss in a reduced scale set-up containing 5 to 10 Mo-100 disks. We use high speed imaging, displacement measurements and microphone measurements combined with signal processing to estimate the vibration frequency of each disk. The effect of disk thickness, target fit and duration of testing on the mass loss is described. We find that in the current configuration of NMR targets, the vibrations and mass loss on the first disk are minimized, while those in the adjacent disks are highest. The microphone and high-speed image data show that increased flow rates and increased duration of testing increases vibration frequency and mass loss. The mass loss is due to both disk rotation and back and forth motion. There are visible wear marks on the disks with the highest mass loss. We also note that the current NMR window gap reduces flow induced vibrations compared to the previous smaller gaps. Improved target holders significantly reduce disk mass loss to almost negligible quantities. This work finds that the larger window to first disk gap and improved target holder geometry should allow NMR to successfully conduct irradiations with minimal mass loss. The window tests were conducted to understand the effect of a pulsed beam on both the window longevity and to estimate the window temperature and displacement during pulsing. The experiments presented here were performed at significantly low power, due to the limitations of the induction heating system. The window temperature rose to approximately 73 °C with a significantly reduced power of 45 W without beam pulsing. With a 5 Hz pulse rate, 12.5% duty cycle, the window temperature remained constant at 26 °C. These experiments will be repeated with improved coil geometry and reported in upcoming journal papers.

42 ENGINEERING↗

Effectiveness of Diffusion Barrier Coatings for Mo-Re Embedded in C/SiC and C/C

Advanced high-temperature cooling applications may often require the elevated-temperature capability of carbon/silicon carbide or carbon/carbon composites in combination with the hermetic capability of metallic tubes. In this paper, the effects of C/SiC and C/C on tubes fabricated from several different refractory metals were evaluated. Though Mo, Nb, and Re were evaluated in the present study, the primary effort was directed toward two alloys of Mo-Re, namely, arc cast Mo-41Re and powder metallurgy Mo-47.5Re. Samples of these refractory metals were subjected to either the PyC/SiC deposition or embedding in C/C. MoSi2(Ge), R512E, and TiB2 coatings were included on several of the samples as potential diffusion barriers. The effects of the processing and thermal exposure on the samples were evaluated by conducting burst tests, microhardness surveys, and scanning electron microscopic examination (using either secondary electron or back scattered electron imaging and energy dispersive spectroscopy). The results showed that a layer of brittle Mo-carbide formed on the substrates of both the uncoated Mo-41Re and the uncoated Mo-47.5Re, subsequent to the C/C or the PyC/SiC processing. Both the R512E and the MoSi2(Ge) coatings were effective in preventing not only the diffusion of C into the Mo-Re substrate, but also the formation of the Mo-carbides. However, none of the coatings were effective at preventing both C and Si diffusion without some degradation of the substrate.

Glass, David E.↗

Corrosion characteristics of Mo and TZM alloy for plasma facing components in molten lithium at 623 K

Here, in this study, the corrosion behaviours of molybdenum (Mo) and a Mo-based alloy (TZM) were investigated using a static immersion corrosion technique. Weight loss, surface microstructure, and corrosion depth of Mo and the TZM alloy were correlated with elements. The compatibility of Mo and the TZM alloy in static liquid Li was suitable. Mo demonstrated uniform corrosion with a homogenous dissolution of free C and Mo, and TZM alloy exhibited a nonuniform corrosion behaviour with a preferential grain boundary attack caused by the selective dissolution of free C, Ti, and Zr. When the surface oxidation layer of the samples was consumed, free C from Mo and TZM diffused into molten Li to form Li 2 C 2 and then was captured by Zr, Ti, and Mo to form thermodynamically stable carbides, which resulted in the enrichment of the C layer near the sample surfaces. In addition, Ti and Zr acted as N-trappers in liquid Li; the formation of Zr and Ti nitrides resulted in the enrichment of N, Ti, and Zr elements on the surface and led to TZM corrosion increase. Thus, Zr and Ti depletion, pitting, and grain boundary corrosion were problematic for TZM under long-term exposure to liquid Li. Reducing the content of free C and nonmetallic N and increasing the amount of Ti and Zr carbides on the surface of and inside the raw TZM alloy helped improve the corrosion resistance of TZM in liquid Li.

36 MATERIALS SCIENCE↗

Alloy designs for high temperature Mo-base systems

For high temperature applications Mo base alloy requirements include both superior structural performance and environmental resistance. To address these requirements alloys in the Mo-Si-B system and refractory multi-principal element alloys (RMPEA) are being developed that exhibit a promising potential, but also have some remaining challenges to improve ductility, lower density and enhance environmental resistance. In the Mo-Si-B system microstructures with a Mo solid solution (Moss) Mo 3 Si and Mo 5 SiB 2 (T2) phases have been the focus of attention. However, the Si solubility in the Moss phase diminishes the ductility and toughness. In order to address this issue a new design based upon Moss, Mo 2 B and T 2 phases lowers the Si solubility in the Moss to improve ductility while the T 2 phase maintains the oxidation performance. Selected additions of Al and Ti enable a density reduction to below 8 g/cm 3 . The RMPEA designs for Mo-rich alloys provide for excellent structural performance, but the complex oxidation products provide no protection. However, in this case a new coating design has been introduced that provides the required environmental resistance.

36 MATERIALS SCIENCE↗