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At least 829 records · Page 46
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Phonon modal analysis of thermal transport in ThO 2 with point defects using equilibrium molecular dynamics

Defects can significantly degrade the thermal conductivity of ThO 2 , an advanced nuclear fuel material as well as a surrogate for other fluorite-structured materials. Here, we investigate how point defects in ThO 2 impact phonon mode-resolved thermal transport. By incorporating phonon modes from lattice dynamics, we decompose the trajectory and heat flux to phonon normal mode space and extract key phonon properties, including phonon relaxation times and their contributions to thermal conductivity. We implement two methods. The first method is based on the Green Kubo formalism to resolve the contribution of each phonon mode to thermal conductivity. The second resolves the lifetime of individual phonon modes and the thermal conductivity is calculated using the Boltzmann transport equation within relaxation time approximation. Notably, a lower contribution of acoustic modes is revealed compared to perturbative approaches considering only three-phonon scattering processes. The effects of four types of point defects are evaluated. The strongest impact on a reduction in thermal conductivity is from Th interstitials, followed by Th vacancies. O interstitials/vacancies have a similar impact, albeit smaller than defects on the thorium sublattice. These observations are consistent with previous studies.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Demystify radiation-enhanced hydrogen isotope diffusion in Fe-Ni-Cr austenitic stainless steels

Understanding and containing hydrogen isotope diffusion is crucial for many nuclear applications. In situ experiments have consistently shown that radiation significantly enhances isotope diffusion in austenitic stainless steels. Despite extensive research, the mechanism behind this phenomenon remains elusive, as most radiation-induced defects (e.g., vacancies, dislocations, and grain boundaries) typically trap hydrogen, thereby slowing diffusion. While grain boundaries may increase in-plane diffusivity and interstitials may enhance diffusion due to material swelling, these effects are relatively minor. Utilizing an Fe-Ni-Cr-H interatomic potential for stainless steels, we conducted extensive molecular dynamics simulations to investigate the origins of radiation-enhanced diffusion. Here, our findings reveal that when a system is resolidified, mimicking defects created by radiation displacements, the resulting structure contains a mixture of phases, boundaries, and dislocation networks. This defective structure significantly increases hydrogen diffusivity, enhancing it by approximately 1.7 times at 900 K. These results suggest that the complex defect structures formed during radiation displacements are the primary drivers of the observed diffusion enhancement, providing valuable insights into the mechanisms underlying radiation-enhanced diffusion in nuclear materials.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Grain boundary self-diffusion and point defect interactions in α -U via molecular dynamics

Though metallic U-Zr fuel has been used in nuclear reactors since the 1960s, many of its fundamental and thermodynamic properties are still unknown. The a-U phase, which has a highly anisotropic crystal structure and physical properties, is present in U-Zr fuel. The character and behavior of a-U grain boundaries will strongly impact fuel thermophysical performance under irradiation. Here, we study the interaction of point defects with grain boundaries, diffusion along grain boundaries, and the predicted diffusional creep behavior of a-U via molecular dynamics. We calculate the segregation energy of vacancies and interstitials to grain boundaries and quantify the biased sink strength of the grain boundaries, and observe that this sink strength is not strongly dependent on the grain boundary orientation. We also find that grain boundary diffusivity is strongly dependent on the grain boundary energy and grain boundary orientation. The presence of point defects within the grain boundary can induce diffusion in grain boundaries with low formation energies and can enhance diffusion in high-energy grain boundaries. We also find that diffusional creep of a-U at prototypical metallic fuel operation conditions is extremely high and could help explain observed metallic fuel swelling behaviors.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Understanding the effect of minor alloying elements on helium bubble formation in ferritic-martensitic steels

Ferritic-martensitic steels are promising structural materials for advanced nuclear reactors. To minimize long-term radioactivity, reduced-activation ferritic-martensitic steels have been developed by substituting high-activation elements like Ni and Mo with low-activation elements such as W. However, the impact of these alloying modifications on helium bubble formation, which plays a key role in material swelling, remains unclear. Here, in this study, we compared helium bubble formation in ferritic-martensitic steel T91 and reduced-activation ferritic-martensitic steel F82H. Both materials were irradiated with sequential 100 keV, 150 keV, and 200 keV helium ions to a dose of 0.5 dpa and a helium concentration of 9,000 appm at 500°C. The helium bubbles in F82H exhibited a larger average size and a lower density than those in T91, suggesting differences in minor alloying elements may influence the bubble growth. Here, to investigate the effects of these alloying elements, we characterized radiation-induced segregation near bubbles and grain boundaries. Prominent Ni-Mn-Si enriched clusters were found near bubbles in T91, while only Mn-Si enriched clusters were found near bubbles in F82H. In addition, the obvious Cr enrichment near grain boundaries was absent around bubbles in both steels. The different segregation trends among elements revealed the variations in element diffusion mechanisms and the different sink biases between bubbles and grain boundaries. Cr enrichment near grain boundaries is mostly driven by interstitial-mediated diffusion. However, since bubble growth relies on net vacancy flux, vacancy-mediated diffusion plays a dominant role in controlling element segregation near bubbles. Therefore, Cr enrichment was not found near bubbles. Because of preferential vacancy-drag diffusion for Ni, Si and Mn, these elements were enriched near bubbles. Due to the strong binding energies of vacancies with these solute atoms, the vacancy diffusivity can be reduced near these solutes. Therefore, the more prominent Ni-Si-Mn clustered near helium bubbles in T91 lead to stronger suppression of helium bubble growth compared to F82H.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Ab-initio informed cluster dynamics simulation of self- and Xe diffusivity in uranium mononitride under irradiation

Uranium mononitride (UN) is one of the ceramic nuclear fuel alternatives to oxide fuels considered for light water reactor and advanced reactor designs, as it presents significant advantages such as high uranium density (better economics) and high thermal conductivity and melting point (increased safety). Self- and fission gas diffusivities need to be better understood, given that they influence key fuel performance phenomena like swelling and fission gas release. Recently, radiation enhanced diffusivity was investigated in UN by means of cluster dynamics simulations relying on empirical potential-based parameterizations, the reliability of which highly depends on the interatomic potential accuracy. Here, in this work, we refine this approach by determining, using ab-initio calculations, the properties of defect clusters containing vacancies, self-interstitials and Xe impurities. We also consider larger clusters than previous studies. The obtained dataset (formation enthalpies, entropies, and migration barriers) is used to parameterize a cluster dynamics model of mobile clusters, and to calculate the defect cluster concentrations under irradiation. This gives us access to the radiation enhanced self- and fission gas diffusivities. Although the resulting diffusivities are close to the values reported in the literature, we find important qualitative differences in the diffusion mechanisms. Capturing the correct mechanisms is crucial to properly describe the chemistry and fission rate dependence of the model.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2026

Helium co-implantation effects on dislocation loop evolution during in situ ion irradiations of a novel additive-manufactured Fe-9Cr steel alloy

This study examines the impact of helium injection rate on dislocation loop evolution during ion irradiation of a novel, additively manufactured (AM) 9Cr reduced-activation ferritic/martensitic (RAFM) steel. Through in situ transmission electron microscopy ion irradiations and post-irradiation characterization, the effects of simultaneous 1 MeV Kr²⁺ and 12 keV He⁺ ion irradiation at 400°C to 5 dpa with varying helium levels were examined. The findings reveal that helium co-injection significantly increases dislocation loop density, primarily through the formation of small defect features exhibiting contrast and projected morphologies consistent with a⟨100⟩ loops (∼1 nm), while suppressing larger a/2⟨111⟩ loops. The findings underscore the complex interplay among continuously increasing helium content, temperature, and alloy composition in the evolution of dislocation loops under irradiation in RAFM steels. The study highlights the need for further investigation into helium-mediated mechanisms, such as proposed interactions between self-interstitial atoms and helium atoms, to enhance the performance of RAFM steels in advanced nuclear reactors.

ANA2↗
DOE OSTI2020

Harbinger of hysteresis in lithium-rich oxides: Anionic activity or defect chemistry of cation migration

In this work, we present findings on the mechanisms of hysteresis in lithium-rich cathode oxides. It is generally reported that the energy inefficiency, observed during electrochemical cycling of Li-rich electrodes, is a direct result of anion redox processes. Similarly, the coupled phenomenon of cation migration has been cited as being a mere consequence of that process with no essential ramification to hysteresis. Such works, however, have only shown correlations and not causation. Specifically, studies that clearly preclude the complete absence of either anion redox or cation migration (down to defect-level concentrations) are not reported yet. Herein, we present first principles calculations and experimental data on a bespoke Li-rich system that is indubitably immune to oxygen activity but yet exhibits significant energy inefficiency. Additionally, the results directly implicate transition metal migration as the fundamental, sole process responsible for hysteresis in this material. This study is of particular importance to the design and development of new Li-rich materials aimed at eliminating the role of oxygen and enhancing the effective cationic redox contribution to the capacity and points out the essential need to develop materials devoid of transition metal migration to interstitial sites in both layered and disordered oxides alike.

25 ENERGY STORAGE↗
DOE OSTI2015

Crystal structures and compressibility of novel iron borides Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} synthesized at high pressure and high temperature

We present here a detailed description of the crystal structures of novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} with various iron content (x=1.01(1), 1.04(1), 1.32(1)), synthesized at high pressures and high temperatures. As revealed by high-pressure single-crystal X-ray diffraction, the structure of Fe{sub 2}B{sub 7} possesses short incompressible B–B bonds, which make it as stiff as diamond in one crystallographic direction. The volume compressibility of Fe{sub 2}B{sub 7} (the bulk modulus K{sub 0}= 259(1.8) GPa, K{sub 0}′= 4 (fixed)) is even lower than that of FeB{sub 4} and comparable with that of MnB{sub 4}, known for high bulk moduli among 3d metal borides. Fe{sub x}B{sub 50} adopts the structure of the tetragonal δ-B, in which Fe atoms occupy an interstitial position. Fe{sub x}B{sub 50} does not show considerable anisotropy in the elastic behavior. - Graphical abstract: Crystal structures of novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} (x=1.01(1), 1.04(1), 1.32(1)). - Highlights: • Novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50}, were synthesized under HPHT conditions. • Fe{sub 2}B{sub 7} has a unique orthorhombic structure (space group Pbam). • Fe{sub 2}B{sub 7} possesses short incompressible B–B bonds that results in high bulk modulus. • Fe{sub x}B{sub 50} adopts the structure of the tetragonal δ-B composed of B{sub 12} icosahedra. • In Fe{sub x}B{sub 50} intraicosahedral bonds are stiffer than intericosahedral ones.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Hydrogenation studies on NdScSi and NdScGe

NdScSi and NdScGe were synthesized from the elements via arc-melting and subsequent annealing. Their ordered La{sub 2}Sb type structures, with space group I4/mmm, were refined from single crystal X-ray diffractometer data: a=428.94(6) and b=1570.5(3) pm, wR2=0.0395, 309 F{sup 2} values for NdScSi and a=431.2(1) and c=1581.3(5) pm, wR2=0.1220, 227 F{sup 2} values for NdScGe, with 11 variables per refinement. Hydrogen insertion was performed on both Nd-based intermetallics by solid/gas reaction. Hydrogen uptake keeps the pristine compound space group but yields an anisotropic expansion of the unit cell with a large increase of c (≈+7%) and a slight decrease of a (≈−1.7%) parameters. Hydrogen absorption at 350 °C and under 5 bar of H{sub 2} pressure shows that the hydride NdScSiH{sub 1.48(5)} is formed. An in-situ neutron diffraction study during the deuteration of NdScSi reveals for the first time in a CeScSi-type compound, the possibility to fill two interstitial sites with deuterium atoms, leading to the composition NdScSiD{sub 1.5} for the deuteride adopting then the La{sub 2}Fe{sub 2}Se{sub 2}O{sub 3}-type structure. From magnetization measurements, we evidence that hydrogenation strongly reduces the Curie temperature of NdScSi (T{sub C}=175 K) and NdScGe (T{sub C}=194 K) since NdScSiH{sub 1.5} and NdScGeH{sub x} undergo a magnetic transition at 4 K and around 2 K, respectively. - Highlights: • Crystal structures of NdScSi and NdScGe were refined from single crystal XRD data. • The hydrogenation of NdScSi leads to the formation of the NdScSiH{sub 1.5} hydride. • NdScSiD{sub 1.5} adopts the La{sub 2}Fe{sub 2}Se{sub 2}O{sub 3}-type structure. • Hydrogenation strongly reduces the ordering temperature of both intermetallics.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Directly obtained τ-phase MnAl, a high performance magnetic material for permanent magnets

The metastable tetragonal τ-phase has been directly obtained from casting Mn{sub 0.54}Al{sub 0.46} and (Mn{sub 0.55}Al{sub 0.45}){sub 100}C{sub 2} using the drop synthesis method. The as-casted samples were ball milled to decrease the particle size and relaxed at 500 °C for 1 h. The phase composition, crystallographic parameters, magnetic properties and microstructure were systematically studied. The results reveal that the τ-phase could be directly obtained from drop synthesis. The highest M{sub s} of 117 emu/g was achieved in the (Mn{sub 0.55}Al{sub 0.45}){sub 100}C{sub 2} where the τ-phase was stabilized by doping with carbon. Carbon doping increased the c/a ratio of the τ-phase as it occupies specific interstitial positions (½, ½, 0) in the structure. Furthermore, ball milling increases the coercivity (H{sub c}) at the expense of a decrease in magnetic saturation (M{sub s}). The increase in coercivity is explained by a decrease of grain size in conjunction with domain wall pinning due to defects introduced during the ball milling process. - Graphical abstract: The tetragonal τ-phase has been directly obtained from casting Mn{sub 0.54}Al{sub 0.46} and (Mn{sub 0.55}Al{sub 0.45}){sub 100}C{sub 2} using the drop synthesis method. The phase composition, crystallographic parameters, magnetic properties and microstructure were systematically studied. The highest M{sub s} of 117 emu/g was achieved for (Mn{sub 0.55}Al{sub 0.45}){sub 100}C{sub 2} ball milling increases the coercivity (H{sub c}) at the expense of a decrease in magnetic saturation (M{sub s}). - Highlights: • The ferromagnetic τ-phase has been directly obtained from casting. • The highest M{sub s} of 117 emu/g was achieved for (Mn{sub 0.55}Al{sub 0.45}){sub 100}C{sub 2}. • Ball milling increases the coercivity but decreases the magnetic saturation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Interplay between crystal and magnetic structures in YFe{sub 2}(H{sub α}D{sub 1−α}){sub 4.2} compounds studied by neutron diffraction

We report a detailed magnetic structure investigation of YFe{sub 2}(H{sub α}D{sub 1−α}){sub 4.2} (α=0, 0.64, 1) compounds presenting a strong (H,D) isotope effect by neutron diffraction and Mössbauer spectroscopy analysis. They crystallize in the same monoclinic structure (Pc space group) with 8 inequivalent Fe sites having different H(D) environment. At low temperature, the compounds are ferromagnetic (FM) and show an easy magnetization axis perpendicular to the b axis and only slightly tilted away from the c axis. Upon heating, they display a first order transition from a ferromagnetic towards an antiferromagnetic (AFM) structure at T{sub M0} which is sensitive to the H/D isotope nature. The AFM cell is described by doubling the crystal cell along the monoclinic b axis. It presents an unusual coexistence of non magnetic Fe layer sandwiched by two thicker ferromagnetic Fe layers which are antiparallel to each other. This FM-AFM transition is driven by the loss of ordered moment on one Fe site (Fe7) through an itinerant electron metamagnetic (IEM) behaviour. The key role of the Fe7 position is assigned to both its hydrogen rich atomic environment and its geometric position. Above T{sub M0} a field induced metamagnetic transition is observed from the AFM towards the FM structure accompanied by a cell volume increase. Both thermal and magnetic field dependence of the magnetic structure are found strongly related to the anisotropic cell distortion induced by (H,D) order in interstitial sites. - Graphical abstract: Representation of the FM-AFM magnetic structures of YFe{sub 2}D{sub 4.2} deuteride. - Highlights: • YFe{sub 2}(H,D){sub 4.2} compounds undergoes a isotope sensitive FM-AFM transition at T{sub M0}. • The FM structure is formed of Fe moments perpendicular to the monoclinic b axis. • AFM structure is formed by antiparallel Fe layers separated by non-magnetic Fe layer. • One Fe site among eight loses its moment at T{sub M0} due to larger Fe–H bonding. • Magnetic properties are driven by the monoclinic distortion induced by D order.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Oxygen-storage behavior and local structure in Ti-substituted YMnO{sub 3}

Hexagonal manganates RMnO{sub 3} (R=Y, Ho, Dy) have been recently shown to exhibit oxygen-storage capacities promising for three-way catalysts, air-separation, and related technologies. Here, we demonstrate that Ti substitution for Mn can be used to chemically tune the oxygen-breathing properties of these materials towards practical applications. Specifically, Y(Mn{sub 1−x}Ti{sub x})O{sub 3} solid solutions exhibit facile oxygen absorption/desorption via reversible Ti{sup 3+}↔Ti{sup 4+} and Mn{sup 3+}↔Mn{sup 4+} reactions already in ambient air at ≈400 °C and ≈250 °C, respectively. On cooling, the oxidation of both cations is accompanied by oxygen uptake yielding a formula YMn{sup 3+}{sub 1−x-y}Mn{sup 4+}{sub y}Ti{sup 4+}{sub x}O{sub 3+δ}. The presence of Ti promotes the oxidation of Mn{sup 3+} to Mn{sup 4+}, which is almost negligible for YMnO{sub 3} in air, thereby increasing the uptake of oxygen beyond that required for a given Ti{sup 4+} concentration. The reversibility of the redox reactions is limited by sluggish kinetics; however, the oxidation process continues, if slowly, even at room temperature. The extra oxygen atoms are accommodated by the large interstices within a triangular lattice formed by the [MnO{sub 5}] trigonal bipyramids. According to bond distances from Rietveld refinements using the neutron diffraction data, the YMnO{sub 3} structure features under-bonded Mn and even more severely under-bonded oxygen atoms that form the trigonal bases of the [MnO{sub 5}] bipyramids. The tensile bond strain around the 5-fold coordinated Mn site and the strong preference of Ti{sup 4+}(and Mn{sup 4+}) for higher coordination numbers likely provide driving forces for the oxidation reaction. Reverse Monte Carlo refinements of the local atomic displacements using neutron total scattering revealed how the excess oxygen atoms are accommodated in the structure by correlated local displacements of the host atoms. Large displacements of the under-bonded host oxygen atoms play a key part in this lattice-relaxation process, facilitating reversible exchange of significant amounts of oxygen with atmosphere. - Graphical abstract: Concurrent redox reactions involving Ti and Mn yield facile absorption/desorption of excess oxygen. - Highlights: • Concurrent redox reactions involving Ti and Mn yield oxygen absorption/desorption. • Excess oxygen is accommodated as interstitials via correlated atomic shifts. • Oxygen breathing is facilitated by the under-bonding of host Mn and O atoms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Identify OH groups in TiOF{sub 2} and their impact on the lithium intercalation properties

A detailed investigation on the chemical composition of the cubic form of titanium oxyfluoride-based compound reveals the presence of OH groups substituting the oxide/ fluoride sublattice. The substitution of oxide by hydroxyl groups induces the presence of titanium vacancies (□) which were characterized by {sup 1}H and {sup 19}F solid-state NMR. {sup 1}H NMR shows that OH groups are present as bridging Ti-OH-Ti or terminal OH groups, i.e. sitting close to a titanium vacancy Ti-OH-□. The electrochemical properties vs. Li{sup +}/Li indicates that the presence of OH groups prevents the intercalation of lithium in the upper voltage region (1.2–3 V vs. Li{sup +}/Li). Indeed, a partial dehydroxylation of the framework enables to improve the reversibility of the lithium insertion/de-insertion processes. Since the presence of OH groups in this type of compounds is usual and depends on the synthesis method employed, this work enables to rationalize the different electrochemical behaviors reported in the literature and further highlights the importance of a good knowledge of the chemical composition with regard to the physico-chemical properties. - Graphical abstract: The substitution of oxide by hydroxyl groups inducing the formation of titanium vacancies (□), i.e., Ti{sub 1−x}□{sub x}O{sub 1-4x}(OH){sub 4x+y}F{sub 2−y}, was characterized by solid-state {sup 1}H and {sup 19}F NMR. - Highlights: • Evidences of the presence of OH groups and titanium vacancies in titanium oxyfluoride. • {sup 1}H NMR showed the presence of Ti-OH-Ti and Ti-OH-□ species. • The presence of OH groups limits the insertion of lithium within the interstitial sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Structural unit charge density and molecular cation templating effects on orientational geometric isomerism and interlayer spacing in 2-D uranyl sulfates

The new uranyl aqua sulfate compound [({CH_3}{sub 3}N{sub 2}C{sub 3}H{sub 3}{CH_2COOH})(H{sub 3}O)] [(UO{sub 2}){sub 2}(SO{sub 4}){sub 3}(H{sub 2}O)]·1.5H{sub 2}O was synthesized and the crystal structure determined. The two-dimensional uranyl-aqua sulfate compound exhibits a previously reported anionic structural unit topology, but features an interstitial complex incorporating hydronium in the form of a disorder Zundel cation and the cation moiety from the ionic liquid 1-carboxymethyl 3-methylimidazolium bistriflimide [HBetMIm][Tf{sub 2}N], which forms hydrogen bonding dimer pairs. An analysis of similar uranyl sulfate complexes from the literature is conducted to explore the relative importance and role of structure directing factors in alkylammonium charge-balanced two-dimensional uranyl sulfates. A correlation is observed between structural unit charge density and interlayer spacing, with a concomitant direction of structural and orientational geometric isomerism of the anionic structural unit. We discuss the role of synthetic conditions and molecular cation properties in directing structural unit formation through charge density matching and hydrogen bonding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Electron doping of NdNiO 3 thin films using dual chamber CaH 2 annealing

Hydrogen donor doping has been exploited as a strategy to manipulate the electronic structure and electrical properties of functional oxide systems. Especially, the development of synthetic methods to achieve electron doping of perovskite rare-earth nickelate thin films utilizing interstitial hydrogen is highly desirable considering the rich electronic phase diagram hosting several functional properties. Here, in this work, we present the hydrogenation of NdNiO 3 (NNO) thin films using CaH 2 annealing and the resulting giant modulation of electrical resistivity in hydrogenated NNO (H–NNO) thin films. Magnetron sputtering was employed to deposit epitaxial ~60 nm-thin NNO films on single crystal LaAlO 3 (LAO) substrates. The formation of the pristine perovskite NNO phase was realized after annealing the films at 500 °C for 24 h. CaH 2 annealing of NNO thin films for time durations ranging from 1 to 6 h was performed in a vacuumed ampule with two interconnected chambers at 280 °C. The two-chamber design enables a simple and clean approach for hydrogen doping without physical contact between the powder and sample of interest. X-ray diffraction and Raman spectroscopy revealed the formation of NNO in pristine samples, and the subsequent hydrogen incorporation upon CaH 2 annealing without forming any impurity phases. The conversion of the oxidation state of Ni towards +2 upon CaH 2 annealing was probed using X-ray photoelectron spectroscopy and X-ray absorption spectroscopy. Consequently, a substantial increase in the room-temperature resistivity was observed upon CaH 2 annealing indicating the formation of a strongly correlated electronic configuration of Ni in H–NNO due to electron doping. Overall, the findings of this study highlight the versatility of CaH 2 annealing as an electron doping method to tune the electrical properties of correlated oxides at low temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Reaction path model of the formation of abiotic immiscible hydrocarbon fluids in subducted carbonated serpentinites, Lanzo Massif (Western Italian Alps)

Fluids generated from subducted slabs participate in the cycling of deep carbon in the crust and upper mantle. In these fluids, aqueous carbon species vary in oxidation state between +IV and -IV depending on whether the fluids are oxidizing or reducing, respectively. Most studies of subduction-zone fluids have focused on oxidized carbon species. However, recent studies of natural samples have demonstrated the occurrence of deep, reducing fluids, generated in both subducted oceanic upper mantle and crustal rocks. CH 4 -H 2 -rich fluid inclusions in subducted carbonated serpentinites have demonstrated the existence of abiotic, immiscible, hydrocarbon fluids at upper mantle conditions. To investigate the formation of such immiscible hydrocarbon fluids during the evolution of subducted carbonated serpentinites, we used equilibrium constants from the Deep Earth Water model to carry out predictive chemical mass transfer modeling to simulate the alteration reactions. A novel feature of the models was the inclusion of an immiscible hydrocarbon fluid containing six components (CH 4,f , C 2 H 6,f , C 3 H 8,f , isoC 4 H 10,f , CO 2,f , H 2,f ). This feature enabled prediction of the formation of a separate immiscible fluid in equilibrium with aqueous species and minerals. We developed a predictive reaction path model of invasive H 2,f reacting with carbonated serpentinites and interstitial aqueous fluids for comparison with the natural samples from the Lanzo Massif, western Italian Alps. Over a range of temperatures and pressures, immiscible hydrocarbon fluids formed in association with altered mineral assemblages. Reaction progress caused the transformation of carbonated serpentinites and the formation of clinopyroxene, brucite, graphite, and hydrocarbon fluids, along with changes of pH, logfO 2 , and aqueous species. CH 4,f was the most abundant hydrocarbon species in all the models. The overall results at 2.0 GPa and 400 to 450 °C were consistent with the natural samples from the Lanzo Massif. Interestingly, large amounts of H 2 O formed due to oxidation of H 2 . More hydrocarbons and H 2 O formed in models with lower fluid/rock mass ratios or with more reactant H 2 . Models at different pressure and temperature conditions showed similar results with some variation in the relative stabilities of aragonite, graphite and olivine solid solution, and associated differences in mineral sequences, hydrocarbon fluids, values of aqueous species, and the final log fO 2 and pH. As a result, our models strongly support the laboratory and field evidence that reduction of carbonated serpentinites by infiltrating H 2 fluids can cause the formation of immiscible, abiotic hydrocarbon fluids in subduction zones.

58 GEOSCIENCES↗