Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Effective diffusivity”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 847 records · Page 47

Role of niobium in the high-temperature oxidation of titanium

Here, we compared the oxidation of Ti and Ti-2 at.% Nb at 800°C in Ar-20% O 2 and in sequential 16 O 2 - 18 O 2 atmospheres to clarify the role of niobium in the high-temperature oxidation of titanium. Niobium had no effect on the amount of oxygen dissolved in the metal or on oxygen diffusion in the metal. Instead, niobium enhanced oxidation resistance by segregating to TiO 2 grain boundaries, where it likely slowed outward Ti diffusion. These findings spotlight doping of TiO 2 grain boundaries as a strategy for improving the oxidation resistance of Ti alloys and, more generally, TiO 2 -forming alloys.

36 MATERIALS SCIENCE↗

Early diagenetic processes in an iron-dominated marine depositional system

The early diagenetic interplay between reactive iron, sulfur, and organic matter in the bathymetrically isolated Santa Monica Basin (SMB) sediments are investigated in this study. Here, we explore solid-phase and porewater profiles from the basin, supplemented with a transect from 71 to 907 m water depth that includes oxygenated (>60 μM O 2 ) bottom waters near the coast and oxygen-deficient waters (~4 µM O 2 ) in the basin. The geochemical data of the basin sediments are further scrutinized by means of reactive transport modeling. The results show that the basin sediments do not follow the traditional geochemical signatures of oxygen-deficient settings. A lack of dissolved sulfide accumulation and sulfurized iron persists despite the sediments being deposited under reducing conditions (without bioturbation/bioirrigation), strong organic carbon input (TOC up to 5.0 wt%), and active dissimilatory sulfate reduction. Not only did we find an exceptional enrichment in highly reactive Fe in the surface sediments (~45 % of total Fe), but the enrichment of reactive Fe, including ferrihydrite, persists downcore and coexists with high levels of dissolved Fe. The enhanced preservation of Fe oxides and lack of iron-sulfide precipitation is in part explained by detection via Mössbauer spectra of iron oxides bounded to organic matter (Fe[III]-OM coprecipitates). The modeled Fe budget shows that most of the Fe oxides in the surface sediments are internally recycled by upward diffusion and subsequent oxidation of Fe 2+ . Sulfide oxidation coupled to Fe reduction effectively precludes sulfide accumulation while enhancing build-up of dissolved Fe, fueling the Fe cycle within the first 5 cm depth. Continuous reoxidation of Fe 2+ enhances the formation of Fe(III)-OM coprecipitates, limiting the amount of reactive organic matter. In the unavailability of labile organic matter, other than within the uppermost layers, the organic-rich sediment profiles are dominated by Fe cycling that limits the production and preservation of sulfides and enhances the preservation of Fe oxides and organic carbon. Finally, this study highlights key local controls on Fe availability in marginal basins and describes an intricate biogeochemical C-Fe-S cycling in modern and possibly ancient marine systems with important implications for Fe availability in the marine realm.

58 GEOSCIENCES↗

An interlaboratory comparison of mid-infrared spectra acquisition: Instruments and procedures matter

Diffuse reflectance spectroscopy has been extensively employed to deliver timely and cost-effective predictions of a number of soil properties. However, although several soil spectral laboratories have been established worldwide, the distinct characteristics of instruments and operations still hamper further integration and interoperability across mid-infrared (MIR) soil spectral libraries. In this study, we conducted a large-scale ring trial experiment to understand the lab-to-lab variability of multiple MIR instruments. By developing a systematic evaluation of different mathematical treatments with modeling algorithms, including regular preprocessing and spectral standardization, we quantified and evaluated instruments' dissimilarity and how this impacts internal and shared model performance. We found that all instruments delivered good predictions when calibrated internally using the same instruments' characteristics and standard operating procedures by solely relying on regular spectral preprocessing that accounts for light scattering and multiplicative/additive effects, e.g., using standard normal variate (SNV). When performing model transfer from a large public library (the USDA NSSCKSSL MIR library) to secondary instruments, good performance was also achieved by regular preprocessing (e. g., SNV) if both instruments shared the same manufacturer. However, significant differences between the KSSL MIR library and contrasting ring trial instruments responses were evident and confirmed by a semi-unsupervised spectral clustering. For heavily contrasting setups, spectral standardization was necessary before transferring prediction models. Non-linear model types like Cubist and memory-based learning delivered more precise estimates because they seemed to be less sensitive to spectral variations than global partial least square regression. In summary, the results from this study can assist new laboratories in building spectroscopy capacity utilizing existing MIR spectral libraries and support the recent global efforts to make soil spectroscopy universally accessible with centralized or shared operating procedures.

58 GEOSCIENCES↗

On the high-temperature stability of the Al 8 Cu 3 Ce intermetallic in an additively manufactured Al-Cu-Ce-Zr alloy

High-temperature resistant eutectic Al alloys are crucial materials for lightweight and energy efficient design in the automotive and aviation industries. Additive manufacturing offers a pathway to refine eutectic microstructures and develop novel alloys with superior high-temperature strength. High-volume fraction intermetallic Al-Cu-Ce alloys have been developed to deliver high-temperature strength in combination with reduced hot-tearing susceptibility. Zr is added to provide additional strengthening via nanoscale Al 3 Zr precipitation, and to stabilize and avoid coarsening of the Al 8 Cu 3 Ce phase. However, the detailed interaction between Zr and Al 8 Cu 3 Ce remains unexplored. In this work, we show with synchrotron X-ray diffraction that laser powder bed fusion fabricated Al-Cu-Ce and Al-Cu-Ce-Zr alloys contain predominantly the Al 8 Cu 3 Ce intermetallic in the as-fabricated condition. Heat treatment of the Al-Cu-Ce alloy results in the Al 8 Cu 3 Ce → Al 8 Cu 4 Ce phase transformation. In the Al-Cu-Ce-Zr alloy, minor fractions of (Al,Cu,Si) 4 Ce and Al 2 Cu-θ are found in the as-fabricated condition, while Al 8 Cu 3 Ce remains stable during heat treatment. Atom probe microscopy quantifies intermetallic stoichiometries and reveals how Zr is enriched at the Al-matrix/Al 8 Cu 3 Ce interface acting as a diffusion barrier against solute exchange. Calibrated thermodynamic modeling underpins this as a kinetic effect. Here, a qualitative microstructural model summarizes, how Zr stabilizes Al 8 Cu 3 Ce against phase transformations and coarsening.

36 MATERIALS SCIENCE↗

Interfacial microstructure and mechanical properties of rotary inertia friction welded dissimilar 422 martensitic stainless steel to 4140 low alloy steel joints

In this work, dissimilar rotary inertia friction welds between 422 martensitic stainless steel and 4140 martensitic low-alloy steel were made to fabricate prototype heavy-duty diesel engine pistons. The influence of the inertia friction welding process and post weld heat treatment (PWHT) temperature on the interfacial microstructure evolutions and corresponding effects on mechanical properties of the 422/4140 welds were evaluated in detail. Carbon diffused from the 4140 side to the 422 side during PWHT at 650 °C for 1.5 h, causing the formation of a hard carbide-rich layer on the 422 side, and a softer but discontinuous C-depleted layer the 4140 side. PWHT at 700 °C for 1.5 h greatly accelerated C diffusion across the interface relative to 650 °C, resulting in a thicker hard carbide-rich layer and a relatively thick and continuous layer of coarse C-depleted grains (ferrite) on the 4140 side. In addition, the PWHT temperature greatly influenced the tensile properties and fracture behavior of the welds, with the 650 °C PWHT-ed samples failing predominately in a ductile manner in the 4140 heat affected zone during tensile testing. Conversely, the 700 °C PWHT specimens exhibited a strength reduction compared with the 650 °C PWHT specimens because of additional coarsening of the interfacial ferrite layer and softening of the base materials during PWHT, with brittle fracture between the hard and soft layers the predominate failure mechanism. Based on the findings, a reduced PWHT temperature and/or time, minimizing the hardness differential of the base metals, and pre-heating the 422 steel prior to welding are the potential pathways to achieve a more optimal balance between desirable tempering and stress relief of the weld microstructure and undesirable C migration across the weld interface, and to reduce the strength mismatch across the weld.

36 MATERIALS SCIENCE↗

Superionic Surface Li-Ion Transport in Carbonaceous Materials

Unlike Li-ion transport in the bulk of carbonaceous materials, little is known about Li-ion diffusion on their surface. Here, in this study, we have discovered an ultrafast Li-ion transport phenomenon on the surface of carbonaceous materials with limited reversible Li insertion capacity and high surface area. An ionic conductivity of 18.1 mS cm –1 at room temperature is observed in lithiated Ketjen black (KB), far exceeding those of most solid-state ion conductors. Theoretical calculations reveal low diffusion barriers for the surface Li species. As a result, lithiated KB functions effectively as an interlayer between Li and solid-state electrolytes (SSEs) to mitigate dendrite growth. Further, lithiated KB acts as a high-performance mixed ionic–electronic conductor and replaces solid electrolytes to enhance graphite anode performance, demonstrating full utilization with ∼85% capacity retention over 300 cycles. The discovery of this surface-mediated ultrafast Li-ion transport mechanism provides new directions for the design of solid-state ion conductors and solid-state batteries.

Li metal batteries↗

The Impact of the 8–10 March 2012 Geomagnetic Storm on Inner Zone Protons as Measured by Van Allen Probes

The Relativistic Electron Proton Telescope (REPT) instrument on the Van Allen Probes observed a double-peaked inner zone proton population throughout the 7 year lifetime of the mission. M. Hudson et al. (2023) showed that a strong SEP event accompanied by a CME-shock in early March 2012 provided the Solar Energetic Proton (SEP) source for the higher L trapped proton population, which then diffused radially inward to be observed by REPT at L = 2. The study followed trajectories of SEP protons launched isotropically from a sphere at 7 Re for 2.5 hr in fields calculated by the LFM-RCM global MHD model, which includes electric fields needed to model the transport and trapping of the protons by the shock, and then a radial diffusion simulation was run for 2 years using the result from the test-particle simulation as the initial condition. The simulation result was compared with REPT measurement in November 2013 and showed reasonable agreement. However, the simulation overestimated the Phase Space Density by a factor of four due to lack of field line curvature scattering during the storm in the model. In this study, a test-particle simulation is performed for 2 days following the injection and trapping of protons in March 2012 using TS05 fields to simulate the field line curvature scattering of the trapped SEP due to the buildup of the ring current during the geomagnetic storm. The resulting sample distribution was then weighted using the flux at the end of the two-hour MHD-test particle simulation. A radial diffusion simulation is then run using the initial profile that included the loss effect, with improved comparison with REPT measurements after 2 years.

79 ASTRONOMY AND ASTROPHYSICS↗

Probing the influence of ion-pairing on ligand-field excited-state dynamics

Exploration of the photophysical and photochemical properties of transition metal complexes has driven ground-breaking advancements in solar energy conversion technologies, including photoredox catalysis. While significant research has been devoted to understanding excited state properties of second- and third-row transition metal complexes, earth-abundant first-row metal complexes have received comparatively little attention in this context until very recently. In particular, the role of ion-pairing – which has been identified as a potentially significant factor for Ir(III)-based photosensitizers – has not been examined with regard to its influence on the ligand-field excited states that dominate much of first-row photophysics. A key challenge in studying ion-pair interactions lies in quantifying the extent and nature of ion-pairing, particularly in non-aqueous media where the vast majority of photophysical studies are performed. Cobalt(III) polypyridyl complexes provide an attractive platform to address such questions due to their demonstrated potential for applications in photoredox catalysis involving ligand-field excited states. In the present study, we prepared a cobalt(III) polypyridyl complex, [Co(4,4′-OMebpy) 3 ](BAr F 4 ) 3 (where 4,4′-OMebpy is 4,4′-dimethoxy-2,2′-bipyridine and BAr F 4 is tetrakis(3,5-bis(trifluoromethyl)-phenyl)borate) to probe ion-pairing in non-aqueous solutions. Specifically, analysis of data acquired from both variable-temperature diffusion ordered spectroscopy (DOSY) NMR and 1-D rotating-frame nuclear Overhauser effect (ROE) experiments allowed us to identify and differentiate between solvent-separated ion pairs in high-dielectric media and contact ion pairs in a low-dielectric solvent. Time-resolved absorption spectroscopy was then used to measure ground-state recovery dynamics under these varying conditions of ion-pairing, the results of which revealed an increase in excited-state lifetime for contact ion-pairs that we suggest arises from a reduction in outer-sphere reorganization energy relative to conditions which favored solvent-separated ion pairs. We believe this study demonstrates that one can leverage broadly available NMR-based methods to understand ion-pairing in non-aqueous solutions, which in turn can provide a microscopic picture of intermolecular interactions that can impact the photophysical properties of transition metal-based chromophores.

Ghosh, Atanu [Michigan State University, East Lans↗

Understanding chemical and physical mechanisms in atomic layer deposition

Atomic layer deposition (ALD) is a powerful tool for achieving atomic level control in the deposition of thin films. However, several physical and chemical phenomena can occur which cause deviation from “ideal” film growth during ALD. Understanding the underlying mechanisms that cause these deviations is important to achieving even better control over the growth of the deposited material. Herein, we review several precursor chemisorption mechanisms and the effect of chemisorption on ALD growth. We then follow with a discussion on diffusion and its impact on film growth during ALD. Together, these two fundamental processes of chemisorption and diffusion underlie the majority of mechanisms which contribute to material growth during a given ALD process, and the recognition of their role allows for more rational design of ALD parameters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning superconductivity of Bi 2 Sr 2 CaCu 2 O 8+x by fluoride ion intercalation with LaF 3 gate dielectric

Here, we demonstrate fluorine intercalation into Bi 2 Sr 2 CaCu 2 O 8+x (BSCCO) flakes, as thick as 100 nm, by back-gating a single crystalline LaF 3 substrate. Element-sensitive analysis not only confirms the presence of fluorine in BSCCO after gating but also reveals lateral diffusion of fluorine in BSCCO. Transport measurements further demonstrate the hole-doping effect of fluoride ions in BSCCO through effective modulation of the superconducting transitions. Our work introduces a distinct type of ions (F - ) that can be intercalated into materials via solid state back-gating. It broadens the toolbox of ion back-gating and is useful for addressing exotic phenomena in the heavily hole doped regime.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Nanoscale structural correlations in a model cuprate superconductor

Understanding the extent and role of inhomogeneity is a pivotal challenge in the physics of cuprate superconductors. While it is known that structural and electronic inhomogeneity is prevalent in the cuprates, it has proven difficult to disentangle compound-specific features from universally relevant effects. Here, in this study, we combine advanced neutron and x-ray diffuse scattering with numerical modeling to obtain insight into bulk structural correlations in HgBa 2 ⁢ CuO 4+δ . This cuprate exhibits a high optimal transition temperature of nearly 100 K, pristine charge-transport behavior, and a simple average crystal structure without long-range structural instabilities, and is therefore uniquely suited for investigations of intrinsic inhomogeneity. We uncover diffuse reciprocal-space patterns that correspond to prominent nanoscale correlations of atomic displacements perpendicular to the CuO 2 planes. The real-space nature of the correlations is revealed through three-dimensional pair distribution function analysis and complementary numerical refinement. We find that relative displacements of ionic and CuO 2 layers play a crucial role, and that the structural inhomogeneity is not directly caused by the presence of conventional point defects. The observed correlations are therefore intrinsic to HgBa 2 ⁢ CuO 4+δ , and thus likely important for the physics of cuprates more broadly. It is possible that the structural correlations are closely related to the unusual superconducting fluctuations and Mott-localization in these complex oxides. As advances in scattering techniques yield increasingly comprehensive data, the experimental and analysis tools developed here for large volumes of diffuse scattering data can be expected to aid future investigations of a wide range of materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Trends of Neutron Skins and Radii of Mirror Nuclei from First Principles

The neutron skin of atomic nuclei impacts the structure of neutron-rich nuclei, the equation of state of nucleonic matter, and the size of neutron stars. Here we predict the neutron skin of selected light- and medium-mass nuclei using coupled-cluster theory and the auxiliary field diffusion Monte Carlo method with two- and three-nucleon forces from chiral effective field theory. We find a linear correlation between the neutron skin and the isospin asymmetry in agreement with the liquid-drop model and compare with data. We also extract the linear relationship that describes the difference between neutron and proton radii of mirror nuclei and quantify the effect of charge symmetry breaking terms in the nuclear Hamiltonian. In conclusion, our results for the mirror-difference charge radii and binding energies per nucleon agree with existing data.

79 ASTRONOMY AND ASTROPHYSICS↗

Optimized in situ crystal growth and disordered quasi-one-dimensional magnetism in Li 2 Mn 2 ( MoO 4 ) 3

We present that the quasi-one-dimensional structure of Li 2 Mn 2 ( MoO 4 ) 3 consists of three mutually distinct chains of Li 1 - x Mn x -centered polyhedra in which Mn ostensibly adopts a J = 5 / 2 Mn 2 + configuration. In situ x-ray scattering experiments carried out as crystallites emerge from a molten oxide solution facilitate the synthesis of large single crystals. Ex situ x-ray diffraction finds no evidence of long-range Li/Mn occupancy ordering, suggesting that the structure is effectively composed of finite chains of Mn moments of statistically varying lengths. UV/visible diffuse reflectance spectroscopy measurements establish a wide 3.43(12)-eV direct charge gap consistent with the local polyhedral coordination of the nominally Mn 2 + species. The temperature T dependence of the DC magnetic susceptibility χ reveals a fluctuating moment of only 2.74 μ B ± 0.01 μ B /Mn, dramatically reduced from the 5.9 μ B /Mn expected for Mn 2 + . Meanwhile, the Weiss temperature Θ W = - 89 ± 1 K reveals antiferromagnetic fluctuations that are stymied from reaching an ordered state apparently by the chemical disorder intrinsic to the polyhedral chains. Measurements of magnetization vs field H at T ≤ 10 K are far from saturation even at H = 5 T and are strongly non-Brillouin-like, instead scaling as H / T 0.24 ( 3 ) and suggesting the presence of quantum fluctuations associated with an eventual quasi-one-dimensional, disordered magnetic phase.

1-dimensional systems↗

Anomalous interfacial dynamics of single proton charges in binary aqueous solutions

Our understanding of the dynamics of charge transfer between solid surfaces and liquid electrolytes has been hampered by the difficulties in obtaining interface, charge, and solvent-specific information at both high spatial and temporal resolution. Here, we measure at the single charge scale the dynamics of protons at the interface between an hBN crystal and binary mixtures of water and organic amphiphilic solvents (alcohols and acetone), evidencing a marked influence of solvation on interfacial dynamics. Applying single-molecule localization microscopy to emissive crystal defects, we observe correlated activation between adjacent ionizable surface defects, mediated by the transport of single excess protons along the solid/liquid interface. Solvent content has a nontrivial effect on interfacial dynamics, leading at intermediate water fraction to an increased surface diffusivity, as well as an increased affinity of the proton charges to the solid surface. Our measurements evidence the notable role of solvation on interfacial proton charge transport.

36 MATERIALS SCIENCE↗

Evaluation of Model Summertime Boundary Layer Cloud Development over Complex Terrain in New York State

Weather forecasting over complex terrain with diverse land cover is challenging. Utilizing the high-resolution observations from New York State Mesonet (NYSM), we are able to evaluate the surface processes of the Weather Research Forecast (WRF) Model in a detailed, scale-dependent manner. Here, in the study, possible impacts of land–atmosphere interaction on surface meteorology and boundary layer cloud development are investigated with different model resolutions, land surface models (LSMs), and planetary boundary layer (PBL) physical parameterizations. The High-Resolution Rapid Refresh, version 3 (HRRR), forecasting model is used as a reference for the sensitivity evaluation. Results show that over complex terrain, the high-resolution simulations (1 km × 60 vertical levels) generally perform better compared to low-resolution (3 km × 50 levels) in both surface meteorology and cloud fields. LSMs play a more important role in surface meteorology compared to PBL schemes. The NoahMP land surface model exhibits daytime warmer and drier biases compared to the Rapid Update Cycle (RUC) due to better prediction of the Bowen ratio in RUC. The PBL schemes would affect the convective strength in the boundary layer. The Shin–Hong (SH) scale-aware scheme tends to produce the strongest convective strength in the PBL, while the ACM2 PBL scheme rarely resolved convection even at 1-km resolution. By considering the radiation effect of subgrid-scale (SGS) clouds, the Mellor–Yamada–Nakanishi–Niino eddy diffusivity mass flux (MYNN-EDMF) predicted the highest cloud coverage and lowest surface solar radiation bias. The configuration of SGS clouds in MYNN-EDMF would not only significantly reduce shortwave radiation bias, but also affect the convection behaviors through land surface–cloud–radiation interaction.

54 ENVIRONMENTAL SCIENCES↗

Tailoring Charge Transport and Magnetism in Complex Half-Heusler/Full-Heusler Nanocomposites (Final Report)

This project exploits (1) the facile co-crystallization of the half-Heusler (HH) and full-Heusler (FH) structures, (2) the high coherency and stability of the HH/FH interfaces, and (3) the solid-state inter-conversion between HH and FH structures through local atomic diffusion, to investigate, for selected compositions of the HH and FH phases, the effect of size, dimensionality, dispersion and volume fraction of FH nanostructures on the electronic, phonon and magnetic behavior of the resulting HH/FH nanocomposites. Our goal is to identify and control key material and growth parameters governing phase formation, microstructural evolution, and to understand the mechanism by which these changes of the internal structure modify the material’s performance. To elucidate the mechanism by which the FH nanostructures regulate electronic charge transport and induce ferromagnetism within non-magnetic and magnetic semiconducting HH matrices, suitable series of HH/0D-FH and HH/2D-FH nanocomposites will be fabricated using synthesis conditions suggested by theoretical calculations of the formation energy and stability of various FH phases (varying M) in HH matrices with known chemical composition. The structure of the HH/FH interfaces (size, chemical composition, volume fraction and dispersion) will be investigated along with the evaluation of the electronic (carrier density, mobility, thermopower, electrical conductivity, effective mass), thermal and magnetic (susceptibility, magnetization etc.) properties of the resulting HH/FH nanocomposites.

36 MATERIALS SCIENCE↗

Supernova-driven Turbulent Metal Mixing in High-redshift Galactic Disks: Metallicity Fluctuations in the Interstellar Medium and its Imprints on Metal-poor Stars in the Milky Way

The extent to which turbulence mixes gas in the face of recurrent infusions of fresh metals by supernovae (SN) could help provide important constraints on the local star formation conditions. This includes predictions of the metallicity dispersion among metal-poor stars, which suggests that the interstellar medium was not very well mixed at these early times. The purpose of this Letter is to help isolate, via a series of numerical experiments, some of the key processes that regulate turbulent mixing of SN elements in galactic disks. We study the gas interactions in small simulated patches of a galaxy disk with the goal of resolving the small-scale mixing effects of metals at parsec scales, which enables us to measure the turbulent diffusion coefficient in various galaxy environments. By investigating the statistics of variations of α elements in these simulations, we are able to derive constraints not only on the allowed range of intrinsic yield variations in SN explosions but also on the star formation history of the Milky Way. We argue that the observed dispersion of [Mg/Fe] in metal-poor halo stars is compatible with the star-forming conditions expected in dwarf satellites or in an early low-star-forming Milky Way progenitor. In particular, metal variations in stars that have not been phase-mixed can be used to infer the star-forming conditions of disrupted dwarf satellites.

79 ASTRONOMY AND ASTROPHYSICS↗

Investigation of Rare Earth Elements Mobility Using Molecular Dynamics

Rare Earth Elements (REE) are critical many applications such as electronics, permanent magnets, agricultural etc. Effective separation of REEs is a challenge due to their similarities in chemical and physical properties. Current separation processes are costly and environmentally detrimental. Therefore, research on REEs mobility in water-based solvents is necessary to design effective separation processes. In this research, the key kinetic and thermodynamic parameters, including diffusion coefficient and hydration shell are determined under the influence of external electric field. The diffusion coefficient of metal ions increases due to electric field in pure water.

99 GENERAL AND MISCELLANEOUS↗