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DOE OSTI2024

Theory-guided design of duplex-phase multi-principal-element alloys

Density-functional theory (DFT) is used to identify phase-equilibria in multi-principal-element and high-entropy alloys (MPEAs/HEAs), including duplex-phase and eutectic microstructures. Here, a combination of composition-dependent formation energy and electronic-structure-based ordering parameters were used to identify a transition from FCC to BCC favoring mixtures, and these predictions experimentally validated in the Al-Co-Cr-Cu-Fe-Ni system. A sharp crossover in lattice structure and dual-phase stability as a function of composition were predicted via DFT and validated experimentally. The impact of solidification kinetics and thermodynamic stability was explored experimentally using a range of techniques, from slow (castings) to rapid (laser remelting), which showed a decoupling of phase fraction from thermal history, i.e., phase fraction was found to be solidification rate-independent, enabling tuning of a multi-modal cell and grain size ranging from nanoscale through macroscale. Strength and ductility tradeoffs for select processing parameters were investigated via uniaxial tension and small-punch testing on specimens manufactured via powder-based additive manufacturing (directed-energy deposition). This work establishes a pathway for design and optimization of next-generation multiphase superalloys via tailoring of structural and chemical ordering in concentrated solid solutions.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Downscaling-Based Segmentation for Unresolved Images of Highly Heterogeneous Granular Porous Samples

Numerical simulations of pore-scale flow and transport in natural sediments require the knowledge of pore-space topology. Limited resolution of X-ray tomography is often insufficient to fully characterize pore-space structure within fine-grained regions. Single and multilevel threshold-based segmentation approaches are customarily employed to identify solid, pore and porous-solid regions by means of grey intensity thresholds. While the choice of cutoff thresholds is often arbitrary, it dramatically affects the effective properties and the dynamical response of the reconstructed porous structure. As such, we propose an algorithm of downscaling, i.e., the process of increasing image resolution, followed by segmentation, i.e., the identification of different phases, to reconstruct the unresolved pore-space from XCT images of natural geological porous media. The method, applicable to moderately unresolved, chemically homogeneous granular media, is based on a map between local pixel porosity and pore size that does not rely on the definition of arbitrary thresholds and it allows to generate a high-resolution binary image of the porous medium from poorly resolved grey-scale images. First, we validate the method on synthetic unresolved images and compare their known pore-space distribution with the extracted one. Then, we consider a synthetic porous medium and compare the pore size distribution, conductivity, and tortuosity between the original and the reconstructed structures. Finally, we apply the method to extract the pore-space distribution from unresolved XCT images of two natural sediment columns and use it (i) to parametrize a capillary-bundle model and (ii) to estimate the hydraulic conductivity by matching breakthrough behavior of passive solute transport.

58 GEOSCIENCES↗
DOE OSTI2018

Wetting Behavior of Calcium Ferrite Slags on Cristobalite Substrates

Calcium ferrite (CF) is a significant intermediate adhesive phase in high-basicity sinters. The wettability between calcium ferrite (CF) and gangue plays an important role in the assimilation process. The wettability of CF-based slags, in which a constant amount (2 mass pct.) of Al{sub 2}O{sub 3}, MgO, SiO{sub 2}, and TiO{sub 2} was added, on solid SiO{sub 2} (cristobalite) substrates at 1523 K (1250 °C) was investigated. The interfacial microstructure and spreading mechanisms were discussed for each sample. All the tested slag samples exhibited good wettability on the SiO{sub 2} substrate. The initial apparent contact angles were in the range of 20 to 50 deg, while the final apparent contact angles were ~ 5 deg. The wetting process could be divided into three stages on the basis of the change in diameter, namely the “linear spreading” stage, “spreading rate reduction” stage, and “wetting equilibrium” stage. It was found that the CF-SiO{sub 2} wetting system exhibits dissolutive wetting and the dissolution of SiO{sub 2} into slag influences its spreading process. The spreading rate increases with a decrease in the ratio of viscosity to interfacial tension, which is a result of the addition of Al{sub 2}O{sub 3}, MgO, SiO{sub 2}, and TiO{sub 2}. After cooling, a deep corrosion pit was formed in the substrate and a diffusion layer was generated in front of the residual slag zone; further, some SiO{sub 2} and Fe{sub 2}O{sub 3} solid solutions precipitated in the slag.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Characterization of Fuel Cladding Chemical Interaction on a High Burnup U-10Zr Metallic Fuel via Electron Energy Loss Spectroscopy Enhanced by Machine Learning

Fuel cladding chemical interaction (FCCI) is one of the main performance limiting factors for metallic nuclear fuels. The interaction destabilizes the martensitic microstructure and deteriorates mechanical properties of HT-9 cladding. The detection of low atomic number elements (Z<10) and overlapping of elemental peaks can be problematic in interpreting energy dispersive X-ray spectroscopy (EDS) data. Electron energy loss spectroscopy (EELS) provides precise elemental edge energy values and can detect elements with a low atomic number. This work utilizes EELS to study the distribution of lanthanides and light elements at the interaction region. The sample was prepared from the FCCI region of a U-10Zr (wt.%) solid fuel with HT-9 cladding, irradiated to a burnup of 13.2 at.%. Processing the EELS data included three major steps: 1) enhance the signal to noise ratio by denoising the spectrum with principal component analysis (PCA) method, removing background and performing deconvolution; 2) identify chemical elements with core energy loss edges; 3) confirm different phases using a popular machine learning method, K-means. This work presents qualitative assessment of lanthanides and light elements like carbon (C) and oxygen (O) enhanced by the application of machine learning algorithms. By comparing with EDS elemental maps, EELS provides higher resolution chemical maps, reveals the distribution of carbon at the interaction region supporting the formation of zirconium carbide, a rind-like microstructure feature that was proposed to mitigate the chemical interaction. Furthermore, the plasmon peak map was also found to indicate an energy shift associated with the formation of phases/compounds. K-means clustering method was used on the processed electron energy loss (EEL) spectrum to automatically reveal different phases. The resulting clustered maps from K-means clustering align well with elemental maps confirming certain phases, especially Fe-Ce and Zr-C, in the FCCI region.

EELS↗
DOE OSTI2016

Nanoscale doping of compound semiconductors by solid phase dopant diffusion

Achieving damage-free, uniform, abrupt, ultra-shallow junctions while simultaneously controlling the doping concentration on the nanoscale is an ongoing challenge to the scaling down of electronic device dimensions. Here, we demonstrate a simple method of effectively doping ΙΙΙ-V compound semiconductors, specifically InGaAs, by a solid phase doping source. This method is based on the in-diffusion of oxygen and/or silicon from a deposited non-stoichiometric silicon dioxide (SiO{sub x}) film on InGaAs, which then acts as donors upon activation by annealing. The dopant profile and concentration can be controlled by the deposited film thickness and thermal annealing parameters, giving active carrier concentration of 1.4 × 10{sup 18 }cm{sup −3}. Our results also indicate that conventional silicon based processes must be carefully reviewed for compound semiconductor device fabrication to prevent unintended doping.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Investigation of electrical behavior and dielectric properties in polycristalline Pr0.8Sr0.2MnO3 manganite perovskite

Highlights: • Transport properties of Pr{sub 0.8}Sr{sub 0.2}MnO{sub 3} are investigated in a large range of temperature (80–500 K) and frequency (40–10{sup 7} Hz). • DC measurements show two conduction mechanisms at low and high temperature. • The complex impedance shows that our structure obeys at Cole-Cole model. • Dielectric results reveal a dielectric transition which is well fitted by Curie-Weiss law. • AC conductivity is described by Jonscher power law. The NSPT and Drude models are used to describe the conduction mechanism. - Abstract: The electrical and dielectric properties of Pr{sub 0.8}Sr{sub 0.2}MnO{sub 3} perovskite prepared by the solid-state method were investigated. The complex impedance results showed the contribution of grain and grain boundaries in the conduction mechanism. The dielectric data have confirmed the presence of interfacial polarization in the structure. Moreover, a dielectric transition fitted by Curie-Weiss law was observed. Besides, the observed relaxation diffuse phase transition is attributed to a strong heterogeneity introduced by the substitution of Pr by Sr ions. DC electrical measurements indicate that the structure exhibits a semiconductor behavior and the conductivity is governed by hopping process. The AC conductivity measurements show a clear semiconductor-metallic transition at high temperatures. The AC conductivity data can be divided into two parts, the first of which is a semiconductor one, described by the NSPT model, at low temperatures and the second is a metallic regime, fitted by the classical Drude model, at high temperatures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Tank 48H Phase 1 Initial Testing Using Sodium Permanganate to Decompose Tetraphenylborate: Simulant Studies with Shaker Oven and 2-L Vessel

Tank 48H currently holds legacy material including organic tetraphenylborate (TPB) compounds from the operation of the In-Tank Precipitation process. The large quantity of TPB is not compatible with the waste treatment facilities at SRS and must be removed or undergo treatment to oxidize the organic compounds before the tank can be returned to routine Tank Farm service. Tank 48H currently holds approximately 270,000 gallons of legacy material comprised of decontaminated salt solution, approximately 20,000 kilograms of TPB solids, 3,400 kilograms of sludge solids, and 1,800 kilograms of monosodium titanate (MST).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2016

Water Ordering Controls the Dynamic Equilibrium of Micelle-Fiber Formation in Self-Assembly of Peptide Amphiphiles

Understanding the role of water in governing the kinetics of the self-assembly processes of amphiphilic peptides has still remained elusive. Here, using a multi-stage atomistic-coarse-grained approach, complemented by circular dichroism/infra-red spectroscopy and dynamic light scattering experiments, we highlight the dual nature of water in dictating the mechanism and dynamics of self-assembly of peptide amphiphiles (PAs). Our computational study shows that (i) Water cage formation and breakage near the hydrophobic groups controls the fusion dynamics and aggregation of PAs in the micellar stage, and (ii) Enhanced structural ordering of vicinal water near the hydrophilic amino acids shifts the equilibrium towards the fiber phase and stimulates structure and order in the PAs when they assemble into a hexagonal nanofiber architecture. Finally, spectroscopy and microscopy studies authenticate our computational observation that water ordering near the PAs increases with increase in time. The measured infra-red O-H bond stretch frequency reminiscent of ice-like suggests that the solvated water becomes increasingly solid-like with increased structural order in the assembled peptide network – thus shedding light on the role of water in a self-assembly process.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Orientation-tunable local crystallization of Si films enabled by atomic imprint crystallization

Here, in this paper, we demonstrate area-selective crystallization of amorphous Si into tunable crystal orientations enabled by atomic imprint crystallization (AIC), where an amorphous Si layer is crystallized by solid phase epitaxy (SPE) from an externally impressed single-crystalline Si template. Using micro-patterned single-crystalline Si templates, a limited area of an amorphous Si film, where the film surface and patterned template surface are in contact, is crystallized via SPE to create an array of crystallographically aligned dots embedded in amorphous matrix. Combining AIC from the top surface and conventional SPE from the substrate, we demonstrate the fabrication of an array of crystalline dots embedded in single-crystalline matrix with tunable in-plane rotation angle. The results indicate the high tunability of the crystallization process enabled by AIC, allowing precise control of crystallographic properties of thin films with area-selectivity; such capability opens opportunities for the design of new materials for a wide range of applications in materials science.

Amorphous↗
DOE OSTI2014

Urinary concentrations of environmental phenols in pregnant women in a pilot study of the National Children's Study

Environmental phenols are a group of chemicals with widespread uses in consumer and personal care products, food and beverage processing, and in pesticides. We assessed exposure to benzophenone-3, bisphenol A (BPA), triclosan, methyl- and propyl parabens, and 2,4- and 2,5-dichlorophenol or their precursors in 506 pregnant women enrolled in the National Children's Study (NCS) Vanguard Study. We measured the urinary concentrations of the target phenols by using online solid-phase extraction–isotope dilution high performance liquid chromatography–tandem mass spectrometry. NCS women results were compared to those of 524 similar-aged women in the National Health and Nutrition Examination Survey (NHANES) 2009–2010, and to 174 pregnant women in NHANES 2005–2010. In the NCS women, we found significant racial/ethnic differences (p<0.05) in regression adjusted mean concentrations of benzophenone-3, triclosan, 2,4- and 2,5-dichlorophenol, but not of BPA. Urinary 2,4- and 2,5-dichlorophenol concentrations were highly correlated (r=0.66, p<0.0001). Except for BPA and triclosan, adjusted mean concentrations were significantly different across the 7 study sites. Education was marginally significant for benzophenone-3, triclosan, propyl paraben, and 2,5-dichlorophenol. Urinary concentrations of target phenols in NCS pregnant women and U.S. women and pregnant women were similar. In NCS pregnant women, race/ethnicity and geographic location determined urinary concentrations of most phenols (except BPA), suggesting differential exposures. NCS Main Study protocols should collect urine biospecimens and information about exposures to environmental phenols. - Highlights: • Limited biomonitoring data are available in pregnant women. • Seven urinary phenols were measured in 506 third trimester women enrolled in the NCS. • Urine benzophenone-3, triclosan, 2,4- and 2,5-dichlorophenol differed by race/ethnicity. • Urinary concentrations of 2,4- and 2,5-dichlorophenol were highly correlated. • Exposure information can expand the utility of biospecimens in the NCS Main Study.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2014

The reaction mechanism of SnSb and Sb thin film anodes for Na-ion batteries studied by X-ray diffraction, 119 Sn and 121 Sb Mössbauer spectroscopies

The electrochemical reaction of Sb and SnSb anode materials with Na results in the formation of amorphous materials. To understand the resulting phases and electrochemical capacities we studied the reaction products local order using 119 Sn and 121 Sb Mössbauer spectroscopies in conjunction with measurements performed on model powder compounds of Na-Sn and Na-Sb to further clarify the reactions steps. For pure Sb the discharge (sodiation) starts with the formation of an amorphous phase composed of atomic environments similar to those found in NaSb, and proceeds further by the formation of environments similar to that present in Na 3 Sb. The reversible reaction takes place during a large portion of the charge process. At full charge the anode material still contains a substantial fraction of Na, which explains the lack of recrystallization into crystalline Sb. The reaction of SnSb yields Na 3 Sb crystalline phase at full discharge at higher temperatures (65 and 95°C) while the room temperature reaction yields amorphous compounds. The electrochemically-driven, solid-state amorphization reaction occurring at room temperature is governed by the simultaneous formation of Na-coordinated Sn and Sb environments, as monitored by the decrease (increase) of the 119 Sn ( 121 Sb) Mössbauer isomer shifts. Overall, the monitoring of the hyperfine parameters enables to correlate the changes in Na content to the individual Sn and Sb local chemical environments.

25 ENERGY STORAGE↗
DOE OSTI2019

Nonaggregating Doped Polymers Based on Poly(3,4-Propylenedioxythiophene)

Electrical doping of organic semiconductors is critical for their use in electrical devices. However, many high-performance semiconductors exhibit drastically reduced solubilities when doped in solution, making it difficult to deconvolute the roles of doping and morphological changes on their electrical properties. We report the synthesis of a semiconducting polymer based on poly(3,4-propylenedioxythiophene) (ProDOT) substituted with oligo(ethylene glycol) (EG) side chains that is designed to solvate dopant molecules. When doped with F 4 TCNQ in solution, the polymer P(ProDOT-EG) undergoes efficient charge transfer while remaining soluble with no indication of aggregation. The electrical conductivity of thin films cast from heavily doped solutions is ~1 S/cm; optical spectroscopy reveals that the doping efficiency is reduced upon formation of the solid film. Diffusion of F 4 TCNQ from the vapor phase into films of neutral P(ProDOT-EG) yields comparable conductivities to films cast from doped solutions. Absorption spectroscopy and X-ray diffraction of doped films reveal that the doping efficiency and nature of charge carriers (polaron or bipolaron) are strongly affected by the processing route. The lack of the localized polaron signature for films doped by infiltration of the dopant from the vapor phase indicates that morphology has a large role in determining the nature of the charge carriers in semiconducting polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Electro-chemo-mechanically Driven Ni Exsolution from (Pr,Ce,Ni)O 2−δ : Controlled Nucleation Density and Enhanced Electrode Kinetics

In situ exsolution of metal nanoparticles is a promising strategy to prepare electrocatalysts with enhanced activity and resistance to agglomeration for efficient chemical transformations and energy conversion. Achieving a high nucleation density of nanoparticles under mild conditions and understanding how to tailor the process is important for performance of these electrodes in electrochemical cells. In this work, we demonstrate facile exsolution of Ni nanoparticles using fluorite-structured (Pr,Ce)O 2−δ as the support oxide, driven by electrochemical potential and aided by the metastability of Ni in the solid solution (elastic driving force). We prepare single-phase oriented thin films of (Pr,Ce,Ni)O 2−δ (NPCO) on (Zr,Y)O 2−δ (YSZ) substrates by pulsed laser deposition. With the aid of a high-throughput electrochemical cell that provides a lateral gradient in Nernst voltage, we apply in situ near-ambient pressure synchrotron X-ray photoelectron spectroscopy and ex situ atomic force microscopy to investigate the impact of electrochemical potential on Ni nucleation density. We find that metallic Ni can be successfully exsolved at 550 °C upon cathodic biasing in 20 mTorr O 2 , and its nucleation density increases with increasing electrochemical driving force/decreasing oxygen chemical potential. We further evaluate the electrochemical performance under highly reducing (fuel electrode) conditions by electrochemical impedance spectroscopy. With the exsolved Ni nanoparticles, the surface exchange coefficient of the NPCO is found to be ∼4× higher than for PCO without exsolution. This work confirms mixed conducting fluorites as beneficial host lattices for facile transition-metal exsolution and suggests the possibility for constructing an all ceria-based electrochemical cell with PCO serving as both the cathode and the anode.

36 MATERIALS SCIENCE↗
DOE OSTI2013

CO 2 capture properties of lithium silicates with different ratios of Li 2 O/SiO 2 : an ab initio thermodynamic and experimental approach

The lithium silicates have attracted scientific interest due to their potential use as high-temperature sorbents for CO 2 capture. The electronic properties and thermodynamic stabilities of lithium silicates with different Li 2 O/SiO 2 ratios (Li 2 O, i 8 SiO 6 , Li 4 SiO 4 , Li 6 Si 2 O 7 , Li 2 SiO 3 , Li 2 Si 2 O 5 , Li 2 Si 3 O 7 , and a-SiO 2 ) have been investigated by combining first-principles density functional theory with lattice phonon dynamics. All these lithium silicates examined are insulators with band-gaps larger than 4.5 eV. By decreasing the Li 2 O/SiO 2 ratio, the first valence bandwidth of the corresponding lithium silicate increases. Additionally, by decreasing the Li 2 O/SiO 2 ratio, the vibrational frequencies of the corresponding lithium silicates shift to higher frequencies. Based on the calculated energetic information, their CO 2 absorption capabilities were extensively analyzed through thermodynamic investigations on these absorption reactions. We found that by increasing the Li 2 O/SiO 2 ratio when going from Li 2 Si 3 O 7 to Li 8 SiO 6 , the corresponding lithium silicates have higher CO 2 capture capacity, higher turnover temperatures and heats of reaction, and require higher energy inputs for regeneration. Based on our experimentally measured isotherms of the CO 2 chemisorption by lithium silicates, we found that the CO 2 capture reactions are two-stage processes: (1) a superficial reaction to form the external shell composed of Li 2 CO 3 and a metal oxide or lithium silicate secondary phase and (2) lithium diffusion from bulk to the surface with a simultaneous diffusion of CO 2 into the shell to continue the CO 2 chemisorption process. The second stage is the rate determining step for the capture process. By changing the mixing ratio of Li 2 O and SiO 2 , we can obtain different lithium silicate solids which exhibit different thermodynamic behaviors. Based on our results, three mixing scenarios are discussed to provide general guidelines for designing new CO2 sorbents to fit practical needs.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Will high-entropy carbides and borides be enabling materials for extreme environments?

Abstract The concept of multi-principal component has created promising opportunities for the development of novel high-entropy ceramics for extreme environments encountered in advanced turbine engines, nuclear reactors, and hypersonic vehicles, as it expands the compositional space of ceramic materials with tailored properties within a single-phase solid solution. The unique physical properties of some high-entropy carbides and borides, such as higher hardness, high-temperature strength, lower thermal conductivity, and improved irradiation resistance than the constitute ceramics, have been observed. These promising properties may be attributed to the compositional complexity, atomic-level disorder, lattice distortion, and other fundamental processes related to defect formation and phonon scattering. This manuscript serves as a critical review of the recent progress in high-entropy carbides and borides, focusing on synthesis and evaluations of their performance in extreme high-temperature, irradiation, and gaseous environments.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Phase-field model of alloy solidification far from chemical equilibrium at the solid-liquid interface

We further develop a recently introduced phase-field model of far-from-equilibrium alloy solidification under additive manufacturing conditions [K. Ji et al., Phys. Rev. Lett. 130, 026203 (2023)]. This model utilizes enhanced solute diffusivity within the spatially diffuse interface region to quantitatively capture solute trapping with a larger interface width, thereby making simulations on experimentally relevant length and timescales computationally feasible. The main developments presented here include testing the robustness of different variational formulations, extending the model to concentrated alloys by incorporating solid and liquid free energies from thermodynamic databases, as illustrated for hypoeutectic Al-Ag alloys with CALPHAD, extending convergence tests as a function of interface width to 3D, and carrying out simulations in both 2D and 3D to examine existing theories of microstructure development. Our results indicate that the simplest variational formulation that interpolates the bulk free-energy density between its solid and liquid forms is the most robust. Remarkably, for hypoeutectic Al-Ag alloys, this formulation yields a high-velocity nonequilibrium phase diagram that is independent of interface width, thereby demonstrating that the framework of enhanced solute diffusivity can be nontrivially extended to concentrated alloys. Other variational formulations have restricted ranges of materials or processing parameters that can be reliably modeled. We use 2D simulations to construct high-velocity microstructure selection maps for dilute Al-Cu alloys. The results validate the important role of latent heat rejection at the interface and extend the limited predictions of linear stability analysis [A. Karma and A. Sarkissian, Phys. Rev. E 47, 513 (1993)] and sharp-interface 1D simulations to fully nonlinear regimes. Furthermore, 3D simulations, carried out using a computationally tractable axisymmetric cellular/dendritic interface shape, demonstrate a good convergence similar to that observed in 2D as a function of interface width. Full 3D simulations, in turn, reveal that the standard theory of absolute stability is a good predictor of the upper critical velocity beyond which steady-state growth becomes unstable, despite the different morphological manifestations of this instability in 2D and 3D.

36 MATERIALS SCIENCE↗