SEARCH · Engineering Papers

Results for “segregation”

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.

SourceResearch connectionFrom yearThrough year

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

At least 109 records · Page 6

All sources NASA NTRS DOE OSTI

DOE OSTI2025

Grain boundary segregation and chemical ordering in CoCrFeMnNi multi-principal element alloy

Owing to their far-from-dilute compositions, multi-principal element alloys (MPEAs) can exhibit unique combinations of engineering properties. As nearly all MPEAs are polycrystalline aggregates, it is necessary to understand the interactions of various elemental species with grain boundaries (GBs). This is of particular importance in extreme environments, such as radiation and elevated temperatures, where such interactions have implications on the properties of MPEAs. Herein, we employ atomistic simulations to generate a series of [001] asymmetric tilt GBs in a model CoCrFeMnNi MPEA and quantify solute interactions and segregation to these boundaries. We employ the Warren-Cowley order parameters to investigate the interplay between GB segregation and chemical short-range order (SRO). At temperatures above 800 K, simulation results reveal the segregation of Cr and Mn to CoCrFeMnNi GBs and show weak dependence of boundary solute excess on GB geometry, at least for the boundaries explored in this work. At temperatures in the range of 673–800 K, formation of domains rich in Cr is observed at GBs in agreement with experimental observations. Quantitative analysis shows that solute excess of various alloying elements decreases rapidly with the increase in temperature in the range of 1000–1200 K. Furthermore, we show that GB regions exhibit SRO characteristics that are distinct from the bulk crystals, leading to spatial variations in SRO. In broad terms, our study highlights the need to account for GB interactions with alloying elements when designing advanced MPEAs with novel chemistries.

Wang, Yitao [Lehigh University, Bethlehem, PA (Uni↗

DOE OSTI2025

Direct observation of strain-enhanced hydrogen segregation and failure at high-angle grain boundaries in nickel

Understanding the mechanisms underlying hydrogen embrittlement remains difficult, even in single-element metals. Both microstructure and stress state influence hydrogen distribution in metals and alloys, which impacts deformation and failure. Here, in this work, we use in-situ Kelvin probe force microscopy (KPFM) to monitor the hydrogen distribution in pure nickel over time at 1.1 % and 3.5 % strain. The sample strained to 3.5 % results in preferential hydrogen segregation to high-angle grain boundaries whereas the sample strained to 1.1 % does not exhibit preferential hydrogen segregation. Optical digital image correlation (DIC) shows that hydrogen charging results in both localized and reduced strains during tensile testing of a notched sample. Later stages of deformation and failure (e.g. microcracking) are studied by using in-situ transmission X-ray microscopy (TXM). TXM reveals nanoscale structural changes to a propagating crack in a hydrogen environment. Localized void growth and secondary cracking occur at grain boundaries near the primary crack front. Correlative electron backscattering diffraction (EBSD) is used to relate the cracking at grain boundaries to the hydrogen segregation observed in KPFM. These findings are unified in a proposed hydrogen embrittlement mechanism that describes the interaction of hydrogen with grain boundaries, and the role of grain boundaries in hydrogen embrittlement.

Grain boundary fracture↗

DOE OSTI2025

Phase segregation dynamics in mixed-halide perovskites revealed by plunge-freeze cryo-electron microscopy

Mixed-halide lead perovskites, with photoexcited charge-carrier properties suitable for high-efficiency photovoltaics, hold significant promise for high-efficiency tandem solar cells. However, phase segregation under illumination, where an iodide-rich phase forms carrier trap states, remains a barrier to application. This study employs plunge-freeze cryoelectron microscopy to visualize nanoscale phase segregation dynamics in CsPb(Br x I 1–x ) 3 films. By rapidly freezing the illuminated samples, we preserve transient photoexcited ion distributions for high-resolution structural and compositional analysis at the nanoscale. Cryogenic scanning transmission electron microscopy (STEM) techniques (electron energy loss spectroscopy [EELS] and 4D-STEM) captured the dynamics of photo-induced iodine migration from grain boundaries to centers, identified the buildup of anisotropic strain, and captured the heterogeneous evolution of this process within a single grain. These findings provide insight into microscopic phase segregation mechanisms and their dynamics, enhancing our understanding of mixed-halide perovskite photostability.

42 ENGINEERING↗

DOE OSTI2023

Strain-Mediated Sn Incorporation and Segregation in Compositionally Graded Ge 1– x Sn x Epilayers Grown by MBE at Different Temperatures

We investigated the process of Sn incorporation and surface segregation for compositionally graded Ge 1–x Sn x epilayers grown on high-quality Ge (001) substrates. Here, the growth resulted in pseudomorphic GeSn layers with a ~6% maximal Sn fraction at a constant substrate temperature. The maximal fraction of Sn was increased to 9.0% when the growth temperature was continuously lowered while increasing the Sn flux. The analysis of surface droplets and SIMS profiles of elemental composition give evidence of Sn rejection during the growth, potentially associated with a critical energy of elastic strain. The intentional reduction of the coherent strain by decreasing the Sn flux near the sample surface has been shown to trap a higher fraction of Sn in the Ge 1–x Sn x layer and lower surface segregation. Our results demonstrate that strain relief by misfit dislocations in the compositionally graded layer is inhibited, which leads to Sn segregation. Specifically, the compressive strain in the graded Ge 1–x Sn x epilayer is effectively “zero” near the interface with the Ge substrate and increases up to about –1.5 × 10 –2 near the surface. Thus, although the nucleation of a dislocation may reduce the compressive strain for the top region of the epilayer, it is not beneficial for the bottom region.

42 ENGINEERING↗

DOE OSTI2026

Surface Segregation of Liquid Metal Plasma-Facing Component Alloys: A ReaxFF Investigation

Engineering liquid metal alloys offers a transformative pathway for plasma-facing components by enabling chemically tailored surfaces that can simultaneously optimize plasma-material interactions, reduce divertor heat flux, and enhance core plasma confinement, thereby advancing the commercial viability of nuclear fusion power plants. This study, employing an atomistic simulation approach, provides direct evidence that incorporating nonmetal surface-active agents (such as O and H, or their combination) enables strong surface segregation. This capability makes tin−aluminum (Sn−Al) and tin−lithium (Sn−Li) alloys, with suitable compositions, good candidates for PFC applications. Specifically, the presence of low-Z solutes (Li, Al) leads to preferential surface enrichment, which imparts low-Z sputtering characteristics, while the Sn solvent maintains thermophysical stability. To systematically examine this behavior, we developed a ReaxFF force field spanning the full Sn/Al/Li/O/H chemistry, validated it against formation energies and elastic constants, and applied it in reactive molecular dynamics simulations at fusion-relevant temperatures. We also introduced an overlapbased segregation index that captures interfacial compositional separation directly from atomistic density distributions. Here, this metric reveals a clear hierarchy of segregation regimes and provides a unified view across all systems studied. Together, these findings establish a mechanistic link between nonmetal chemistry and interfacial structure, providing a predictive framework for designing self-adaptive, low-sputtering liquid metal alloys for fusion applications.

Alloys↗

DOE OSTI2021

Understanding interfacial segregation in polymer blend films with random and mixed side chain bottlebrush copolymer additives

Bottlebrush polymers are complex macromolecules with tunable physical properties dependent on the chemistry and architecture of both the side chains and the backbone. Prior work has demonstrated that bottlebrush polymer additives can be used to control the interfacial properties of blends with linear polymers but has not specifically addressed the effects of bottlebrush side chain microstructures. Here, using a combination of experiments and self-consistent field theory (SCFT) simulations, we investigated the effects of side chain microstructures by comparing the segregation of bottlebrush additives having random copolymer side chains with bottlebrush additives having a mixture of two different homopolymer side chain chemistries. Specifically, we synthesized bottlebrush polymers with either poly(styrene-ran-methyl methacrylate) side chains or with a mixture of polystyrene (PS) and poly(methyl methacrylate) (PMMA) side chains. Furthermore, the bottlebrush additives were matched in terms of PS and PMMA compositions, and they were blended with linear PS or PMMA chains that ranged in length from shorter to longer than the bottlebrush side chains. Experiments revealed similar behaviors of the two types of bottlebrushes, with a slight preference for mixed side-chain bottlebrushes at the film surface. SCFT simulations were qualitatively consistent with experimental observations, predicting only slight differences in the segregation of bottlebrush additives driven by side chain microstructures. Specifically, these slight differences were driven by the chemistries of the bottlebrush polymer joints and side chain end-groups, which were entropically repelled and attracted to interfaces, respectively. Using SCFT, we also demonstrated that the interfacial behaviors were dominated by entropic effects with high molecular weight linear polymers, leading to enrichment of bottlebrush near interfaces. Surprisingly, the SCFT simulations showed that the chemistry of the joints connecting the bottlebrush backbones and side chains played a more significant role compared with the side chain end groups in affecting differences in surface excess of bottlebrushes with random and mixed side chains. This work provides new insights into the effects of side chain microstructure on segregation of bottlebrush polymer additives.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Glyceraldehyde-3-phosphate dehydrogenase homologs as bifunctional gatekeepers of metabolic segregation in Pseudomonas putida

Metabolically versatile Pseudomonas species can assimilate various glycolytic and gluconeogenic substrates. Simultaneous assimilation is known to segregate carbons from each substrate type into different metabolic pathways. However, the mechanisms of this metabolic segregation remain unresolved. Here, we investigate Pseudomonas putida KT2440 during processing of the sugar glucose through glycolysis versus the phenolic acid ferulate through gluconeogenesis. Metabolome profiling reveals up to twofold less tricarboxylic acid cycle metabolites but up to 10-fold higher metabolites of upper glycolysis, pentose-phosphate, and Entner–Doudoroff pathways in glucose-grown cells compared to ferulate-grown cells. After 13C-substrate switching, kinetic isotopic profiling captures rapid assimilation of new substrate carbons into initial catabolic pathways, but incorporation into downstream pathways is absent or incomplete. Proteomics identifies a 22-fold higher abundance of one homolog of glyceraldehyde-3-phosphate dehydrogenase (GAPDH, GapA) in cells fed on glucose relative to ferulate, while abundance of another homolog (GapB) remains unchanged. Growth phenotypes and quantitative metabolomics for single and double knockout mutants of these GAPDH homologs indicate only GapA involvement in glycolytic flux, which can be compensated by the Entner–Doudoroff pathway, and distinct preference of GapB with minimal role of GapA for gluconeogenic flux. Accordingly, growth of triple knockout mutant with deletion of gapA, gapB, and edd is possible only when glycolytic and gluconeogenic substrates are provided together to meet metabolic demands in a segregated fashion, but metabolic tradeoffs lead to slow growth. A mathematical, experimentally constrained, model of the GAPDH node shows that tuning of GapA and GapB concentrations enables transition between flux regimes for nutritional adaptability.

Zhou, Nanqing [Northwestern University, Evanston]↗

DOE OSTI2025

Interstitial solute segregation at triple junctions: Implications for nanomaterials and a case study of hydrogen in palladium

At very fine grain sizes, grain boundary segregation can deviate from conventional behavior due to triple junction effects. While this issue has been addressed in prior work for substitutional alloys, here we develop a framework that accounts for interstitial sites in the grains, grain boundaries, and triple junctions of model Pd(H) polycrystals. This approach allows computation of interstitial segregation spectra separately at both defect types, which permits an understanding of segregation at all grain sizes via a size-scaling spectral isotherm. Here, the size dependencies of dilute Pd(H) are found to be influenced not only by the triple junction content, but also by grain size–dependent lattice strains; the latter effect is evidenced by size dependencies of individual grain boundary and junction subspectra. The framework proposed here is applicable to interstitial alloys in general and may serve as a basis for interfacial engineering in interstitial nanocrystalline alloys. As an example, we show that using the dilute limit isotherm, hydrogen density can triple in nanocrystalline vis-à-vis microcrystalline Pd due to hydrogen adsorption at intergranular defect sites.

Alloys↗

DOE OSTI2024

Topological grain boundary segregation transitions

Engineering the structure of grain boundaries (GBs) by solute segregation is a promising strategy to tailor the properties of polycrystalline materials. Solute segregation triggering phase transitions at GBs has been suggested theoretically to offer different pathways to design interfaces, but an understanding of their intrinsic atomistic nature is missing. Here, we combined atomic resolution electron microscopy and atomistic simulations to discover that iron segregation to GBs in titanium stabilizes icosahedral units (“cages”) that form robust building blocks of distinct GB phases. Owing to their five-fold symmetry, the iron cages cluster and assemble into hierarchical GB phases characterized by a different number and arrangement of the constituent icosahedral units. Our advanced GB structure prediction algorithms and atomistic simulations validate the stability of these observed phases and the high excess of iron at the GB that is accommodated by the phase transitions.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Stabilized Nanocrystalline Alloys: The Intersection of Grain Boundary Segregation with Processing Science

Processing science for nanocrystalline metals has largely focused on far-from-equilibrium methods that can generate many grain boundaries with excess defect energy. Conversely, the science of stabilizing nanocrystalline alloys has largely focused on the lowering of that excess defect energy through grain boundary segregation, bringing nanocrystalline structures closer to equilibrium. With increasing technological adoption of stabilized nanocrystalline alloys, there is a substantial need for research at the intersection of these two fields. This review lays out the basic thermodynamic issues of the two subfields and surveys the literature on the most common processing methods, including severe plastic deformation, ball milling, physical vapor deposition, and electrodeposition. We provide an overview of studies that have examined grain boundary segregation through each of these methods and identify general themes. We conclude that there is substantial scope for more systematic work at the intersection of these fields to understand how nonequilibrium processing affects grain boundary segregation.

Materials Science↗

NASA NTRS1972

Thermal effects in equilibrium surface segregation in a copper/10-atomic-percent-aluminum alloy using Auger electron spectroscopy

Equilibrium surface segregation of aluminum in a copper-10-atomic-percent-aluminum single crystal alloy oriented in the /111/ direction was demonstrated by using Auger electron spectroscopy. This crystal was in the solid solution range of composition. Equilibrium surface segregation was verified by observing that the aluminum surface concentration varied reversibly with temperature in the range 550 to 850 K. These results were curve fitted to an expression for equilibrium grain boundary segregation and gave a retrieval energy of 5780 J/mole (1380 cal/mole) and a maximum frozen-in surface coverage three times the bulk layer concentration. Analyses concerning the relative merits of sputtering calibration and the effects of evaporation are also included.

Ferrante, J.↗

NASA NTRS1980

Exploratory models of the earth's thermal regime during segregation of the core

Some simple exploratory theoretical models of the thermal effects of core segregation have been investigated, assuming an initially homogeneous earth and including convective heat transport through a 'parameterized convection' approximation. The results indicate that either (1) mantle temperatures 30% or more above present values may have resulted from the gravitational energy released during core segregation, (2) the earth retained very little of its accretional energy, (3) core segregation lasted for one billion years or more, or (4) the earth accreted heterogeneously. Option 3 seems to be precluded by terrestrial lead isotope data, and the alternatives each raise substantial questions concerning the mechanics, chemistry, and petrology of the earth's early history. There is no recognized evidence for the early hot phase of option 1, and option 4 implies, among other things, an analogous early hot phase. Although it has not been favored, option 2 may be viable.

Davies, G. F.↗

NASA NTRS1982

Finite element analysis of the effect of a non-planar solid-liquid interface on the lateral solute segregation during unidirectional solidification

The effect of solid-liquid interface shape on lateral solute segregation during steady-state unidirectional solidification of a binary mixture is calculated under the assumption of no convection in the liquid. A finite element technique is employed to compute the concentration field in the liquid and the lateral segregation in the solid with a curved boundary between the liquid and solid phases. The computational model is constructed assuming knowledge of the solid-liquid interface shape; no attempt is made to relate this shape to the thermal field. The influence of interface curvature on the lateral compositional variation is investigated over a range of system parameters including diffusivity, growth speed, distribution coefficient, and geometric factors of the system. In the limiting case of a slightly nonplanar interface, numerical results from the finite element technique are in good agreement with the analytical solutions of Coriell and Sekerka obtained by using linear theory. For the general case of highly non-planar interface shapes, the linear theory fails and the concentration field in the liquid as well as the lateral solute segregation in the solid can be calculated by using the finite element method.

Carlson, F. M.↗

NASA NTRS1983

Radial segregation induced by natural convection and melt/solid interface shape in vertical Bridgman growth

The roles of natural convection in the melt and the shape of the melt/solid interface on radial dopant segregation are analyzed for a prototype of vertical Bridgman crystal growth system by finite element methods that solve simultaneously for the velocity field in the melt, the shape of the solidification isotherm, and the temperature distribution in both phases. Results are presented for crystal and melt with thermophysical properties similar to those of gallium-doped germanium in Bridgman configurations with melt below (thermally destabilizing) and above (stabilizing) the crystal. Steady axisymmetric flow are classified according to Rayleigh number as either being nearly the growth velocity, having a weak cellular structure or having large amplitude cellular convention. The flows in the two Bridgman configurations are driven by different temperature gradients and are in opposite directions. Finite element calculations for the transport of a dilute dopant by these flow fields reveal radial segregation levels as large as sixty percent of the mean concentration. Segregation is found most severe at an intermediate value of Rayleigh number above which the dopant distribution along the interface levels as the intensity of the flow increases.

Chang, C. J.↗

NASA NTRS1985

Solutal Convection and Its Effects on Crystal Growth and Segregation in Binary and Pseudo-Binary System with Large Liquidus-Solidus Separation

This research program is composed of theoretical and experimental studies of solutal convection and its effects on crystal growth and segregation in binary and pseudo-binary systems with large liquidus-solidus separation. The theoretical program has resulted in the development of a transient simulation of the growth of concentrated alloys in microgravity and has been used to study the dynamics of GeSi, PbSnTe, HgCdTe growth. Finite element analysis has also been developed for studying the interactions of buoyancy-driven convection in the melt caused by temperature and concentration variations with melt-solid interface morphology and alloy segregation in the grown crystal. These calculations are being compared directly to experimental measurements of segregation and interface shape for GeSi growth and GaGe growth. The results for SiGe indicate that careful design of the thermal system can result in almost diffusion-controlled growth on Earth because of the stablizing influence of the concentration gradient ahead of the solidification front.

Brown, R. A.↗

NASA NTRS1993

Experimental segregation of iron-nickel metal, iron-sulfide, and olivine in a thermal gradient: Preliminary results

Speculation about the possible mechanisms for core formation in small asteroids raises more questions than answers. Petrologic evidence from iron meteorites, pallasites, and astronomical observations of M asteroids suggests that many small bodies were capable of core formation. Recent work by Taylor reviews the geochemical evidence and examines the possible physical/mechanical constraints on segregation processes. Taylor's evaluation suggests that extensive silicate partial melting (preferably 50 vol. percent or greater) is required before metal can segregate from the surrounding silicate and form a metal core. The arguments for large degrees of silicate partial melting are two-fold: (1) elemental trends in iron meteorites require that the metal was at is liquidus; and (2) experimental observations of metal/sulfide inclusions in partially molten silicate meteorites show that the metal/sulfide tends to form spherules in the liquid silicate due to surface tension effects. Taylor points out that for these metal spherules to sink through a silicate mush, high degrees of silicate partial melting are required to lower the silicate yield strength. Although some qualitative experimental data exists, little is actually known about the behavior of metals and liquid sulfides dispersed in silicate systems. In addition, we have been impressed with the ability of cumulative olivine to expel trapped liquid when placed in a thermal gradient. Consequently, we undertook to accomplish the following: (1) experimentally evaluate the potential for metal/sulfide/silicate segregation in a thermal gradient; and (2) obtain quantitative data of the wetting parameters of metal-sulfide melts among silicate grains.

Jurewicz, Stephen R.↗

NASA NTRS1994

Numerical formulation of composition segregation at curved solid-liquid interface during steady state solidification process

The lateral solute segregation that results from a curved solid-liquid interface shape during steady state unidirectional solidification of a binary alloy system has been studied both analytically and numerically by Coriell, Bosivert, Rehm, and Sekerka. The system under their study is a two dimensional rectangular system. However, most real growth systems are cylindrical systems. Thus, in a previous study, we have followed Coriell etc. formalism and obtained analytical results for lateral solute segregation for an azimuthal symmetric cylindrical binary melt system during steady state solidification process. The solid-liquid interface shape is expressed as a series combination of Bessel functions. In this study a computer program has been developed to simulate the lateral solute segregation.

Wang, Jai-Ching↗

NASA NTRS1998

Experiment 13: The Study of Dopant Segregation Behavior During the Growth of GaAs in Microgravity on USML-2

An investigation into the segregation behavior of selenium doped gallium arsenide (Se/GaAs) during directional solidification in the microgravity environment was conducted using the Crystal Growth Furnace (CGF) aboard the second United States Microgravity Laboratory (USML-2). Two crystals were successfully processed on USML-2, which lasted from October 20 to November 7, 1995. The first sample was processed for 67 hours, 45 minutes (MET 5/04:53:45-8/00:23:50) and included 19 hours of growth at 0.5 microns/sec which yielded 3.42 cm of sample length, and 5 hours of growth at 1.5 microns/sec which yielded 2.7 cm of sample. During the second experiment, the furnace temperature was adjusted to move the melt-solid interface position towards the hot end of the furnace. The second sample was processed for 50 hours, 10 minutes (MET 8/18:48:49-10/21:58:54) and included 11 hours of growth at 0.5 microns/sec which yielded 1.98 cm of sample, and 1 hour, 25 minutes of growth at 5.0 microns/sec which yielded 2.6 cm of sample. This sample provides an order of magnitude change in growth rate and reproduces one of the growth rates used during USML-1. In contrast to the results from USML-1, no voids were present in either crystal grown on USML-2. The absence of voids in either sample indicates that growth rate changes alone were not responsible for the formation of voids found in the crystals grown on USML-1. Sections of the ground-based and flight crystals grown on USML-2 were cut and polished. All of the interface demarcation lines expected from the current pulse interface demarcation (CPID) system have been identified. These measurements have been analyzed for interface positions, interface shapes, and growth rates. Using a newly developed technique, based on experimental and numerical results, the seeding interface reproducibility from run to run was <= 2.5 mm. The seeding interface position could be controllably moved, with respect to the furnace zones, by adjusting the control set points of the heating zones. The interface shapes flattened slightly as the interface position moved closer to the hot zone but was always an unfavorable concave into the solid shape. The growth rate was found to equal the furnace translation rate, after a 2 -hour transient, for growth rates <= 1.0 microns/sec. Segregation measurements for the ground-based crystals are indicative of complete mixing behavior, as expected. Segregation measurements of the flight crystals are still in progress.

Matthiesen, David H.↗