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At least 307 records · Page 17

Mechanisms of Three-Dimensional Solid-Phase Epitaxial Crystallization of Strontium Titanate

Strontium titanate (SrTiO 3 , STO) is a complex metal oxide with a cubic perovskite crystal structure. Due to its easily described and understood crystal structure in the cubic phase, STO is an ideal model system for exploring the mechanistic details of solid-phase epitaxy (SPE) in complex oxides. SPE is a crystallization approach that aims to guide crystal growth at low homologous temperatures to achieve targeted microstructures. Beyond planar thin films, SPE can also exploit the addition of a chemically inert, noncrystallizing, amorphous obstacle in the path of crystallization to generate complex three-dimensional structures. The introduction of this mask fundamentally alters the SPE process, inducing a transition from two- to three-dimensional geometries and from vertical to lateral crystal growth under the influence of the crystal/mask/amorphous boundary. Using a combination of molecular dynamics simulations and experiments, we identify several unique phenomena in the nanoscale growth behaviors in both conventional (unmasked) and masked SPE. Examining conventional SPE of STO, we find that crystallization at the interface is strongly correlated to, and potentially driven by, density fluctuations in the region of the amorphous STO near the crystalline/amorphous interface with a strong facet dependence. In the masked case, we find that the crystalline growth front becomes nonplanar near contact with the mask. We also observe a minimum vertical growth requirement prior to lateral crystallization. Both phenomena depend on the relative bulk and interfacial free energies of the three-phase (crystal/mask/amorphous) system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In situ x-ray and electron scattering studies of oxide molecular beam epitaxial growth

We perform the first in situ synchrotron X-ray ray diffraction (SXRD) / reflection high energy electron diffraction (RHEED) studies on the growth of complex oxide thin films by molecular beam epitaxy. The unique deposition chamber, located at the Advanced Photon Source, allows the preparation of complex oxide samples with monolayer precision and facilitates the formation of direct correlations between in situ X-ray studies and the more prevalent RHEED investigations. Importantly, because SXRD and RHEED probe different atomic-scale processes during thin film synthesis, their concomitant use enables the extraction of details concerning growth behavior than one cannot determine from either probe alone. We describe the results of such in situ studies on the epitaxial growth of perovskite LaNiO3on (La 0.18 Sr 0.82 )(Al 0.59 Ta 0.41 )O 3 (001). We find that during the earliest stages of growth, the RHEED and X-ray signals do not agree with each other, demonstrating that while regular RHEED oscillations may imply high quality growth, the film-substrate interface can undergo significant changes during deposition due to the occurrence of interdiffusion at the growth temperature.

36 MATERIALS SCIENCE↗

Convergent Manufacturing of Large-Scale Components for Nuclear Applications, via Additive Manufacturing and Powder Metallurgy Hot Isostatic Pressing

Powder metallurgy (PM)–hot isostatic pressing (PM-HIP) has long been recognized as a powerful route for producing fully dense, near net shape metallic components. By consolidating powders under high temperature and pressure, HIP provides isotropic properties, uniform microstructures, and scalability to complex geometries that are vital for sectors such as aerospace, energy, and nuclear power. Yet despite these advantages, the technology has remained constrained by costly trial and error canister fabrication, limitations of conventional forging, and incomplete knowledge about how the canister design influences final part properties. Additive manufacturing (AM), by contrast, thrives on design freedom and geometric flexibility but struggles with speed, scalability, and cost when applied to very large structures. The research presented in this report investigated how a convergent manufacturing approach, combining AM with PM-HIP, can merge the strengths of both technologies, leveraging AM’s flexibility for canister design and HIP’s consolidation capability to deliver reliable, large, and complex parts. The work progressed through three case studies that built on one another in scale and complexity. Small cylindrical canisters fabricated by conventional methods, laser powder bed fusion, and directed energy deposition were filled with stainless steel powders and subjected to HIP. The resulting parts demonstrated near-full density and mechanical properties on par with wrought stainless steel, showing for the first time that AM canisters can be a direct substitute for conventional ones without sacrificing quality. The next step involved a medium-scale, noncentrosymmetric T-valve, which is an enclosed, multibranch geometry that tested the limits of AM + PM-HIP integration. The T-valve achieved predictable shrinkage and uniform densification, confirming feasibility for enclosed designs. However, this study also revealed oxide inclusions and interfacial challenges at the AM + HIP boundary, underscoring the critical importance of controlling interface chemistry and employing robust, in situ strategies, such as melt pool monitoring and thermal monitoring, coupled with nondestructive evaluation techniques such as x-ray computed tomography. Finally, the effort culminated in fabricating a large-scale impeller weighing nearly 2000 lb and spanning 5 ft in diameter. Produced via multirobot wire arc AM and hot isostatic pressed to near-full density, the impeller validated industrial-scale feasibility. Predictive models closely matched experimental shrinkage, tensile properties were spatially uniform across the component, and the AM + PM-HIP interface proved mechanically sound despite the presence of oxide-decorated prior particle boundaries. This large-scale demonstration is a major milestone, showing that hybrid AM + PM‑HIP can reliably deliver components at reactor-relevant scales. Collectively, these studies charted a logical pathway: small-scale work built scientific confidence, medium-scale work highlighted opportunities and challenges, and large-scale work proved industrial impact. The overarching conclusion of this report is that AM + PM-HIP should not be seen as a replacement for forging but as a complementary pathway that provides the US with flexibility, resilience, and new options for manufacturing nuclear-grade components. Looking ahead, several directions emerge as critical to sustaining progress. Predictive modeling must become faster, more accessible, and more accurate, with digital twins and machine learning reducing reliance on trial and error. Powders and alloys must be optimized for HIP, with improved cleanliness, reduced oxides, and tailored chemistries that enhance creep, fatigue, and irradiation resistance. Interfaces between AM and HIP regions must be better engineered through coatings, machining strategies, and surface treatments to mitigate oxide formation and ensure reliable bonding to explore opportunities for HIP of targeted compositional parts, as well as multimaterial HIP cladding applications. Monitoring and nondestructive evaluation need to expand, incorporating multimodal sensors, x-ray computed tomography, and real-time data integration through platforms such as Pelican. At the same time, the pathway to industrial adoption requires techno-economic analysis, machinability studies, and qualification frameworks aligned with industry and regulatory standards. Finally, workforce and academic engagement must be strengthened. Programs that train technicians and engineers for US Navy and US Department of Energy manufacturing challenges should be paired with academic partnerships to support fundamental research, with open sharing of non-export-controlled data to accelerate innovation and build the next generation of experts. In conclusion, this report demonstrates that hybrid AM + PM-HIP is scientifically viable and strategically important. By combining the design agility of AM with the consolidation strength of HIP and embedding modeling, monitoring, and workforce development, this approach provided a transformative new capability for US manufacturing. The path forward is clear: hybrid AM + PM-HIP is not just a promising research direction but is also potentially an industrially relevant pathway that can reshape how nuclear-grade components are designed, qualified, and deployed.

36 MATERIALS SCIENCE↗

Electronically induced defect creation at semiconductor/oxide interface revealed by time-dependent density functional theory

Carrier induced defect creation at the semiconductor-oxide interface has been known as the origin of electronic device degradation for a long time, but how exactly the interface lattice can be damaged by carriers (especially low-energy ones) remains unclear. Here we carry out real-time time-dependent density functional theory simulations on concrete Si/SiO 2 interfaces to study the interaction between excited electrons and interface bonds. We show that the normal interface Si-H bonds are generally resistant to electrons due to the delocalized nature and high energy level of the Si-H antibonding states, and due to the high-energy barrier to break the Si-H bond. However, if an additional hydrogen atom exists by attaching to a nearby oxygen atom (forming a “Si-H···H-O” complex), the Si-H bond will be greatly weakened, including the reduction of energy barrier for bond breaking, and the lowering of the antibonding state energy level which favors electron injection. Together with the multiple vibrational excitation process, the corresponding Si-H bond can be broken much more easily. Thus we propose that the Si-H···H-O complex will be the center for defect creation and device degradation. Finally, we also explain why such a center might be relatively easy to form during the hydrogen annealing process.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Buffer-layer effect on the ferromagnetism of manganite heterojunctions

Identifying and understanding interfacial magnetic structures of transition-metal oxides are of great importance not only for fundamental physics but also for potential device applications. Among them, manganite and ruthenate heterostructures have attracted considerable interest due to their intriguing interfacial properties induced by complex magnetic interactions. Here, we report the observation of dramatic buffer-layer dependence of ferromagnetism in ultrathin (L⁢a 2/3 ⁢C⁢a 1/3 )⁢Mn⁢O 3 (LCMO)-based heterostructures. Though all trilayers are nonmetallic, the SrRu⁢O 3 -buffered LCMO trilayer exhibits enhanced ferromagnetism with the Curie temperature (𝑇 C ∼ 198K) much higher than for CaRu⁢O 3 (𝑇 C ∼ 99K)- and SrTi⁢O 3 (𝑇 C ∼ 42K)-buffered counterparts, as well as the monolithic LCMO films with similar thickness. Combining atomically resolved scanning transmission electron microscopy imaging with electron energy loss spectroscopy mapping, we reveal that asymmetric interfaces exist in the SrRu⁢O 3 buffered trilayer, with one exhibiting 1 unit-cell Sr diffusion into LCMO, which is responsible for the 𝑇 C enhancement. In contrast, charge transfer, which has been proposed previously as a possible mechanism, is excluded in this study. In conclusion, our results may pave a promising road toward effective atomic control of interfacial magnetism.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Enhanced ferroelectricity in ultrathin films grown directly on silicon

Ultrathin ferroelectric materials could potentially enable low-power logic and nonvolatile memories. As ferroelectric materials are made thinner, however, the ferroelectricity is usually suppressed. Size effects in ferroelectrics have been thoroughly investigated in perovskite oxides—the archetypal ferroelectric system. Perovskites, however, have so far proved unsuitable for thickness scaling and integration with modern semiconductor processes. In this paper we report ferroelectricity in ultrathin doped hafnium oxide (HfO 2 ), a fluorite-structure oxide grown by atomic layer deposition on silicon. We demonstrate the persistence of inversion symmetry breaking and spontaneous, switchable polarization down to a thickness of one nanometre. Our results indicate not only the absence of a ferroelectric critical thickness but also enhanced polar distortions as film thickness is reduced, unlike in perovskite ferroelectrics. This approach to enhancing ferroelectricity in ultrathin layers could provide a route towards polarization-driven memories and ferroelectric-based advanced transistors. This work shifts the search for the fundamental limits of ferroelectricity to simpler transition-metal oxide systems—that is, from perovskite-derived complex oxides to fluorite-structure binary oxides—in which ‘reverse’ size effects counterintuitively stabilize polar symmetry in the ultrathin regime.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Differential structure and functional gene response to geochemistry associated with the suspended and attached shallow aquifer microbiomes from the Illinois Basin, IL

Despite the clear ecological significance of the microbiomes inhabiting groundwater and connected ecosystems, our current understanding of their habitats, functionality, and the ecological processes controlling their assembly have been limited. In this study, an efficient pipeline combining geochemistry, high-throughput Fluidigm TM functional gene amplification and sequencing was developed to analyze the suspended and attached microbial communities inhabiting five groundwater monitoring wells in the Illinois Basin, USA. The dominant taxa in the suspended and the attached microbial communities exhibited significantly different spatial and temporal changes in both alpha- and beta-diversity. Further analyses of representative functional genes affiliated with N 2 fixation (nifH), methane oxidation (pmoA), and sulfate reduction (dsrB, and aprA), suggested functional redundancy within the shallow aquifer microbiomes. While more diversified functional gene taxa were observed for the suspended microbial communities than the attached ones except for pmoA, different levels of changes over time and space were observed between these functional genes. Notably, deterministic and stochastic ecological processes shaped the assembly of microbial communities and functional gene reservoirs differently. While homogenous selection was the prevailing process controlling assembly of microbial communities, the neutral processes (e.g., dispersal limitation, drift and others) were more important for the functional genes. The results suggest complex and changing shallow aquifer microbiomes, whose functionality and assembly vary even between the spatially proximate habitats and fractions. As a result, this research underscored the importance to include all the interface components for a more holistic understanding of the biogeochemical processes in aquifer ecosystems, which is also instructive for practical applications.

54 ENVIRONMENTAL SCIENCES↗

Status of LBNF/DUNE near site liquid argon proximity and external cryogenics systems development.

The Deep Underground Neutrino Experiment (DUNE) near site located at Fermilab will host the neutrino beam complex. It includes a high voltage liquid argon time projection chamber located 60-meter underground used as beamline instrumentation. The LAr cryogenic system provided by the Long-Baseline Neutrino Facility (LBNF) regulates thermohydraulic conditions of the membrane cryostat hosting the detector with 285 Ton purified LAr. The purification system uses molecular sieve and copper oxide pellets to manage the argon contamination below 100 ppt (parts per trillion) oxygen equivalent. The detector and its cryogenics are capable to move a stroke of 30 meters on/off beam. The cryogenic system modes of operation include the cryostat pressure test, purge in open loop, detector cooldown, cryostat fill, closed loop purification, liquid empty, and purification system activation/regeneration process. The system design status and schedule, and technical details such as operating modes and interfaces are reported in this paper.

43 PARTICLE ACCELERATORS↗

Electrostatic modulation of the lateral carrier density profile in field effect devices with nonlinear dielectrics

The properties of two-dimensional (2D) electronic systems are often effectively controlled using electrostatic gating. The geometry of such field effect devices influences the effectiveness of the gate and the carrier density profile in the 2D device. Here, in this work, we analyze the gate-induced spatial variations in the lateral carrier density in patterned LaAlO 3 /SrTiO 3 devices. We model the electrostatics of the 2D interface using the Thomas-Fermi approximation and compute the gate-induced charge distribution at the interface. We show that the electric field lines generated by the gate are focused at the edges of the device, causing an increased depletion near its edges. This effect is accentuated in LaAlO 3 /SrTiO 3 due to the large, nonlinear dielectric constant of the substrate, and the large distance between the gate electrode and the interface. We experimentally demonstrate one consequence of this effect by directly imaging current distributions in gated heterostructures, finding that insulating regions nucleate at the edges of the device due to the gate. Our results suggest that device geometry and choice of dielectric materials control the charge distribution in 2D systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Nodeless High- T c Superconductivity in the Highly Overdoped CuO 2 Monolayer

We study the electronic structure and superconductivity in a CuO 2 monolayer grown recently on the d-wave cuprate superconductor Bi 2 Sr 2 CaCu 2 O 8+δ . Density functional theory calculations indicate a significant charge transfer across the interface such that the CuO 2 monolayer is heavily overdoped into the hole-rich regime yet inaccessible in bulk cuprates. We show that both the Cu d x 2 –y 2 and d 3z 2 –r 2 orbitals become important and the Fermi surface contains one electron and one hole pocket associated with the two orbitals, respectively. Constructing a minimal correlated two-orbital model for the e g complex, we show that the spin-orbital exchange interactions produce a nodeless superconductor with extended s-wave pairing symmetry and a pairing energy gap comparable to the bulk d-wave gap, in agreement with recent experiments. Here, the findings point to a direction of realizing new high-T c superconductors in ozone grown transition-metal-oxide monolayer heterostructures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

An Interdisciplinary View of Interfaces: Perspectives Regarding Emergent Phase Formation

A perspective on emergent phase formation is presented using an interdisciplinary approach gained by working at the “interface” between diverse application areas, including solid oxide fuel cells (SOFCs) and ionic membrane systems, solid state lithium batteries, and ceramics for nuclear waste immobilization. The grain boundary interfacial characteristics of model single-phase materials in these application areas, including (i) CeO2, (ii) Li7La3Zr2O12 (LLZO), and (iii) hollandite of the form BaxCsyGa2x+yTi8-2x-yO16, as well as the potential for emergent phase formation in composite systems, are discussed. The potential physical properties resulting from emergent phase structure and distribution are discussed, including an overview of existing three-dimensional (3D) imaging techniques recently used for characterization. Finally, an approach for thermodynamic characterization of emergent phases based on melt solution calorimetry is outlined, which may be used to predict the energy landscape including phase formation and stability of complex multiphase systems.

25 ENERGY STORAGE↗

Orion European Structural Test Article Propellant Tank Fill and Drain Carts

Environmental testing of the Orion European Structural Test Article (E-STA), which contains the Orion European Service Module (ESM), required that the onboard propellant tanks be filled and drained with fuel and oxidizer simulant fluids as well as pressurized and depressurized with an ullage gas. This conference paper will elaborate on how these objectives were fulfilled by presenting the development of derived requirements definition, initial fill and drain concepts, selection of simulant fluids, finalization of pump and pressurization design, selection of components, and selection of transfer hoses and interface connections as well as development and maintenance of budgets, schedules, reviews, construction, documentation, and test procedures. This paper also describes the implementation of checkout and commissioning activities leading to successful fluid cart pumping and pressurization operations for the test campaign. The development, construction, and operation of the fluid cart pumping and pressurization systems for the environmental testing of the Orion E-STA, took place at NASA's Plum Brook Station Space Environments Complex (SEC) during 2015 and 2016.

FLUID TRANSFER↗

Atom Probe Tomography Unveils Formation Mechanisms of Wear-Protective Tribofilms by ZDDP, Ionic Liquid, and Their Combination

The development of advanced lubricant additives has been a critical component in paving the way for increasing energy efficiency and durability for numerous industry applications. However, the formation mechanisms of additive-induced protective tribofilms are not yet fully understood because of the complex chemomechanical interactions at the contact interface and the limited spatial resolution of many characterizing techniques currently used. In this paper, the tribofilms on a gray cast iron surface formed by three antiwear additives are systematically studied; a phosphonium-phosphate ionic liquid (IL), a zinc dialkyldithiophosphate (ZDDP), and an IL+ZDDP combination. All three additives provide excellent wear protection, with the IL+ZDDP combination exhibiting a synergetic effect, resulting in further reduced friction and wear. Atom probe tomography (APT) and scanning transmission electron microscopy (STEM) imaging and electron energy loss spectroscopy (EELS) were used to interrogate the subnm chemistry and bonding states for each of the tribofilms of interest. The IL tribofilm appeared amorphous and was Fe, P, and O rich. Wear debris particles having an Fe-rich core and an oxide shell were present in this tribofilm and a transitional oxide (Fe 2 O 3 )-containing layer was identified at the interface between the tribofilm and the cast iron substrate. The ZDDP+IL tribofilm shared some of the characteristics found in the IL and ZDDP tribofilms. Finally, tribofilm formation mechanisms are proposed on the basis of the observations made at the atomic level.

36 MATERIALS SCIENCE↗

The roles of SDHAF2 and dicarboxylate in covalent flavinylation of SDHA, the human complex II flavoprotein

Mitochondrial complex II, also known as succinate dehydrogenase (SDH), is an integral-membrane heterotetramer (SDHABCD) that links two essential energy-producing processes, the tricarboxylic acid (TCA) cycle and oxidative phosphorylation. A significant amount of information is available on the structure and function of mature complex II from a range of organisms. However, there is a gap in our understanding of how the enzyme assembles into a functional complex, and disease-associated complex II insufficiency may result from incorrect function of the mature enzyme or from assembly defects. Here, we investigate the assembly of human complex II by combining a biochemical reconstructionist approach with structural studies. We report an X-ray structure of human SDHA and its dedicated assembly factor SDHAF2. Importantly, we also identify a small molecule dicarboxylate that acts as an essential cofactor in this process and works in synergy with SDHAF2 to properly orient the flavin and capping domains of SDHA. This reorganizes the active site, which is located at the interface of these domains, and adjusts the pK a of SDHA R451 so that covalent attachment of the flavin adenine dinucleotide (FAD) cofactor is supported. We analyze the impact of disease-associated SDHA mutations on assembly and identify four distinct conformational forms of the complex II flavoprotein that we assign to roles in assembly and catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-temperature active oxidation of nanocrystalline silicon-carbide: A reactive force-field molecular dynamics study

Flexible woven SiC ceramics are prone to accelerated fiber embrittlement under high temperature oxidation in dynamic oxygen environments. The nanocrystalline structure of the constituent fibers impacts the reaction kinetics and phase transformations during active oxidation. However, fundamental understanding and quantification of grain boundary effects on oxidation behavior in nanocrystalline SiC remain elusive when temperatures exceed 1500 K. This study deploys large-scale molecular dynamics simulations with a reactive force-field to elucidate the complex roles of atomic oxygen reservoir conditions and grain size on oxidation kinetics and the nature of oxides produced in both monocrystalline and nanocrystalline 3C-SiC between 1100 K and 2000 K. The simulations with dynamically replenished oxygen provide good agreement with oxidation kinetics and activation energies for the monocrystalline Si(100) and C(100) orientations published in the available literature. This study reveals that, by contrast, nanocrystalline SiC samples exhibit two distinct oxidation kinetics with a transition point at 1500 K due to surface melting, which is supported by experimental evidence. The introduction of a grain-boundary network produces a two-fold decrease in oxidation activation energies compared to monocrystalline SiC below 1500 K. Above 1500 K, however, the activation energies rise substantially due to the formation of a liquid Si phase at the SiC/Si oxide interface. Further, it is shown that the stability of the interfacial liquid phase is promoted by incoherent grain boundaries in the crystalline SiC. These findings are important for the deployment of nanocrystalline SiC fibers in advanced thermal protection systems for high-temperature applications.

36 MATERIALS SCIENCE↗

Kinetically versus thermodynamically controlled factors governing elementary pathways of GaP(111) surface oxidation

GaP and related III-V semiconductors have attracted interest as high-efficiency photoelectrochemical electrodes for solar water splitting. However, their efficacy is linked to the presence, identity, and integrity of native surface oxides, which are structurally and chemically complex and evolve during operation. Using ambient pressure X-ray photoelectron spectroscopy (APXPS) coupled with ab initio simulations, we track key chemical motifs expressed during evolution of GaP(111) surface oxides, their associated reaction kinetics, and their correlations with electronic properties. We identify two distinct thermal regimes corresponding to kinetically and thermodynamically controlled oxidation. Below 600 K, exposure to O2 generates kinetically facile Ga-O-Ga configurations, whereas higher temperatures cause activated oxygen to insert into Ga–P bonds as part of a thermodynamically driven transformation into a complex, heterogeneous 3D network of surface POx (1≤x ≤ 4) groups and Ga2O3 species, the latter of which eventually dominates upon depletion of surface phosphorus. Here our study highlights the critical competition between kinetic and thermodynamic factors during GaP oxidation, yielding insights for fabricating stable III-P-based photoelectrodes with precisely engineered surface properties.

08 HYDROGEN↗

Orion European Structural Test Article Propellant Tank Fill and Drain Carts

Environmental testing of the Orion European Structural Test Article (E-STA), which contains the Orion European Service Module (ESM), required that the onboard propellant tanks be filled and drained with fuel and oxidizer simulant fluids as well as pressurized and de-pressurized with an ullage gas. This conference paper will elaborate on how these objectives were fulfilled by presenting the development of derived requirements definition, initial fill and drain concepts, selection of simulant fluids, finalization of pump and pressurization design, selection of components, selection of transfer hoses and interface connections, as well as development and maintenance of budgets, schedules, reviews, construction, documentation, and test procedures. This paper also describes implementation of checkout and commissioning activities leading to successful fluid cart pumping and pressurization operations for the test campaign. The development, construction, and operation of the fluid cart pumping and pressurization systems for the Environmental testing of the Orion European Structural Test Article (E-STA), took place at the NASA Glenn Research Center's Plum Brook Station Space Environments Complex (SEC) during 2015 and 2016.

Pressurization↗

STEM and APT characterization of scale formation on a La,Hf,Ti-doped NiCrAl model alloy

A thermally grown scale formed on a cast NiCrAl model alloy doped with lanthanum, hafnium, and titanium was examined after isothermal exposure at 1100 °C for 100 h in dry flowing O 2 to understand the dopant segregation along scale grain boundaries. The complex scale formed on the alloy surface was composed of two types of substrates: phase-dependent, thin (<250 nm) outer layers and a columnar-grained ~3.5 μm inner alumina layer. Two types of oxides formed between the inner and outer scale layers: small (3–15 nm) La 2 O 3 and larger (≤50 nm) HfO 2 oxide precipitates. Nonuniform distributions of the hafnium, lanthanum, and titanium dopants were observed along the inner scale grain boundaries, with hafnium dominating in most of the grain boundaries of α-Al 2 O 3 . The concentration of reactive elements (RE) seemed to strongly depend on the grain boundary structure. The level of titanium grain boundary segregation in the inner scale decreased toward the model alloy (substrate), confirming the fast outward diffusion of titanium. Hafnium was also observed at the metal–scale interface and in the γ' (Ni 3 Al) phase of the alloy. High-resolution scanning transmission electron microscopy (STEM) confirmed the substitution of REs for aluminum atoms at the scale grain boundaries, consistent with both the semiconducting band structure and the site-blocking models. Both STEM and atom probe tomography allowed quantification of REs along the scale grain boundaries across the scale thickness. Analysis of the scale morphology after isothermal exposure in flowing oxygen revealed a myriad of new precipitate phases, RE segregation dependence on grain boundary type, and atomic arrangement along scale grain boundaries, which is expected to influence the scale growth rate, stability, and mechanical properties.

36 MATERIALS SCIENCE↗