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The impact of oxygen nonstoichiometry upon partial molar thermodynamic quantities in PrBaCo{sub 2}O{sub 5+δ}
The coulometric titration data are utilized in order to calculate changes of oxygen partial entropy and enthalpy in PrBaCo{sub 2}O{sub 5+δ} with variations of oxygen content and temperature. The thermodynamic equilibrium of the cobaltite with the ambient gas phase is analyzed based on the interface of oxygen exchange and oxidation, and the intrinsic reaction of thermal excitation of Co{sup 3+} cations. The partial thermodynamic functions of the movable oxygen in PrBaCo{sub 2}O{sub 5+δ} are shown to be interrelated with the thermodynamic parameters of the defect formation reactions. The existence of a band gap of about 0.4 eV in the electronic spectrum of the cobaltite follows from a favorable comparison of the calculated and experimental dependencies of the partial thermodynamic functions of the movable oxygen. - Graphical abstract: Partial thermodynamic functions of movable oxygen in PrBaCo{sub 2}O{sub 5+δ}. - Highlights: • Thermodynamic functions of oxygen in PrBaCo{sub 2}O{sub 5+δ} are obtained from pO{sub 2}–T–δ diagram. • The defect model is developed to describe changes in thermodynamic functions. • Thermodynamic analysis gives evidence to a band gap in PrBaCo{sub 2}O{sub 5+δ}.
Frank-van der Merwe growth in bilayer graphene
Bilayer graphene has attracted significant interest because of its unique properties, including fascinating electrical behavior when one layer is slightly rotated relative to the other. However, the quality of large-area bilayer graphene is often limited by the layer-plus-island growth mode in which islands of thicker graphene present as unavoidable impurities. Here, we report the observation of the layer-by-layer, Frank-van der Merwe (FM) growth mode in bilayer graphene where multilayer impurities are suppressed. Instead of the conventional surface adhesive energy, we found it possible to tune interface adhesive energy with an oxidative pretreatment. Finally, the FM-grown bilayer graphene is of AB stacking or with small twisting angle (θ = 0°–5°), which is more mechanically robust compared with monolayer graphene, facilitating a free-standing wet transfer technology.
Manifestations of two-dimensional electron gas in molecular crystals
The existence of two-dimensional electron gas in molecular materials has not been reported or discussed. Intriguing properties of two-dimensional electron gas observed on interfaces of polar and nonpolar oxides spurred oxide electronics and advanced nanotechnology. Here, in this study, we discover how an electrostatic instability occurs on polar surfaces of molecular crystals and explore its manifestations, chemical degradation of surfaces, charge separation, electrical conductivity, optical band-gap closure and surface metallization. A thin layer of polar surface of a dielectric molecular crystal becomes metallic due to interactions of polar molecules. Our findings are illustrated with two polymorphs of cyclotetramethylene-tetranitramine crystals, the polar δ-phase and nonpolar β-phase. Our theory offers an explanation to a relative stability of the β-phase versus the explosive reactivity of δ-phase and to the experimentally observed difference in conductivity of these crystals. We predict that the electrostatic instability takes place on all polar molecular materials.
Lead-Free Flexible Perovskite Solar Cells with Interfacial Native Oxide Have >10% Efficiency and Simultaneously Enhanced Stability and Reliability
Here we demonstrate an innovative compositional and interfacial engineering approach to achieve Pb-free flexible perovskite solar cells (f-PSCs) with an unprecedented combination of the highest efficiency reported to date (10.43%), together with enhanced operational stability and mechanical reliability. The key to this approach is alloying of an FASnI3 metal halide perovskite (MHP) thin film with Ge2+ to stabilize the Sn2+ oxidation state in the MHP, together with the use of a NiOx hole-transport layer. We show that this results in the in situ formation of a thin amorphous GeO2 native oxide layer at the NiOx/FASn0.9Ge0.1I3 interface. This layer not only passivates that critical interface but also enhances the interfacial mechanical bonding.
Atomistic Computer Simulations of Water Interactions and Dissolution of Inorganic Glasses
Computational simulations at the atomistic level play an increasing important role in understanding the structures, behaviors, and the structure-property relationships of glass and amorphous materials. In this paper, we reviewed atomistic simulation methods ranging from first principles calculations and ab initio molecular dynamics (AIMD), to classical molecular dynamics (MD) and meso-scale kinetic Monte Carlo (KMC) simulations and their applications to glass-water interactions and glass dissolutions. Particularly, the use of these simulation methods in understanding the reaction mechanisms of water with oxide glasses, water-glass interfaces, hydrated porous silica gels formation, the structure and properties of multicomponent glasses, and microstructure evolution are reviewed. Here, the advantages and disadvantageous of these methods are discussed and the current challenges and future direction of atomistic simulations in glass dissolution are presented.
The effect of oxygen vacancies on water wettability of transition metal based SrTiO 3 and rare-earth based Lu 2 O 3
Understanding the structural, physical and chemical properties of the surface and interfaces of different metal-oxides and their possible applications in photo-catalysis and biology is a very important emerging research field. Motivated in this direction, this article would enable understanding of how different fluids, particularly water, interact with oxide surfaces. We have studied the water contact angle of 3d transition metal oxide thin films of SrTiO 3 , and of 4f rare-earth oxide thin films of Lu 2 O 3 . These metal oxides were grown using pulsed laser deposition and they are atomically flat and with known orientation and explicitly characterized for their structure and composition. Further study was done on the effects of oxygen vacancies on the water contact angle of the 3d and 4f oxides. For 3d SrTiO 3 oxide with oxygen vacancies, we have observed an increase in hydroxylation with consequent increase of wettability which is in line with the previous reports whereas an interesting opposite trend was seen in the case of rare-earth Lu 2 O 3 oxide. Density functional theory simulations of water interaction on the above mentioned systems have also been presented to further substantiate our experimental findings.
Large electron concentration modulation using capacitance enhancement in SrTiO{sub 3}/SmTiO{sub 3} Fin-field effect transistors
Solid-state modulation of 2-dimensional electron gases (2DEGs) with extreme (∼3.3 × 10{sup 14 }cm{sup −2}) densities corresponding to 1/2 electron per interface unit cell at complex oxide heterointerfaces (such as SrTiO{sub 3}/GdTiO{sub 3} or SrTiO{sub 3}/SmTiO{sub 3}) is challenging because it requires enormous gate capacitances. One way to achieve large gate capacitances is by geometrical capacitance enhancement in fin structures. In this work, we fabricate both Au-gated planar field effect transistors (FETs) and Fin-FETs with varying fin-widths on 60 nm SrTiO{sub 3}/5 nm SmTiO{sub 3} thin films grown by hybrid molecular beam epitaxy. We find that the FinFETs exhibit higher gate capacitance compared to planar FETs. By scaling down the SrTiO{sub 3}/SmTiO{sub 3} fin widths, we demonstrate further gate capacitance enhancement, almost twice compared to the planar FETs. In the FinFETs with narrowest fin-widths, we demonstrate a record 2DEG electron concentration modulation of ∼2.4 × 10{sup 14 }cm{sup −2}.
Superconductivity from the Slater mode: Application to KTaO 3 heterostructures
Superconductivity has been observed for the 2D electron gas (2DEG) at the interface of KTaO 3 with other oxides, with a transition temperature about an order of magnitude higher than its 3𝑑 cousin SrTiO 3 . Here, the superconducting transition temperature is strongly dependent on the orientation of the interface. Motivated by this observation, we study pairing due to the exchange of the soft transverse optic phonon mode characteristic of quantum paraelectrics and use the resulting theory to comment on the nature of superconductivity of this 2DEG. We find (1) an orientation dependence consistent with experiment along with an anisotropic gap function, but (2) a BCS coupling constant that is smaller than needed and so must be augmented by contributions from other phonons to be consistent with the observed values of 𝑇 𝑐 .
Anomalously deep polarization in SrTiO3 (001) interfaced with an epitaxial ultrathin manganite film
Using atomically-resolved imaging and spectroscopy, we reveal a remarkably deep polarization in non-ferroelectric SrTiO 3 near its interface with an ultrathin nonmetallic film of La 2/3 Sr 1/3 MnO 3 . Electron holography shows an electric field near the interface in SrTiO 3 , yielding a surprising spontaneous polarization density of ~ 21 μC/cm 2 . Combining the experimental results with first principles calculations, we propose that the observed deep polarization is induced by the electric field originating from oxygen vacancies that extend beyond a dozen unit-cells from the interface, thus providing important evidence of the role of defects in the emergent interface properties of transition metal oxides.
Development of high performance ODS alloys
This project aims to capitalize on insights developed from recent high-dose self-ion irradiation experiments in order to develop and test the next generation of optimized ODS alloys needed to meet the nuclear community's need for high strength, radiation-tolerant cladding and core components, especially with enhanced resistance to void swelling. Two of these insights are that ferrite grains swell earlier than tempered martensite grains, and oxide dispersions currently produced only in ferrite grains require a high level of uniformity and stability to be successful. An additional insight is that ODS particle stability is dependent on as-yet unidentified compositional combinations of dispersoid and alloy matrix, such as dispersoids are stable in MA957 to doses greater than 200 dpa but dissolve in MA956 at doses less than 200 dpa. These findings focus attention on candidate next-generation alloys which address these concerns. Collaboration with two Japanese groups provides this project with two sets of first-round candidate alloys that have already undergone extensive development and testing for unirradiated properties, but have not yet been evaluated for their irradiation performance. The first set of candidate alloys are dual phase (ferrite + martensite) ODS alloys with oxide particles uniformly distributed in both ferrite and martensite phases. The second set of candidate alloys are ODS alloys containing non-standard dispersoid compositions with controllable oxide particle sizes, phases and interfaces.
Aluminum Clad Spent Nuclear Fuel Task 1: Oxyhydroxide Layer Behavior and Chemistry Experimental Test Plan
This document presents the test plan for Task 1 of the Aluminum Clad Spent Nuclear Fuel Long Term Dry Storage Technical Issues Action Plan, which covers aluminum clad spent nuclear fuel (ASNF) fuel that is currently or may in the future be held in dry storage for an extended period. The objectives of the Task 1 test plan are to: 1. Understand how ASNF performs over extended dry storage periods. 2. Understand mechanisms that could alter aluminum hydroxide/oxyhydroxide layers during extended storage. 3. Characterize thickness and growth rates of oxyhydroxide layers based on fuel history and provide anticipated H2 gas generation rates based on chemical corrosion. 4. Characterize materials properties for oxides present on ASNF. 5. Interface with canister modeling activity to deliver degradation rates for package performance for both sealed and vented configurations. 6. Understand implications of higher temperature drying (250°C) on stability in dry storage. This test plan lays out the technical activities that will be performed to achieve the test objectives described above. Experiments will be performed at Idaho National Laboratory in-town facilities. Specimens for testing will include those supplied by Savannah River National Laboratory. Activities will include both experiments and modeling and will coordinate with other tasks within the project.
Development of Polycrystalline Photoelectrodes with Optimum Compositions and Morphologies for Solar Fuel Production via Electrochemical Synthesis (Final Technical Report)
Photoelectrochemical cells (PECs) can utilize solar energy for water splitting to produce H 2 as a clean fuel. The most critical components of a water-splitting PEC are semiconductor electrodes (photoelectrodes) that absorb solar energy to generate photoexcited charge carriers and transport them to the electrode/electrolyte interface for water reduction and oxidation reactions. While efficient PEC hydrogen production has been successfully demonstrated on the laboratory scale, the commercial viability of PECs depends critically on the cost of H 2 produced by the PECs, which is affected by the cost of PEC construction. Therefore, identifying promising inexpensive semiconductor electrodes is important. The goal of this project was to bring an advancement in the synthesis and understanding of inexpensive polycrystalline photoelectrodes based on oxides. Oxide-based semiconductors are inexpensive, easy to fabricate, and relatively more stable in aqueous media compared to other types of semiconductors. This project developed new electrodeposition methods to produce a variety of oxide-based semiconductor electrodes with precisely controlled compositions and morphologies to enhance photon absorption, electron-hole separation, and the use of electrons and holes for desired chemical reactions. The resulting high-quality photoelectrodes were investigated to establish the structure-composition-morphology-photoelectrochemical property relationships to identify the advantages and limitations of each oxide semiconductor system.
Microstructure of Neutron-Irradiated Al 3 Hf-Al Thermal Neutron Absorber Materials
A thermal neutron-absorbing metal matrix composite (MMC) comprised of Al 3 Hf particles in an aluminum matrix was developed to filter out thermal neutrons and create a fast flux environment for material testing in a mixed-spectrum nuclear reactor. Intermetallic Al 3 Hf particles capture thermal neutrons and are embedded in a highly conductive aluminum matrix that provides conductive cooling of the heat generated due to thermal neutron capture by the hafnium. These Al 3 Hf-Al MMCs were fabricated using powder metallurgy via hot pressing. The specimens were neutron-irradiated to between 1.12 and 5.38 dpa and temperatures ranging from 286 °C to 400 °C. The post-irradiation examination included microstructure characterization using transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy. This study reports the microstructural observations of four irradiated samples and one unirradiated control sample. All the samples showed the presence of oxide at the particle–matrix interface. The irradiated specimens revealed needle-like structures that extended from the surface of the Al 3 Hf particles into the Al matrix. An automated segmentation tool was implemented based on a YOLO11 computer vision-based approach to identify dislocation lines and loops in TEM images of the irradiated Al-Al 3 Hf MMCs. This work provides insight into the microstructural stability of Al 3 Hf-Al MMCs under irradiation, supporting their consideration as a novel neutron absorber that enables advanced spectral tailoring.
Microstructure and fracture in SiC whisker reinforced 2124 aluminum composite
The microstructures of extruded and hot-rolled 2124 Al-15 percent (by weight) SiC whisker composites have been investigated, experimentally. Among the specific factors studied were: the strength of the whisker-matrix interfaces; (2) the presence of oxides; (3) the presence of defective whiskers; (4) and the presence of distribution of intermetallic compounds, impurities in the SiC(w) powder, and microstructural inhomogeneities. Modifications in the microstructure of the SiC/AL composites due to hot rolling and extrusion are illustrated in a series of microphotographs. It was found that hot rolling along the axis of extrusion was associated with some types of whisker damage, while the whiskers still retain their original orientation. Hot-rolling perpendicular to the axis of extrusion, however, tended to rotate the whiskers and produced a nearly isotropic material. Whisker free zones were virtually eliminated or reduced in size by hot rolling. In situ Auger fractography of the composite showed that the interfacial bonding between the SiC and the Al matrix was good and that Al2O2 had no significant influence on the fracture mechanics of the composite.
Isothermal Damage and Fatigue Behavior of SCS-6/Timetal 21S [0/90](Sub S) Composite at 650 Deg C
The isothermal fatigue damage and life behaviors of SCS-6/Timetal 21S (0/90)s were investigated at 650 C. Strain ratcheting and degradation of the composite's static elastic modulus were carefully monitored as functions of cycles to indicate damage progression. Extensive fractographic and metallographic analyses were conducted to determine damage/failure mechanisms. Resulting fatigue lives show considerable reductions in comparison to (0) reinforced titanium matrix composites subjected to comparable conditions. Notable stiffness degradations were found to occur after the first cycle of loading, even at relatively low maximum stress levels, where cyclic lives are greater than 25,000 cycles. This was attributed to the extremely weak fiber/matrix bond which fails under relatively low transverse loads. Stiffness degradations incurred on first cycle loadings and degradations thereafter were found to increase with increasing maximum stress. Environmental effects associated with oxidation of the (90) fiber interfaces clearly played a role in the damage mechanisms as fracture surfaces revealed environment assisted matrix cracking along the (90) fibers. Metallographic analysis indicated that all observable matrix fatigue cracks initiated at the (90) fiber/matrix interfaces. Global de-bonding in the loading direction was found along the (90) fibers. No surface initiated cracks were evident and minimal if any (0) fiber cracking was visible.
Transient Mixing Driven by Buoyancy Flows
Mixing driven by buoyancy-induced flows is of particular interest to microgravity processes, as the body force that governs the intensity of flow fields can be directly controlled. We consider a model experimental system to explore the dynamics of mixing which employs two miscible liquids inside a cavity separated initially by a divider. The two liquids are oriented vertically inside a rectangular cavity with constant width and height, and varying depths to span the range of a Hele-Shaw cell to a 3-[) configuration. The two miscible liquids can be sufficiently diluted and died, for example water and deuterium oxide, such that a distinct interface exists across the divider. The transient mixing characteristic of the two fluids is addressed by following the Lagrangian history of the interface for various aspect ratios in the z-plane (depth variation) as well as a range of pulling velocities of the divider. The mixing characteristics of the two fluids are quantified from measurement of the length stretch of the interface and its flow field using respectively image processing techniques and Particle Imaging Velocimetry. Scaling analysis shows that the length stretch depends on four governing parameters, namely the Grashof number (Gr), Schmidt number (Sc), aspect ratio (Ar), and Reynolds number (Re). Variation of the Schmidt number is taken into account through thermophysical property variation. Thus our problem reduces to a codimension three bifurcation in parametric space for Gr, Ar, and Re. Our experimental results show that for Gr on the order of 106 and a nominal cavity aspect ratio Ar = 0.2, the net effect of removal of the divider and the overwhelming buoyancy force causes an overturning motion which stretches and folds the interface to produce ml internal breakwave. The structure of the breakwave is similar to the ubiquitous Rayleigh-Taylor instability morphology. The breakwave is dissipated either through internal or wall collision depending on the impulsive velocity of the divider as prescribed by the Reynolds number. The decay of the collision event occurs through sloshing oscillations over a short time scale. The two fluids then become stably stratified with a diffusive band at the interface indicating local mass transport. The local bifurcation of the internal breakwave is investigated as a function of aspect ratio. Results show that for narrow cavities on the order of 2mm (Ar = 0.04) folding does not occur, the interface only stretches. As the cavity size increases folding occurs through a supercritical bifurcation. Insight into the mechanism of folding is obtained from measurement of the flow field which shows that in the neighborhood of the folding event, there exists hyperbolic points caused by multiple vortex interactions. The global length stretch of the interface as a function of time is nearly Gaussian; calculations of finite-time Liapunov exponents as well as construction of horseshoe maps indicate the likelihood of a chaotic transient.
Solute transport and the prediction of breakaway oxidation in gamma + beta Ni-Cr-Al alloys
The Al transport and the condition leading to breakaway oxidation during the cyclic oxidation of gamma + beta NiCrAl alloys have been studied. The Al concentration/distance profiles were measured after various cyclic oxidation exposures at 1200 C. It was observed that cyclic oxidation results in a decreasing Al concentration at the oxide/metal interface, maintaining a constant flux of Al to the Al2O3 scale. It was also observed that breakaway oxidation occurs when the Al concentration at the oxide/metal interface approaches zero. A numerical model was developed to simulate the diffusional transport of Al and to predict breakaway oxidation in gamma + beta NiCrAl alloys undergoing cyclic oxidation. In a comparison of two alloys with similar oxide spalling characteristics, the numerical model was shown to predict correctly the onset of breakaway oxidation in the higher Al-content alloy.