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At least 811 records · Page 45

Textural variations and impact history of the Millbillillie eucrite

We have investigated 10 new specimens of the Millbillillie eucrite to study its textures and mineral compositions by electron probe microanalyser and scanning electron microscope. Although originally described as having fine-grained texture, the new specimens show diversity of texture. The compositions (Mg/Fe ratios) of the host pigeonites and augite lamellae are homogeneous, respectively, in spite of the textural variation. In addition to their chemical homogeneity, pyroxenes in coarse and fine-grained clasts are partly inverted to orthopyroxene. Chemical zoning of plagioclase during crystal growth is preserved. This eucrite includes areas of granulitic breccias and impact melts. Large scale textures show a subparallel layering suggesting incomplete mixing and deposition of impact melt and lithic fragments. An Ar-39-Ar-40 age determination for a coarse-grained clast indicates a strong degassing event at 3.55 +/- 0.02 Ga. We conclude that Millbillillie is among the most equilibriated eucrites produced by thermal annealing after impact brecciation. According to the classificcation of impact breccias, Millbillillie can be classified as a mixture of granulitic breccias and impact melts. The last significant thermal event is characterized by network-like glassy veins that run through clasts and matrices. Consideration of textual observations and requirements for Ar-degassing suggests that the Ar-39-Ar-40 age could in principle date either the earlier brecciation and annealing event or the event which produced the veins.

Yamaguchi, Akira↗

Time-resolved 3D characterisation of early-age microstructural development of Portland cement

Abstract Time-resolved in-situ synchrotron X-ray microtomography reveals new levels of detail about the chemical and physical processes that take place as Portland cement hardens. The conversion of a fluid paste into a hardened product can be monitored on a sub-minute time-scale, and with sample movement/settlement corrections applied to enable individual particles to be tracked as they react, hydrate, and become interconnected into a single strong monolith. The growth of the strength-giving hydrate phases surrounding cement grains, and of the fluid-filled pore network that surrounds them, is able to be directly viewed at the level of individual cement particles through the application of this tracking protocol. When cement is brought into contact with water, a layer which differs in density from the bulk of the cement grains becomes observable on the grain surfaces during the induction period (during which time the heat evolution from the paste is relatively low). As hydration continues, reaction products grow both from particle surfaces into the initially fluid-filled region, and also into the space originally occupied by the cement particles, forming a density gradient within the microstructure. As the reaction accelerates and larger volumes of solid phases precipitate, the newly-formed solid structure percolates via interconnection of agglomerated low-density outer hydrates, which then densify as hydration continues. This eventually leads to solidification of the structure into a hardened porous matrix. Graphical abstract

36 MATERIALS SCIENCE↗

Predicting and Controlling Corrosion (Abbreviated Final Report)

Corrosion accumulates significant replacement costs in the transportation, utility, manufacturing, and infrastructure sectors. It also underpins several of LLNL’s core missions in stockpile stewardship, defense, and energy security. Whereas most corrosion and aging models are empirically parameterized to describe well-defined conditions late in the reaction, the factors that determine the early stages of corrosion—during which mitigation could be most impactful— are poorly understood. This project addressed the critical need for new approaches to predict the kinetics of corrosion initiation based on firm physical and chemical understanding. The activities encompassed degradation of relevant metals in both hydrogen-rich and environmental corrosion scenarios. The team integrated state-of-the-art multiscale simulation, in situ characterization, and data science within three technical thrusts: hydriding of Ti alloys; aqueous corrosion of Al and Ni-Cr alloys; and degradation of additively manufactured 316L stainless steel. In each case, novel capabilities were developed to identify and track the impacts of key atomistic, compositional, and microstructural features on the metal systems. For hydriding, protocols were developed to tightly integrate multiscale models, advanced multimodal characterization, and machine learning to determine how hydrogen interacts with native passivating surface oxides and nucleates new undesired phases, shedding new light on the critical role of grain boundaries, interfaces, and atomically disordered regions. For aqueous corrosion, the project demonstrated methods to predict dissolution rates of metal surfaces in corrosive solutions, to measure and understand microstructural and grain orientation effects on corrosion susceptibility, and to investigate competing growth and dissolution kinetics of surface oxides. For additively manufactured metals, analysis using state-of-the-art microscopy techniques revealed the role of specific heterogeneities invoked during laser processing, including cellular structure, dislocations, and precipitates, on corrosion susceptibility. In addition to new capabilities and understanding, the project provided an avenue for workforce development, as well as key partnerships with stakeholders in corrosion science.

08 HYDROGEN↗

Collaborative R&D with First Solar on Understanding Performance Limitations in CdTe (Project 1 "CdTe" - Mods 0-10, 13, 14-A1, 17)

This CRADA involves analyses on a variety of CdTe and CdTe-PV related materials, test structures, and solar cells produced at FSLR or NREL. Single-crystal (sx) material will be primarily MBE grown and provided by FSLR. Joint activities are focused on establishing the appropriate quality metrics as a basis for high performing sx devices and to study the dopability of the material. Polycrystalline (px) materials will be provided by NREL, FSLR, or fabricated jointly. Px activities are focused on the characterization of performance limiting mechanisms including bulk defects, grain boundaries, and the hetero-interface. A combination of growth, characterization, and theory will be applied. Analysis will include techniques that are well established in CdTe research at NREL (e.g., LIV/DIV/CV, AS/DLTS, LTPL, TRPL) as well as techniques that have not been widely applied to the PV part of CdTe technology (e.g., PCD, CL, uPL, SE).

14 SOLAR ENERGY↗

Fractographic analysis of gaseous hydrogen induced cracking in 18Ni maraging steel

Electron microscope fractographic analysis supplemented an extensive study of the kinetics of gaseous hydrogen assisted cracking in 18Ni maraging steel. Temperature determined the crack path morphology in each steel which, in turn, was directly related to the temperature dependence of the crack growth rate. Crack growth in the low temperature regime proceeded along prior austenite grain boundaries. Increasing the temperature above a critical value produced a continuously increasing proportion of transgranular quasi-cleavage associated with lath martensite boundaries. The amount of transgranular cracking was qualitatively correlated with the degree of temperature-induced deviation from Arrhenius behavior. Fractographic observations are interpreted in terms of hypothesized mechanisms for gaseous hydrogen embrittlement. It is concluded that hydrogen segregation to prior austenite and lath martensite boundaries must be considered as a significant factor in developing mechanisms for gaseous embrittlement of high strength steels.

Gangloff, R. P.↗

Materials for high-temperature thermoelectric conversion

The development of materials for high temperature thermoelectric energy conversion devices was investigated. The development of new criteria for the selection of materials which is based on understanding of the fundamental principles governing the behavior of high temperature thermoelectric materials is discussed. The synthesis and characterization of promising new materials and the growth of single crystals to eliminate possible problems associated with grain boundaries and other defects in polycrystalline materials are outlined.

Feigelson, R. S.↗

On the fatigue crack propagation behavior of superalloys at intermediate temperatures

Two superalloys used in gas-turbine disks, Rene 95 and IN-100 were tested in several forms at 0.33 Hz in air, and the results were compared with earlier data on Astroloy to gain a better understanding of the effects of grain size, strength, and alloy composition on the fatigue crack propagation behavior. In addition, selected forms of Rene 95 were tested at 0.33 Hz in vacuum and in air using a cycle with a 120-sec tensile dwell to evaluate the effects of environment and creep. Results of the study emphasize the beneficial effect of large grain size on the fatigue and crep-fatigue crack growth resistance of the superalloys in the temperature range corresponding to the operating temperatures of aircraft gas-turbine engine disk rims.

Gayda, J.↗

Grain boundary oxidation and its effects on high temperature fatigue life

Fatigue lives at elevated temperatures are often shortened by creep and/or oxidation. Creep causes grain boundary void nucleation and grain boundary cavitation. Grain boundary voids and cavities will accelerate fatigue crack nucleation and propagation, and thereby shorten fatigue life. The functional relationships between the damage rate of fatigue crack nucleation and propagation and the kinetic process of oxygen diffusion depend on the detailed physical processes. The kinetics of grain boundary oxidation penetration was investigated. The statistical distribution of grain boundary penetration depth was analyzed. Its effect on high temperature fatigue life are discussed. A model of intermittent micro-ruptures of grain boundary oxide was proposed for high temperature fatigue crack growth. The details of these studies are reported.

Liu, H. W.↗

Experiments on the formation, properties and processing of cosmic dust

The results from various experiments on the formation, properties, and processing of potential silicate components of cosmic dust are reviewed. Consideration is given to the role of evaporation and condensation in grain formation, nucleation experiments using volatile compounds and refractory species, and efforts to produce particles that might represent cosmic grains. Other studies include particle scattering experiments, studies on the growth of clusters, the sputtering process, the impact of temperature on sputtering yield and optical properties, and experimental and theoretical studies of the structure of particulate aggregates.

Donn, B. D.↗

Intergranular fracture of lithium fluoride-22 percent calcium fluoride hypereutectic salt at 800 K

Substantial strain-hardening was noted during the initial stages of deformation in constant-velocity compression tests conducted on as-cast samples of the LiF-22 mol pct CaF2 hypereutectic salt at 800 K. The deformed specimens exhibited extensive grain-boundary cracking and cavitation, suggesting that such cracking, in conjunction with interfacial sliding, is important for cavity nucleation at grain boundaries and at the LiF-CaF2 interfaces. Cavity growth and interlinkage occur through the preferential failure of the weaker LiF phase.

Raj, Subramanium V.↗

Identifying Challenges in Safeguards for Metallic Fuel Fabrication Facilities

As new advanced reactors gain popularity, there is an increasing interest in metallic fuel fabrication for fast reactors. While metallic fuels themselves are not a new idea, as many of the first reactors employed metallic fuels, new designs, compositions, and fabrication methods are appearing throughout the nuclear community. As the interest grows and facilities are constructed, both domestic and international safeguards will need to be heavily involved to support safeguards-by-design (SBD) measures from the start. This work compiles a review of historical and modern fuel types and fabrication methods, fabrication processes, safeguards gaps, and potential safeguards solutions. Metallic nuclear fuel types have been around for many decades and were included in some of the first reactors including the Experimental Breeder Reactor (EBR)-I and -II, the Fermi 1 reactor, the Integral Fast Reactor (IFR), and the Dounreay Fast Reactor (DFR). These reactors used various compositions including pure uranium (U) metal, U-zirconium (Zr) alloys, plutonium (Pu)-aluminum (Al) alloys, U-fissium (Fs) alloys, U-Pu-Zr alloys, and U-molybdenum (Mo) alloys [1, 2, 3, 4, 5]. These small alloying additions are included to improve the material properties of the pure U metal. The alpha-phase U (stable below 661C) suffers elongation in one direction causing grain boundary cracking and increasing creep rate due to irradiation growth, thermal cycling, and preferential crystal orientation. It is ideal to utilize the gamma-phase U (typically stable above 769C) by adding small amounts of alloying elements such as Zr or Mo to stabilize this phase down to room temperature [3]. Additionally, some research has been focused on U with transuranic (TRU) elements present, typically coming from the used fuel recycling process. Including these elements in fast reactor fuel can aid in the reduction of nuclear waste by burning minor long-lived actinides. However, the additions of TRU elements can cause concerns to arise when trying to fabrication or safeguard metallic fuels. A typical metallic fuel element is shown in Figure 1. Sodium is added into the cladding to create a thermal bond between the fuel slug and cladding wall. The fuel slug is then inserted and the end plug is welded on to the top of the fuel element. A gas plenum is left to create a headspace for gaseous fission products to escape rather than continue to build in the fuel itself [1, 5]. Other fuel element geometries exist as well, such as the Lightbridge twisted cruciform geometry shown in Figure 2 [6]. This design allows for better cooling performance and provides room for fuel rod swelling without impacting the fuel rod diameter. There are many different fabrication methods for metallic fuels, which is one of the many benefits of these fuel types. Many of these fabrication methods are relatively easy and cost-efficient. The most popular fabrication method is injection casting, sometimes called vacuum induction melting (VIM), shown in Figure 3 [4, 8, 9, 7, 10]. This method was largely used for EBR-II fuel fabrication. The injection casting system is contained inside of a vessel consisting of a Y2O3-coated graphite crucible surrounded by an induction coil with ZrO2-coated quartz molds suspended above the crucible. The fuel feedstock is placed inside of the graphite crucible and melted using the induction furnace. The induction furnace utilizes a dual frequency with the high frequency melting the feedstock and the low frequency causing stirring of the melted feedstock to form a homogeneous mixture. The mixture is heated to approximately 1600C in an argon environment. The vessel is evacuated and then the quartz molds are lowered into the graphite crucible containing the molten metal and the vessel is repressurized to inject the metal fuel upwards into the molds. The molds are removed and then shattered to release the fuel slugs. This fabrication method was used to fabricate 39,000 metallic fuel pins for EBR-II. While injection casting has been the most common metallic fuel fabrication method throughout the decades, many other methods have been explored including low-pressure gravity casting, microwave casting, continuous casting, centrifugal casting, coextrusion, and many others [11, 12, 8, 13, 14, 15]. Some of these methods aim to mitigate challenges that arise with americium (Am) volatilization during the casting process for TRU-containing fuel feedstocks, an issue with injection casting. Coextrusion is one of the methods explored at the Idaho National Laboratory (INL) and has been utilized for the initial fabrication tests of Lightbridge's unique fuels, as well as other metallic fuels with cladding coextruded. In this process, large billets are formed and machined and then inserted into a molten salt bath for approximately 30 minutes. The billets are then loaded into the extrusion press and extruded. This process can be seen in Figure 4 [15].

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Crystal Growth of ZnSe and Related Ternary Compound Semiconductors by Vapor Transport

Interest in optical devices which can operate in the visible spectrum has motivated research interest in the II-VI wide band gap semiconductor materials. The recent challenge for semiconductor opto-electronics is the development of a laser which can operate at short visible wavelengths, In the past several years, major advances in thin film technology such as molecular beam epitaxy and metal organic chemical vapor deposition have demonstrated the applicability of II-VI materials to important devices such as light-emitting diodes, lasers, and ultraviolet detectors.The demonstration of its optical bistable properties in bulk and thin film forms also make ZnSe a possible candidate material for the building blocks of a digital optical computer. Despite this, developments in the crystal growth of bulk II-VI semiconductor materials has not advanced far enough to provide the low price, high quality substrates needed for the thin film growth technology. The electrical and optical properties of semiconductor materials depend on the native point defects, (the deviation from stoichiometry), and the impurity or dopant distribution. To date, the bulk growth of ZnSe substrates has been plagued with problems related to defects such as non-uniform distributions of native defects, impurities and dopants, lattice strain, dislocations, grain boundaries, and second phase inclusions which greatly effect the device performance. In the bulk crystal growth of some technologically important semiconductors, such as ZnTe, CdS, ZnSe and ZnS, vapor growth techniques have significant advantages over melt growth techniques due to the high melting points of these materials.

Su, Ching-Hua↗

Quantized Grain Boundary States Promote Nanoparticle Alignment During Imperfect Oriented Attachment

Oriented attachment (OA) has become a well-recognized mechanism for the growth of metal, ceramic, and biomineral crystals. While many computational and experimental studies of OA have shown that particles can attach with some misorientation then rotate to remove adjoining grain boundaries, the underlying atomistic pathways for this “Imperfect OA” process remain the subject of debate. In this paper, molecular dynamics and in situ TEM were used to probe the crystallographic evolution of up to 30 gold and copper nanoparticles during aggregation. It was found that Imperfect OA occurs because (1) grain boundaries become quantized when their size is comparable to the separation between constituent dislocations and (2) kinetic barriers associated with the glide of grain boundary dislocations are small. In support of these findings, TEM experiments show the formation of a single crystal aggregate after annealing 9 initially misoriented, agglomerated particles with evidence of dislocation slip and twin formation during particle/grain alignment. These observations motivate future work on assembled nanocrystals with tailored defects and call for a revision of Read-Shockley models for grain boundary energies in nanocrystalline materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Troilite formation kinetics and growth mechanism in the solar nebula

Troilite formation via the reaction Fe(s) + H2S(g) + H2(g) is the major mechanism for S retention in grains in the solar nebula. Thermodynamic calculations predict that troilite condenses from a solar composition gas. We present experimental results on the kinetics and growth of troilite crystals on Fe metal at temperature (450-650 C) and composition (50-1000 ppm H2S in H2) conditions similar to those in the solar nebula. The fraction of Fe reacted (based on gravimetric data) is plotted at 450, 505, 575, and 650 C. The thickness change of unreacted iron (measured by optical microscopy) is plotted at 575 and 650 C vs. time. the weight change per unit area varies as the square root of time at the lower temperatures and varies linearly with time at the highest temperature. The growth behavior along the lower isotherms is due to diffusion. This behavior suggests sulfide diffusion to the metal-sulfide interface and suggests Fe(2+) diffusion to the sulfide-gas interface. The reaction along the highest isotherm appears to be interface controlled. The formation of troilite crystals is a rapid process forming measurable layers in a few hours. The crystalgrowth is complicated. Initially there are intergrowths of troilite into the pure Fe metal. As the reaction progresses two distinct layers of troilite crystals form. One is in contact with the Fe metal and consists of small randomly oriented crystals with pore space between them. The outermost layer contains large crystals that are all oriented in the same direction. The intergrowth layer is much smaller at 650 C than at 575 C. This suggest that FeS nucleation is inhibited at the higher temperature, accounting for the initially slower reaction rate. Once nucleated, the reaction kinetics are apparently controlled by the growth of the crystals at the interface.

Lauretta, D. S.↗

Predicting microstructurally sensitive fatigue‐crack path in WE43 magnesium using high‐fidelity numerical modeling and three‐dimensional experimental characterization

Abstract Microstructurally small fatigue‐crack growth in polycrystalline materials is highly three‐dimensional due to sensitivity to local microstructural features (e.g., grains). One requirement for modeling microstructurally sensitive crack propagation is establishing the criteria that govern crack evolution, including crack deflection. Here, a high‐fidelity finite‐element modeling framework is used to assess the performance and validity of various crack‐growth criteria, including slip‐based metrics (e.g., fatigue‐indicator parameters), as potential criteria for predicting three‐dimensional crack paths in polycrystalline materials. The modeling framework represents cracks as geometrically explicit discontinuities and involves voxel‐based remeshing, mesh‐gradation control, and a crystal‐plasticity constitutive model. The predictions are compared to experimental measurements of WE43 magnesium samples subject to fatigue loading, for which three‐dimensional grain structures and fatigue‐crack surfaces were measured post‐mortem using near‐field high‐energy x‐ray diffraction microscopy and x‐ray computed tomography. Findings from this work are expected to improve the predictive capabilities of simulations involving microstructurally small fatigue‐crack growth in polycrystalline materials.

Engineering↗

An Electron Backscatter Diffraction Analysis of Grain Boundary Initiated Discontinuous Precipitation in U-10Mo

The effect of varied thermomechanical processing on discontinuous precipitation (DP) in U-10Mo was investigated, with specific emphasis on understanding the role of grain boundary misorientation in DP. Varied prior homogenization heat treatment and thermomechanical processing resulted in differences in both the fraction of DP and the colony width, and was attributed to variations in the grain boundary misorientation distribution. Regardless of the degree of DP-based transformation, extensive growth of DP colonies was dominant on 30°–45° misorientation boundaries. Interestingly, misorientation histograms of the deformed and annealed specimens suggest the processing steps involved may have inhibited DP colony growth along a small fraction of these high angle boundaries. Large-area electron backscatter diffraction montages coupled with high resolution mapping suggest symmetric {110}-type interfaces may be important considerations for mitigating extensive DP growth in this alloy system.

Discontinuous Precipitation, Uranium, Electron Bac↗

Recrystallization of A Shot Peened Single Crystal Nickel-Base Superalloy

Single crystal nickel-base superalloys used as turbine engine airfoils can have much higher creep and thermal fatigue resistance required for blades and vanes than polycrystalline superalloys due to the absence of weak grain boundaries, as well as the low elastic modulus in the [001] single crystal growth direction (Refs. 1 and 2). This has allowed an increase in the turbine rim inlet temperatures for improved performance and efficiency. However, these advantages in performance require constraints on acceptable levels of single crystal defects, such as macroscopic grain boundaries at low angles to the primary grain (i.e., low angle boundaries or LAB), higher angle boundaries, small new grains nucleated at the blade surface (a.k.a. freckles), larger new grains, and also the single crystal blades’ orientation, typically degrees off of the [001] direction and the orientation of a transverse [010] direction with respect to blade geometry. Therefore, single crystal turbine airfoils, which are frequently used with as-cast surfaces, are grain etched and inspected before and after heat treatments to ensure these aspects conform to acceptability limits.

single crystal↗

A once-molten, coarse-grained, Ca-rich inclusion in Allende

A compact, spheroidal Type B inclusion in Allende contains melilite laths that project radially inward from the inclusion edge which show interference growth textures. The combined textural and chemical features of this object cannot be explained by independent vapor-solid condensation of grains in space, followed by random aggregation of these grains into an inclusion. Instead, it probably formed from a once-molten droplet that crystallized in response to radiative cooling from its outer surface. The crystallization sequence in this and another similar inclusion in which oxygen isotopes have been measured is melilite-spinel-anorthite-fassaite; this sequence shows that oxygen isotopic heterogeneities in coarse-grained inclusions were formed after complete solidification of these objects by partial exchange with a less O-16-rich gas, and not during or before a melting event.

Macpherson, G. J.↗