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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.

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At least 685 records · Page 38
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Structure and Properties of VT6 Alloy Obtained by Layered Selective Sintering of a Powder

This paper is focused on a clarification and analysis of the regularities of formation of the structure and properties of samples of the titanium-based alloy VT6, obtained by methods of conventional metallurgy and formed by layered selective electron-beam sintering in vacuum (using the Arcam A2X (3D printer) system (Arcam, Sweden)) of VT6 titanium powder with particle size 40–100 μm. Additional modification of the samples was realized by irradiating the surface with an intense pulsed electron beam (15 keV, 45 J/cm{sup 2}, 200 μs, 10 pulses, 0.3 s{sup –1}, 3.5·10{sup –2} Pa). It is shown that the action of a pulsed electron beam on the surface of samples formed by layered selective electron-beam sintering leads to a significant reduction in the porosity of the surface layer of the material and formation in the surface layer of a polycrystalline structure (grain size 15–60 μm) with a substructure in the form of crystallization cells (cell size 0.5–1.2 μm). Electron-beam processing of samples prepared by methods of conventional metallurgy for the indicated electron-beam parameters leads to the formation in the surface layer of a polycrystalline structure (grain size 50–800 μm) with a laminar intragrain substructure. Mechanical tests, performed by stretching flat samples, showed that the highest combination of mechanical strength and plasticity is possessed by samples obtained by layered selective electron-beam sintering with subsequent irradiation by an intense pulsed electron beam.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Structural and Phase Transformations in Superlocalization Band in Ni{sub 3}Ge Single Crystal

The paper studies the high-temperature plastic deformation in Ni{sub 3}Ge alloy single crystals localizing in a band a few tens of microns wide that reaches the shear strain of thousands of percent. The electron backscatter diffraction and synchrotron radiation techniques allow investigating the structure of the single crystal in the band of super-localized plastic deformation. It is shown that super-localization of plastic deformation occurs due to the formation of polycrystalline multi-level substructure in the initial single crystal. The grain size and grain misorientation bimodal distributions are determined in the polycrystalline substructure. Also, regions of amorphous state are observed in the super-localization band at high homologous temperature Т > 0.5T{sub m}. A partial destruction of the far atomic order is detected.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

High-Temperature Properties and Microstructural Stability of the AISI H13 Hot-Work Tool Steel Processed by Selective Laser Melting

The microstructural stabilities, softening resistance, and high-temperature tensile properties of the H13 hot-work tool steel by selective laser melting (SLM) were systematically studied. A series of tempering procedures were performed on the as-SLMed specimens. Afterwards, the mechanism of softening resistance behavior was discussed based on the XRD, SEM, EBSD observations, hardness measurements, and high-temperature tensile tests. It was found that the as-SLMed H13 consisted of α-iron and γ-iron. The carbide-stabilizing elements aggregated as the cell-like substructures for the rapid solidification of the SLM process. After the softening resistance treatment, the retained austenite transformed to ferrite and carbide mixtures. The cell-like substructures dissolved slowly into the matrix when the temperature was below 550 °C. These factors increased the hardness and retarded the softening of the material. When the temperature was 600 °C, the microstructural constituents transformed to soft ferrite and globular carbides, which lead to a considerable decrease of the hardness. Due to the grain refinement, solid solution strengthening, and residual stress, the as-SLMed H13 exhibited better mechanical properties than that of the wrought counterparts.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Micromechanism of High-Temperature Tensile Deformation Behavior of a Directionally Solidified Nickel Base Superalloy

High-temperature tensile deformation behavior of directionally solidified nickel base superalloy CM 247 DS is studied by conducting tensile tests in temperature range RT-955 °C employing a constant strain rate of 10{sup −3} s{sup −1} and carrying out extensive electron microscopic examinations to understand the concomitant substructural evolution. The alloy exhibits yield strength anomaly (YSA) behavior like many other superalloys, and the yield strength maxima occur at 750 °C. However, unlike in most of the superalloys, ductility continuously increases with temperature. The deformation behavior of the alloy changes significantly with temperature. Transmission electron microscopic examination confirmed that at lower temperature (≤ 750 °C), γ′ shearing is the dominant deformation mechanism; whereas at temperatures above 750 °C, thermally activated dislocation looping around γ′ precipitate is dominant. Substructures evolved during deformation at 750 °C consists mainly of superlattice stacking faults (SSFs) inside γ′ precipitates, whereas at 850 °C uniform dislocation tangles are observed in γ matrix. Superlattice stacking faults result from shearing of γ′ precipitate by a/3〈112〉 dislocations, which arise from the decomposition of a/2〈110〉 matrix dislocations. YSA in this alloy is attributed to dislocation interactions inside γ′; however, the enhanced ductility even at 750 °C is due to formation of SSFs.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Whipple Bumper Shield Tests at Over 10 KM/S [Book Chapter]

A series of experiments has been performed on the Sandia HyperVelocity Launcher (HVL) to evaluate the effectiveness of a thin Whipple bumper shield at impact velocities up to 10.5 km/s by orbital space debris. Upon impact by an 0.67gm (0.87 mm thick) flier plate the thin aluminum bumper shield completely disintegrates into a debris cloud. The debris cloud front propagates axially at velocities in excess of 14 km/s and expands radially at a velocity of ~ 7 km/s. Subsequent loading on a 3.2 mm thick aluminum substructure by the debris cloud penetrates the substructure completely.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Dislocation decorrelation and relationship to deformation microtwins during creep of a y' precipitate strengthened Ni-based superalloy

The evolution of microtwins during high temperature creep deformation in a strengthened Ni-base superalloy has been investigated through a combination of creep testing, TEM characterization, theoretical modeling and computer simulation. Experimentally, microtwin nucleation sources were identified and their evolution was tracked by characterizing the deformation substructure at different stages of the creep deformation. Initially, deformation is highly localized around stress concentrators such as carbides, borides and serrated grain boundaries, which act as sources of a/2<110> matrix type dislocations. Due to microstructural effects such as fine channels between particles and low matrix stacking fault energies, the a/2<110> matrix dislocations dissociate into a/6<112> Shockley partials, which were commonly observed to be decorrelated from one another, creating extended intrinsic stacking faults in the matrix. As deformation progress further, microtwins form via partial dislocations cooperatively shearing both and phases on adjacent {111} glide planes. The TEM observations lead directly to an analysis of dislocation-precipitate interactions. Through phase field simulations and theoretical analysis based on Orowan looping, the important processes of dislocation dissociation and decorrelation are modeled in detail, providing comprehensive insight into the microstructural features and applied stress conditions that favor the microtwinning deformation mode in strengthened Ni-based superalloys.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Selective laser melting of 304L stainless steel: Role of volumetric energy density on the microstructure, texture and mechanical properties

The role of volumetric energy density on the microstructural evolution, texture and mechanical properties of 304L stainless steel parts additively manufactured via selective laser melting process is investigated. 304L is chosen because it is a potential candidate to be used as a matrix in a metal matrix composite with nanoparticles dispersion for energy and high temperature applications. The highest relative density of 99 %±0.5 was achieved using a volumetric energy density of 1400 J/mm 3 . Both XRD analysis and Scheil simulation revealed the presence of a small trace of the delta ferrite phase, due to rapid solidification within the austenitic matrix of 304L. Here, a fine cellular substructure ranged between 0.4–1.8 μm, was detected across different energy density values. At the highest energy density value, a strong texture in the direction of [100] was identified. At lower energy density values, multicomponent texture was found due to high nucleation rate and the existing defects. Yield strength, ultimate tensile strength, and microhardness of samples with a relative density of 99 % were measured to be 540 ± 15 MPa, 660 ± 20 MPa and 254 ± 7 HV, respectively and higher than mechanical properties of conventionally manufactured 304L stainless steel. Heat treatment of the laser melted 304L at 1200 °C for 2 h, resulted in the nucleation of recrystallized equiaxed grains followed by a decrease in microhardness value from 233 ± 3 HV to 208 ± 8 HV due to disappearance of cellular substructure.

304L stainless steel↗
DOE OSTI2014

Simulation of Thermal Stratification in BWR Suppression Pools with One Dimensional Modeling Method

The suppression pool in a boiling water reactor (BWR) plant not only is the major heat sink within the containment system, but also provides the major emergency cooling water for the reactor core. In several accident scenarios, such as a loss-of-coolant accident and extended station blackout, thermal stratification tends to form in the pool after the initial rapid venting stage. Accurately predicting the pool stratification phenomenon is important because it affects the peak containment pressure; the pool temperature distribution also affects the NPSHa (available net positive suction head) and therefore the performance of the Emergency Core Cooling System and Reactor Core Isolation Cooling System pumps that draw cooling water back to the core. Current safety analysis codes use zero dimensional (0-D) lumped parameter models to calculate the energy and mass balance in the pool; therefore, they have large uncertainties in the prediction of scenarios in which stratification and mixing are important. While three-dimensional (3-D) computational fluid dynamics (CFD) methods can be used to analyze realistic 3-D configurations, these methods normally require very fine grid resolution to resolve thin substructures such as jets and wall boundaries, resulting in a long simulation time. For mixing in stably stratified large enclosures, the BMIX++ code (Berkeley mechanistic MIXing code in C++) has been developed to implement a highly efficient analysis method for stratification where the ambient fluid volume is represented by one-dimensional (1-D) transient partial differential equations and substructures (such as free or wall jets) are modeled with 1-D integral models. This allows very large reductions in computational effort compared to multi-dimensional CFD modeling. One heat-up experiment performed at the Finland POOLEX facility, which was designed to study phenomena relevant to Nordic design BWR suppression pool including thermal stratification and mixing, is used for validation. Comparisons between the BMIX++, GOTHIC, and CFD calculations against the POOLEX experimental data are discussed in detail.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2016

Comparative study of lignin characteristics from wheat straw obtained by soda-AQ and kraft pretreatment and effect on the following enzymatic hydrolysis process

With this study, to understand the structural changes of lignin after soda-AQ and kraft pretreatment, milled straw lignin, black liquor lignin and residual lignin extracted from wheat straw were characterized by FT-IR, UV, GPC and NMR. The results showed that the main lignin linkages were β-aryl ether substructures (β-O-4'), followed by phenylcoumaran (β-5') and resinol (β-β') substructures, while minor content of spirodienone (β-1'), dibenzodioxocin (5-5') and α,β-diaryl ether linkages were detected as well. After pretreatment, most lignin inter-units and lignin-carbohydrate complex (LCC) linkages were degraded and dissolved in black liquor, with minor amount left in residual pretreated biomass. In addition, through quantitative 13 C and 2D-HSQC NMR spectral analysis, lignin and LCC were found to be more degraded after kraft pretreatment than soda-AQ pretreatment. Furthermore, the subsequent enzymatic hydrolysis results showed that more cellulose in wheat straw was converted to glucose after kraft pretreatment, indicating that LCC linkages were important in the enzymatic hydrolysis process.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Phonons reveal coupled cholesterol-lipid dynamics in ternary membranes

Experimental studies of collective dynamics in lipid bilayers have been challenging due to the energy resolution required to observe these low-energy phonon-like modes. However, inelastic X-ray scattering (IXS) measurements — a technique for probing vibrations in soft and biological materials — are now possible with sub-meV resolution, permitting direct observation of low energy, phonon-like modes in lipid membranes. Here, in this study, IXS measurements with sub-meV energy resolution reveal a low-energy optic-like phonon mode at roughly 3 meV in the liquid-ordered (L o ) and liquid-disordered (L d ) phases of a ternary lipid mixture. This mode is only observed experimentally at momentum transfers greater than 5 nm -1 in the L o system. A similar gapped mode is also observed in all-atom molecular dynamics (MD) simulations of the same mixture, indicating that the simulations accurately represnt the fast, collective dynamics in the L o phase. It’s optical nature and the Q range of the gap together suggest that the observed mode is due to the coupled motion of cholesterol-lipid pairs, separated by several hydrocarbon chains within the membrane plane. Analysis of the simulations provide molecular insight into the origin of the mode in transient, nanoscale substructures of hexagonally packed hydrocarbon chains. This nanoscale hexagonal packing was previously reported based on molecular dynamics simulations and later by NMR measurements. Here, however, the integration of IXS and MD simulations identifies a new signature of the L o substructure in the collective lipid dynamics, thanks to the recent confluence of IXS sensitivity and MD simulation capabilities.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Discovery of multi-functional polyimides through high-throughput screening using explainable machine learning

Polyimides have been widely used in modern industries because of their excellent mechanical and thermal properties, e.g., high-temperature fuel cells, displays, and aerospace composites. However, it usually takes decades of experimental efforts to develop a successful product. Aiming to expedite the discovery of high-performance polyimides, we utilize computational methods of machine learning (ML) and molecular dynamics (MD) simulations. Our study provides compelling evidence for the effectiveness of a data-driven approach in discovering novel polyimides. We first build a comprehensive library of more than 8 million hypothetical polyimides based on the polycondensation of existing dianhydride and diamine/diisocyanate molecules. Then we establish multiple ML models for the thermal and mechanical properties of polyimides based on their experimentally reported values, including glass transition temperature, Young’s modulus, and tensile yield strength. The obtained ML models demonstrate excellent predictive performance in identifying the key chemical substructures influencing the thermal and mechanical properties of polyimides. The use of explainable machine learning describes the effect of chemical substructures on individual properties, from which human experts can understand the cause of the ML model decision. Applying the well-trained ML models, we obtain property predictions of the 8 million hypothetical polyimides. Then, we screen the whole hypothetical dataset and identify three (3) best-performing novel polyimides that have better-combined properties than existing ones through Pareto frontier analysis. For an easy query of the discovered high-performing polyimides, we also create an online platform https://polyimide-explorer.herokuapp.com/ that embeds the developed ML model with interactive visualization. Furthermore, we validate the ML predictions through all-atom MD simulations and examine their synthesizability. The MD simulations are in good agreement with the ML predictions and the three novel polyimides are predicted to be easy to synthesize via Schuffenhauer’s synthetic accessibility score. Following the proposed ML guidance, we successfully synthesized a novel polyimide and the experimentally obtained high glass transition/thermal decomposition temperature demonstrated its excellent thermal stability. Here our study demonstrates an efficient way to expedite the discovery of novel polymers using ML prediction and MD validation. The high-throughput screening of a large computational dataset can serve as a general approach for new material discovery in other polymeric material exploration problems, such as organic photovoltaics, polymer membranes, and dielectrics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

A parallel discrete dislocation dynamics/kinetic Monte Carlo method to study non-conservative plastic processes

Non-conservative processes play a fundamental role in plasticity and are behind important macroscopic phenomena such as creep, dynamic strain aging, loop raft formation, etc. In the most general case, vacancy-induced dislocation climb is the operating unit mechanism. While dislocation/vacancy interactions have been modeled in the literature using a variety of methods, the approaches developed rely on continuum descriptions of both the vacancy population and its fluxes. However, there are numerous situations in physics where point defect populations display heterogeneous concentrations and/or non-smooth kinetics. Here, a kinetic Monte Carlo (kMC) approach for modeling vacancy transport in response to arbitrary stress fields is used. Vacancies are treated as point particles and are coupled to the dislocation substructure representing a deformed material via an advection term defined by the local stress gradients. The stress fields and the dislocation substructure are evolved using a discrete dislocation dynamics (DDD) module. To extend the coupled model to the treatment of large systems, we have implemented it in the massively-parallel DDD code ParaDiS. To avoid numerical incompatibilities associated with merging deterministic (DDD) and stochastic (kMC) integration algorithms, we cast the entire elasto-plastic-diffusive problem within a single stochastic framework, taking advantage of a parallel kMC algorithm to evolve the system as a single event-driven process. The large-scale implementation enables the study of the evolution of a variety of dislocation-defect scenarios governed by non-conservative transport kinetics. After carrying out an exhaustive numerical and computational analysis of our parallel algorithm, we show results that emphasize situations where inhomogeneous vacancy dynamics are of relevance, and compare discrete kinetics to continuum solutions for several cases.

36 MATERIALS SCIENCE↗
DOE OSTI2019

High-throughput screening and chemotype-enrichment analysis of ToxCast phase II chemicals evaluated for human sodium-iodide symporter (NIS) inhibition

In support of the Endocrine Disruptor Screening Program (EDSP), the U.S.EPA's Office of Research and Development (ORD) is developing high-throughput screening (HTS) approaches to identify chemicals that alter target sites in the thyroid hormone (TH) pathway. The sodium iodide symporter (NIS) is a transmembrane glycoprotein that mediates iodide uptake into the thyroid as the initial step of TH biosynthesis. Previously, we screened 293 ToxCast chemicals (ph1v2) using a HEK293T cell line expressing human NIS in parallel radioactive iodide uptake (RAIU) and cell viability assays to identify potential environmental NIS inhibitors. Here, we expanded NIS inhibitor screening for a set of 768 ToxCast Phase II (ph2) chemicals, and applied a novel computational toxicology approach based on the ToxPrint chemotype to identify chemical substructures associated with NIS inhibition. Following single-concentration screening (at 1 × 10 -4 M with a 20% inhibition cutoff), 235 samples (228 chemicals) were further tested in multipleconcentration (1 × 10 -9 - 1 × 10 -4 M) format in both RAIU and cell viability assays. The 167 chemicals that exhibited significant RAIU inhibition were then prioritized using combined RAIU and cell viability responses that were normalized relative to the known NIS inhibitor sodium perchlorate. Some of the highest ranked chemicals, such as PFOS, tributyltin chloride, and triclocarban, have been previously reported to be thyroid disruptors. In addition, several novel chemicals were identified as potent NIS inhibitors. The present results were combined with the previous ph1v2 screening results to produce two sets of binary hit-calls for 1028 unique chemicals, consisting of 273 positives exhibiting significant RAIU inhibition, and 63 positives following application of a cell viability filter. A ToxPrint chemotype-enrichment analysis identified > 20 distinct chemical substructural features, represented in > 60% of the active chemicals, as significantly enriched in each NIS inhibition hit-call space. A shared set of 9 chemotypes enriched in both hit-call sets indicates stable chemotype signals (insensitive to cytotoxicity filters) that can help guide structure-activity relationship (SAR) investigations and inform future research.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

Concomitant Imaging Dose and Cancer Risk in Image Guided Thoracic Radiation Therapy

Purpose: Kilovoltage cone beam computed tomography (CT) (kVCBCT) imaging guidance improves the accuracy of radiation therapy but imposes an extra radiation dose to cancer patients. This study aimed to investigate concomitant imaging dose and associated cancer risk in image guided thoracic radiation therapy. Methods and Materials: The planning CT images and structure sets of 72 patients were converted to CT phantoms whose chest circumferences (C{sub chest}) were calculated retrospectively. A low-dose thorax protocol on a Varian kVCBCT scanner was simulated by a validated Monte Carlo code. Computed doses to organs and cardiac substructures (for 5 selected patients of various dimensions) were regressed as empirical functions of C{sub chest}, and associated cancer risk was calculated using the published models. The exposures to nonthoracic organs in children were also investigated. Results: The structural mean doses decreased monotonically with increasing C{sub chest}. For all 72 patients, the median doses to the heart, spinal cord, breasts, lungs, and involved chest were 1.68, 1.33, 1.64, 1.62, and 1.58 cGy/scan, respectively. Nonthoracic organs in children received 0.6 to 2.8 cGy/scan if they were directly irradiated. The mean doses to the descending aorta (1.43 ± 0.68 cGy), left atrium (1.55 ± 0.75 cGy), left ventricle (1.68 ± 0.81 cGy), and right ventricle (1.85 ± 0.84 cGy) were significantly different (P<.05) from the heart mean dose (1.73 ± 0.82 cGy). The blade shielding alleviated the exposure to nonthoracic organs in children by an order of magnitude. Conclusions: As functions of patient size, a series of models for personalized estimation of kVCBCT doses to thoracic organs and cardiac substructures have been proposed. Pediatric patients received much higher doses than did the adults, and some nonthoracic organs could be irradiated unexpectedly by the default scanning protocol. Increased cancer risks and disease adverse events in the thorax were strongly related to higher imaging doses and smaller chest dimensions.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2017

A dislocation-based crystal plasticity framework for dynamic ductile failure of single crystals

We developed a framework for dislocation-based viscoplasticity and dynamic ductile failure to model high strain rate deformation and damage in single crystals. The rate-dependence of the crystal plasticity formulation is based on the physics of relativistic dislocation kinetics suited for extremely high strain rates. The damage evolution is based on the dynamics of void growth, which are governed by both micro-inertia as well as dislocation kinetics and dislocation substructure evolution. Furthermore, an averaging scheme is proposed in order to approximate the evolution of the dislocation substructure in both the macroscale as well as its spatial distribution at the microscale. In addition, a concept of a single equivalent dislocation density that effectively captures the collective influence of dislocation density on all active slip systems is proposed here. Together, these concepts and approximations enable the use of semi-analytic solutions for void growth dynamics developed in [J. Wilkerson and K. Ramesh. A dynamic void growth model governed by dislocation kinetics. J. Mech. Phys. Solids, 70:262–280, 2014.], which greatly reduce the computational overhead that would otherwise be required. The resulting homogenized framework has been implemented into a commercially available finite element package, and a validation study against a suite of direct numerical simulations was carried out.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Reactive gas atomization processing for Fe-based ODS alloys

Gas atomization reaction synthesis was employed as a simplified method for processing oxide dispersion forming precursor Fe-based powders (e.g., Fe–Cr–Y–Hf). During this process a reactive atomization gas (i.e., Ar–O2) was used to oxidize the powder surfaces during primary break-up and rapid solidification of the molten alloy. This resulted in envelopment of the powders by an ultra-thin (t < 50 nm) metastable Cr-enriched oxide shell that was used as a vehicle to transport oxygen into the consolidated microstructure. Subsequent elevated temperature heat treatment promoted thermodynamically driven oxygen exchange reactions between trapped films of Cr-enriched oxide and internal (Y, Hf)-enriched intermetallic precipitates, resulting in highly stable nano-metric mixed oxide dispersoids (i.e., Y–Hf–O) that were identified with X-ray diffraction. Transmission electron microscopy and atom probe tomography results also revealed that the size and distribution of the dispersoids were found to depend strongly on the original rapidly solidified microstructure. To exploit this, several oxide dispersion strengthened microstructures were engineered from different powder particle size ranges, illustrating microstructural control as a function of particle solidification rate. Additionally, preliminary thermal–mechanical processing was used to develop a fine scale dislocation substructure for ultimate strengthening of the alloy.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Uranyl carboxyphosphonates that incorporate Cd(II)

The hydrothermal treatment of UO{sub 3}, Cd(CH{sub 3}CO{sub 2}){sub 2}.2H{sub 2}O, and triethyl phosphonoacetate results in the formation of Cd{sub 2}[(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 3}O{sub 3}(OH)(H{sub 2}O){sub 2}].16H{sub 2}O (CdUPAA-1), [Cd{sub 3}(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 6}(H{sub 2}O){sub 13}].6H{sub 2}O (CdUPAA-2), and Cd(H{sub 2}O){sub 2}[(UO{sub 2})(PO{sub 3}CH{sub 2}CO{sub 2})(H{sub 2}O)]{sub 2} (CdUPAA-3). CdUPAA-1 adopts a cubic three-dimensional structure constructed from planar uranyl oxide clusters containing both UO{sub 7} pentagonal bipyramids and UO{sub 8} hexagonal bipyramids that are linked by Cd(II) cations and phosphonoacetate to yield large cavities approximately 16 A across that are filled with disordered water molecules. CdUPAA-2 forms a rhombohedral three-dimensional channel structure that is assembled from UO{sub 7} pentagonal bipyramids that are bridged by phosphonoacetate. CdUPAA-3 is layered with the hydrated Cd(II) cations incorporated directly into the layers linking one-dimensional uranyl phosphonate substructures together. In this structure, there are complex networks of hydrogen bonds that exist within the sheets, and also stitch the sheets together. -- Graphical abstract: A view of part of the cubic structure of Cd{sub 2}[(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 3}O{sub 3}(OH)(H{sub 2}O){sub 2}].16H{sub 2}O. Display Omitted highlights: > High symmetry uranyl compounds. > Three-dimensional structures. > Porous materials. > Heterobimetallic compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Pronounced matrix effect in YbMo{sub 2}Al{sub 4}-type Ca(Au{sub x}Zn{sub 2−x})Au{sub 4} (x=0.09–0.89)

Electron-poor polar intermetallics Ca(Au{sub x}Zn{sub 2−x})Au{sub 4} have been synthesized through fusion of stoichiometric metals in sealed tantalum tubes at 800 °C and annealing at 400 °C for one week. Single crystal X-ray diffraction analyses reveal that this phase belongs to the YbMo{sub 2}Al{sub 4}-type structure (I4/mmm, Pearson symbol tI14), a≈6.943–7.017 Å, c≈5.278–5.286 Å, Z=2, with homogeneous composition range of x=0.09(1)–0.89(1). The structure exhibits a three-dimensional framework of (Au{sub 8}){sub 1/2} featuring square and octagonal channels extending in c, in which Ca and the infinite linear chains of [(Au,Zn){sub 2}]{sub 1/2} are located, respectively. Mulliken population analyses demonstrate that Zn prefers to form the linear chains in the whole homogeneous composition range, consistent with experimental observations. Crystal orbital Hamilton population (COHP) analyses reveal that the channel-to-chain Au–Zn contact has strong bonding interactions regardless of its large interatomic distance (∼2.85 Å), a signature of pronounced matrix effect. The last mentioned effect in YbMo{sub 2}Al{sub 4}-type structures is expected in case the linear chains are defined by small size atoms. - Graphical abstract: Pronounced matrix effect incurred by Au–Au bonding within the gold substructure in Ca(Au{sub x}Zn{sub 2−x})Au{sub 4} results in an elongation of the channel-to-chain Au–Zn interatomic distance without weakening bonding interactions. - Highlights: • The complete solid solution of Ca(Au{sub x}Zn{sub 2−x})Au{sub 4} was accomplished. • Site preference was explained by “coloring” analyses. • Abnormally large Au–Zn distance but with strong bonding was observed. • Pronounced matrix effect incurred by Au–Au bonding in gold substructure was found.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗