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At least 1,765 records · Page 98

Influence of slag chemistry on the hydration of alkali-activated blast-furnace slag - Part II: Effect of Al{sub 2}O{sub 3}

The hydration and microstructural evolution of three alkali activated slags (AAS) with Al{sub 2}O{sub 3} contents between 7 and 17% wt.% have been investigated. The slags were hydrated in the presence of two different alkaline activators, NaOH and Na{sub 2}SiO{sub 3}{center_dot}5H{sub 2}O. The formation of C(-A)-S-H and hydrotalcite was observed in all samples by X-ray diffraction, thermal analysis and scanning electron microscopy. Higher Al{sub 2}O{sub 3} content of the slag decreased the Mg/Al ratio of hydrotalcite, increased the Al incorporation in the C(-A)-S-H and led to the formation of straetlingite. Increasing Al{sub 2}O{sub 3} content of the slag slowed down the early hydration and a lower compressive strength during the first days was observed. At 28 days and longer, no significant effects of slag Al{sub 2}O{sub 3} content on the degree of hydration, the volume of the hydrates, the coarse porosity or on the compressive strengths were observed.

36 MATERIALS SCIENCE↗

An in situ transmission electron microscopy study of the ion irradiation induced amorphisation of silicon by He and Xe

We used transmission electron microscopy with in situ ion irradiation to examine the ion-beam-induced amorphisation of crystalline silicon under irradiation with light (He) and heavy (Xe) ions at room temperature. Analysis of the electron diffraction data reveal the heterogeneous amorphisation mechanism to be dominant in both cases. Moreover, for the differences in the amorphisation curves are discussed in terms of intra-cascade dynamic recovery, and the role of electronic and nuclear loss mechanisms.

36 MATERIALS SCIENCE↗

One-Step Synthesis of Zeolite Membranes Containing Catalytic Metal Nanoclusters

Metal-loaded zeolitic membranes are promising candidates as catalytic membrane reactors. We report a one-step synthesis method to synthesize zeolite membranes containing metal nanoclusters, that has advantages in comparison to multistep methods such as impregnation and ion exchange. Pure-silica MFI zeolite-Pt hybrid membranes were prepared by hydrothermal synthesis with addition of 3-mercaptopropyl-trimethoxysilane (MPS) and a platinum precursor. Composition analysis and mapping by energy-dispersive X-ray spectroscopy (EDX) reveal that Pt ions/clusters are uniformly distributed along the membrane cross-section. High-magnification scanning transmission electron microscopy (STEM) analysis shows that Pt metal clusters in the hybrid zeolite membrane have a diameter distribution in the range of 0.5–2.0 nm. In contrast, a pure-silica MFI membrane synthesized from an MPS-free solution shows negligible incorporation of Pt metal clusters. To characterize the properties of the hybrid (zeolite/metal) membrane, it was used as a catalytic membrane reactor (CMR) for high-temperature propane dehydrogenation (PDH) at 600 °C and 1 atm. The results indicate that Pt metal clusters formed within the MFI zeolite membrane can serve as effective catalysts for high-temperature PDH reaction along with H 2 removal via membrane permeation, thereby increasing both conversion and selectivity in relation to a conventional membrane reactor containing an equivalent amount of packed Pt catalyst in contact with an MFI membrane. In conclusion, the hybrid zeolite-Pt CMR also showed stable conversion and selectivity upon extended high-temperature operation (12 h), indicating that encapsulation in the zeolite allowed thermal stabilization of the Pt nanoclusters and reduced catalyst deactivation.

36 MATERIALS SCIENCE↗

Orbitals for Analyzing Bonding and Magnetism of Heavy-Metal Complexes

Electron orbitals are ubiquitous in chemistry for the description of bonding and molecular properties. Furthermore, this article outlines a theoretical framework for the generation and application of orbitals for the analysis of the electronic structure, chemical bonding, and magnetic properties of metal complexes from relativistic quantum chemical wavefunction calculations. Examples from the author’s research of f-element complexes are used to illustrate these concepts, with emphasis on open-shell systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lunar deep drill apparatus

Proposed as a baseline configuration, this rotary drill apparatus is designed to produce 100-mm diameter holes in the lunar surface at depths up to 50 meters. The drill is intended to acquire samples for scientific analysis, mineral resource location, calibration of electronic exploration devices, and foundation analysis at construction sites. It is also intended to prepare holes for emplacement of scientific instruments, the setting of structural anchors, and explosive methods in excavation and mining activities. Defined as a deep drill because of the modular drill string, it incorporates an automatic rod changer. The apparatus is teleoperated from a remote location, such as earth, utilizing supervisory control techniques. It is thus suitable for unmanned and man-tended operation. Proven terrestrial drilling technology is used to the extent it is compatible with the lunar environment. Augers and drive tubes form holes in the regolith and may be used to acquire loose samples. An inertial cutting removal system operates intermittently while rock core drilling is in progress. The apparatus is carried to the work site by a three-legged mobile platform which also provides a 2-meter feed along the hole centerline, an off-hole movement of approximately .5 meters, an angular alignment of up to 20 deg. from gravity vertical, and other dexterity required in handling rods and samples. The technology can also be applied using other carriers which incorporate similar motion capabilities. The apparatus also includes storage racks for augers, rods, and ancillary devices such as the foot-plate that holds the down-hole tooling during rod changing operations.

Source record↗

Quantum criticality in Ce 1 - x Sm x Co In 5

Motivated by the possibility of observing the coexistence between magnetism and unconventional superconductivity in heavy-fermion Ce 1-x Sm x CoIn 5 alloys, we studied how the samarium substitution on the cerium site affects the magnetic field-tuned-quantum criticality of stoichiometric CeCoIn 5 by performing specific heat and resistivity measurements. By applying an external magnetic field, we have observed Fermi-liquid to non-Fermi-liquid crossovers in the temperature dependence of the electronic specific heat normalized by temperature and of the resistivity. We obtained the magnetic-field-induced quantum critical point (QCP) by extrapolating to zero temperature the temperature-magnetic field dependence at which the crossovers take place. Furthermore, a scaling analysis of the electronic specific heat is used to confirm the existence of the QCP. We have found that the magnitude of the magnetic-field-induced QCP decreases with increasing samarium concentration. Our analysis of heat capacity and resistivity data reveals a zero-field QCP for x cr ≈0.15, which falls inside the region where Sm ions antiferromagnetism and superconductivity coexist.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Molybdenum Disilicide Oxidation Kinetics in High Temperature Steam

The Fuel Cycle Research and Development program’s Advanced Fuels Campaign is currently supporting a range of experimental efforts aimed at the development and qualification of ‘accident tolerant’ nuclear fuel forms. One route to enhance the accident tolerance of nuclear fuel is to replace the zirconium alloy cladding, which is prone to rapid oxidation in steam at elevated temperatures, with a more oxidation-resistant cladding. Several cladding replacement solutions have been envisaged. The cladding can be completely replaced with a more oxidation resistant alloy, a layered approach can be used to optimize the strength, creep resistance, and oxidation tolerance of various materials, or the existing zirconium alloy cladding can be coated with a more oxidation-resistant material. Molybdenum is one candidate cladding material favored due to its high temperature creep resistance. However, it performs poorly under autoclave testing and suffers degradation under high temperature steam oxidation exposure. Development of composite cladding architectures consisting of a molybdenum core shielded by a molybdenum disilicide (MoSi 2 ) coating is hypothesized to improve the performance of a Mo-based cladding system. MoSi 2 was identified based on its high temperature oxidation resistance in O 2 atmospheres (e.g. air and “wet air”). However, its behavior in H 2 O is less known. This report presents thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and x-ray diffraction (XRD) results for MoSi 2 exposed to 670-1498 K water vapor. Synthetic air (80-20%, Ar-O 2 ) exposures were also performed, and those results are presented here for a comparative analysis. It was determined that MoSi 2 displays drastically different oxidation behavior in water vapor than in dry air. In the 670-1498 K temperature range, four distinct behaviors are observed. Parabolic oxidation is exhibited in only 670-773 K water vapor, a temperature range in which the material pests in dry O 2 environments. From 877-1084 K in water vapor, MoSi 2 undergoes rapid mass gain resulting in oxidation throughout the bulk of the sample at 980 K and 1084 K. The resulting material displays swelling and warping after the 980-1084 K exposures. A pre-passivation heat treatment performed at 1395 K was found capable of producing a coarse SiO 2 layer that limited pesting at lower temperatures in water vapor over the time periods investigated.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Defect evolution in Ni and NiCoCr by in situ 2.8 MeV Au irradiation

The evolution of radiation-induced defects in Ni and the single-phase concentrated solid solution alloy, NiCoCr, were investigated during in situ 2.8 MeV Au ion irradiation and post-irradiation analysis using transmission electron microscopy. Compared to Ni, both the size and area density of defect clusters decreased in NiCoCr under the same irradiation conditions, suggesting that the chemical complexity, i.e., randomness of lattice site occupations, of NiCoCr suppressed radiation-induced damage. One-dimensional glide of defect clusters was observed in Ni but not in the NiCoCr alloy. The structural nature of small defect clusters in NiCoCr were further investigated using high-angle annular dark field scanning transmission electron microscopy.

36 MATERIALS SCIENCE↗

Quantifying the Impact of Nanoparticle Coatings and Non-uniformities on XPS Analysis: Gold/silver Core-shell Nanoparticles

Abstract or short description: Spectral modeling of photoelectrons can serve as a valuable tool when combined with X-ray photoelectron spectroscopy (XPS) analysis. Herein, a new version of the NIST Simulation of Electron Spectra for Surface Analysis (SESSA 2.0) software, capable of directly simulating spherical multilayer NPs, was applied to model citrate stabilized Au/Ag-core/shell nanoparticles (NPs). The NPs were characterized using XPS and scanning transmission electron microscopy (STEM) to determine the composition and morphology of the NPs. The Au/Ag-core/shell NPs were observed to be polydispersed in size, non-circular, and contain off-centered Au-cores. Using the average NP dimensions determined from STEM analysis, SESSA spectral modeling indicated that washed Au/Ag-core shell NPs were stabilized with a 0.8 nm l

Core-shell nanoparticles↗

MAGNETIC VARIANCES AND PITCH-ANGLE SCATTERING TIMES UPSTREAM OF INTERPLANETARY SHOCKS

Recent observations of power-law time profiles of energetic particles accelerated at interplanetary shocks have shown the possibility of anomalous, superdiffusive transport for energetic particles throughout the heliosphere. Those findings call for an accurate investigation of the magnetic field fluctuation properties at the resonance frequencies upstream of the shock's fronts. Normalized magnetic field variances, indeed, play a crucial role in the determination of the pitch-angle scattering times and then of the transport regime. The present analysis investigates the time behavior of the normalized variances of the magnetic field fluctuations, measured by the Ulysses spacecraft upstream of corotating interaction region (CIR) shocks, for those events which exhibit superdiffusion for energetic electrons. We find a quasi-constant value for the normalized magnetic field variances from about 10 hr to 100 hr from the shock front. This rules out the presence of a varying diffusion coefficient and confirms the possibility of superdiffusion for energetic electrons. A statistical analysis of the scattering times obtained from the magnetic fluctuations upstream of the CIR events has also been performed; the resulting power-law distributions of scattering times imply long range correlations and weak pitch-angle scattering, and the power-law slopes are in qualitative agreement with superdiffusive processes described by a Levy random walk.

79 ASTRONOMY AND ASTROPHYSICS↗

Electronic Structure of the [Cu 3 (μ-O) 3 ] 2+ Cluster in Mordenite Zeolite and Its Effects on the Methane to Methanol Oxidation

Identifying Cu-exchanged zeolites able to activate C–H bonds and selectively convert methane to methanol is a challenge in the field of biomimetic heterogeneous catalysis. Recent experiments point to the importance of trinuclear [Cu 3 (μ-O) 3 ] 2+ complexes inside the micropores of mordenite (MOR) zeolite for selective oxo-functionalization of methane. The electronic structures of these species, namely, the oxidation state of Cu ions and the reactive character of the oxygen centers, are not yet fully understood. In this study, we performed a detailed analysis of the electronic structure of the [Cu 3 (μ-O) 3 ] 2+ site using multiconfigurational wave-function-based methods and density functional theory. The calculations reveal that all Cu sites in the cluster are predominantly present in the Cu(II) formal oxidation state with a minor contribution from Cu(III), whereas two out of three oxygen anions possess a radical character. These electronic properties, along with the high accessibility of the out-of-plane oxygen center, make this oxygen the preferred site for the homolytic C–H activation of methane by [Cu 3 (μ-O) 3 ] 2+ . These new insights aid in the construction of a theoretical framework for the design of novel catalysts for oxyfunctionalization of natural gas and suggest further spectroscopic examination.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and structural characterization of the new Zintl phases Eu 10 Mn 6 Bi 12 and Yb 10 Zn 6 Sb 12

Two new ternary compounds, Eu 10 Mn 6 Bi 12 and Yb 10 Zn 6 Sb 12 , were synthesized and structurally characterized. The synthesis was achieved either through reactions in sealed niobium tubes or in alumina crucibles by combining the elements in excess molten Sb. Their structures were elucidated using single-crystal X-ray diffraction, and they were determined to crystallize in the orthorhombic space group Cmmm (no. 65) with the Eu 10 Cd 6 Bi 12 structure type. Akin to the archetype phase, both Mn and Zn sites contain about 25% of vacancies. Furthermore, the anionic substructure of the title phases can be described as [M 6 Pn 12 ] (M = Zn, Mn; Pn = Sb, Bi) double layers composed of the corner and edge-sharing [MPn 4 ] tetrahedra, linked by [Pn 2 ] 4– dumbbells. Eu 2+ /Yb 2+ cations fill the space between the layers, with the valence electron counts adhering closely to the Zintl–Klemm rules, i.e., both Eu 10 Mn 6 Bi 12 and Yb 10 Zn 6 Sb 12 are expected to be valence-precise compounds. Analysis of the electronic structure and transport properties of Yb 10 Zn 6 Sb 12 indicate semimetallic behavior with relatively low Seebeck coefficient and resistivity that slightly decreases as a function of temperature.

36 MATERIALS SCIENCE↗

Optical and electronic properties of doped p -type CuI: Explanation of transparent conductivity from first principles

In this paper, we report the properties of the reported transparent conductor CuI, including the effect of heavy p-type doping. The results, based on first-principles calculations, include an analysis of the electronic structure and calculations of optical and dielectric properties. We find that the origin of the favorable transparent conducting behavior lies in the absence in the visible of strong interband transitions between deeper valence bands and states at the valence-band maximum that become empty with p-type doping. Instead, strong interband transitions to the valence-band maximum are concentrated in the infrared with energies below 1.3 eV. This is contrast to the valence bands of many wide-band-gapmaterials. Turning to the mobility,we find that the states at the valence-band maximum are relatively dispersive. This originates from their antibonding Cu d–I p character. We find a modest enhancement of the Born effective charges relative to nominal values, leading to a dielectric constant ε(0) = 6.3. This is sufficiently large to reduce ionized impurity scattering, leading to the expectation that the properties of CuI can still be significantly improved through sample quality.

14 SOLAR ENERGY↗

Preparation and Characterization of Iminodiacetate Group Containing Nonwoven Polyethylene Fabrics and Its Application in Chromium Adsorption

An iminodiacetate (IDA) group containing nonwoven polyethylene (PE) film was prepared by radiation induced graft polymerization of an epoxy group containing monomer, glycidyl methacrylate (GMA) onto nonwoven PE fabric and subsequent chemical modification to IDA group. The effect of solvents (water, methanol, ethanol, isopropyl alcohol and dimethyl sulfoxide) on modification of epoxy group of GMA grafted PE (GMA-g-PE) fabric to IDA group was investigated. Ethanol provided a higher density of IDA group on GMA-g-PE fabric. Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis and dynamic mechanical analysis of IDA-GMA-PE adsorbent, GMA-g-PE fabric and pure PE fabric were studied. The ability of resultant IDA adsorbent to absorb chromium from aqueous medium was evaluated by batch method. The parameters such as feeding chromium concentration, pH of chromium solution and adsorption time of IDA adsorbent were discussed. The obtained results illustrate that the IDA adsorbent could be fruitful to absorb chromium from water. The equilibrium experimental data for the adsorption of chromium on IDA adsorbent fitted Langmuir isotherm model.

36 MATERIALS SCIENCE↗

Summary of Blast Shield and Material Testing for Development of Solid Debris Collection at the National Ignition Facility (NIF)

The ability to collect solid debris from the target chamber following a NIF shot has application for both capsule diagnostics, particularly for fuel-ablator mix, and measuring cross sections relevant to the Stockpile Stewardship program and nuclear astrophysics. Simulations have shown that doping the capsule with up to 10 15 atoms of an impurity not otherwise found in the capsule does not affect its performance. The dopant is an element that will undergo nuclear activations during the NIF implosion, forming radioactive species that can be collected and measured after extraction from the target chamber. For diagnostics, deuteron or alpha induced reactions can be used to probe the fuel-ablator mix. For measuring neutron cross sections, the dopant should be something that is sensitive to the 14 MeV neutrons produced through the fusion of deuterium and tritium. Developing the collector is a challenge due to the extreme environment of the NIF chamber. The collector surface is exposed to a large photon flux from x-rays and unconverted laser light before it is exposed to a debris wind that is formed from vaporized material from the target chamber center. The photons will ablate the collector surface to some extent, possibly impeding the debris from reaching the collector and sticking. In addition, the collector itself must be mechanically strong enough to withstand the large amount of energy it will be exposed to, and it should be something that will be easy to count and chemically process. In order to select the best material for the collector, a variety of different metals have been tested in the NIF chamber. They were exposed to high-energy laser shots in order to evaluate their postshot surface characterization, morphology, degree of melt, and their ability to retain debris from the chamber center. The first set of samples consisted of 1 mm thick pieces of aluminum that had been fielded in the chamber as blast shields protecting the neutron activation diagnostic. Ten of these pieces were fielded at the equator and one was fielded on the pole. The shields were analyzed using a combination of scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), x-ray fluorescence (XRF), neutron activation analysis (NAA) and chemical leaching followed by mass spectrometry. On each shield, gold debris originating from the gold hohlraum was observed, as well as large quantities of debris that were present in the center of the target chamber at the time of the shot (i.e., stainless steel, indium, copper, etc.) Debris was visible in the SEM as large blobs or splats of material that had encountered the surface of the aluminum and stuck. The aluminum itself had obviously melted and condensed, and some of the large debris splats arrived after the surface had already hardened. Melt depth was determined by cross sectioning the pieces and measuring the melted surface layers via SEM. After the SEM analysis was completed, the pieces were sent for NAA at the USGS reactor and were analyzed by U. Greife at the Colorado School of Mines. The NAA showed that the majority of gold mass present on the shields was not in the form of large blobs and splats, but was present as small particulates that had most likely formed as condensed vapor. Further analysis showed that the gold was entrained in the melted aluminum surface layers and did not extend down into the bulk of the aluminum. Once the gold mass was accounted for from the NAA, it was determined that the aluminum fielded at the equator was collecting a fraction of the total gold hohlraum mass equivalent to 120% ± 10% of the solid angle subtended by the shield. The attached presentation has more information on the results of the aluminum blast shield analysis. In addition to the information given in the presentation, the surfaces of the shields have been chemically leached and submitted for mass spectrometric analysis. The results from that analysis are expected to arrive after the due date of this report and will be written up at a later time. Based on the results of the aluminum blast shield analysis, it was determined that additional materials needed to be tested as potential collectors in the NIF chamber. 1-2 mm thick pieces of tantalum, niobium, vanadium, silver, titanium, molybdenum, and graphite foil were fielded in the Wedge Range Filter (WRF) mount at a distance of 50 cm from target chamber center during the shock timing campaign. The pieces were subsequently removed and analyzed in a similar fashion to the aluminum shields. As of this writing, the pieces are still under analysis, but initial results indicate that gold debris was collected on the various materials. Currently, the pieces are being cross-sectioned so that the melt depths of each material can be compared. In addition, NAA and/or mass spectrometry will be performed in order to determine the total gold mass that was collected on each surface.

36 MATERIALS SCIENCE↗

Laterally self-ordered silicon-germanium islands with optimized confinement properties

We present an analysis of the electronic confinement properties of self-assembled islands forming via silicon and germanium co-deposition in molecular beam epitaxy. This approach allows the fabrication of laterally self-ordered three dimensional islands in the Stranski-Krastanow growth mode. Using a systematic structural analysis, we derive a realistic fit-parameter free island model for band structure simulations. A comparison between these band structure simulations and photoluminescence spectroscopy shows that such islands have a significant three dimensional spatial electron-hole wave function overlap. In addition, we show that this spatial wave function overlap overcompensates a weak wave function spreading in k-space.

36 MATERIALS SCIENCE↗

Unveiling the underlying interactions in Ta 2 NiSe 5 from photoinduced lifetime change

We present a generic procedure for quantifying the interplay of electronic and lattice degrees of freedom in photodoped insulators through a comparative analysis of theoretical many-body simulations and time- and angle-resolved photoemission spectroscopy (TR-ARPES) of the transient response of the candidate excitonic insulator Ta 2 NiSe 5 . Our analysis demonstrates that the electron-electron interactions dominate the electron-phonon ones. In particular, a detailed analysis of the TR-ARPES spectrum enables a clear separation of the dominant broadening (electronic lifetime) effects from the much smaller band-gap renormalization. Theoretical calculations show that the observed strong spectral broadening arises from the electronic scattering of the photoexcited particle-hole pairs and cannot be accounted for in a model in which electron-phonon interactions are dominant. The competing interactions were quantified using the scaling analysis in the weak fluence regime. We demonstrate that the magnitude of the weaker subdominant band-gap renormalization sensitively depends on the distance from the semiconductor/semimetal transition in the high-temperature state, which could explain the apparent contradictions between various TR-ARPES experiments. The analysis presented here indicates that electron-electron interactions play a vital role (albeit not the sole one) in stabilizing the insulating state, and establishes the comparison between lifetime and gap evolution as an important probe of correlated insulators.

36 MATERIALS SCIENCE↗