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At least 973 records · Page 54

Effect of Added Gadolinium Oxide on the Thermal Air Oxidation of Uranium Dioxide

To develop a more reliable and stable UO2-based nuclear fuel, the Pacific Northwest National Laboratory (PNNL) investigated modifying fuel with several soluble lanthanides and zirconium. This article provides the results of these studies investigating gadolinium doping at levels up to 10 mass%. The authors characterized and compared commercially- and PNNL-prepared gadolinium-doped UO2 to determine the oxygen-to-metal ratio, elemental distribution, chemical composition, physical appearance, lattice parameters, and grain structure using atomic force microscopy, scanning electron microscopy coupled with energy dispersive spectroscopy, and X-ray diffractometry. After confirming PNNL-prepared UO2 and (Gd,U)O2 were similar to commercially prepared UO2 and (Gd,U)O2, we measured the thermal behavior of these gadolinium-doped UO2 materials to air oxidation using differential scanning calorimetry and thermogravimetric analysis. Addition of gadolinium stabilized the first oxidation product U4¬O9/U3O7 and slowed the subsequent oxidation to U3O8. Comparison of our measured two-step oxidation of UO2 to U3O8 at 325°C to common gas/solid kinetic reaction models found that each oxidation step is best described as a convolution of kinetic behaviors; the gadolinium insertion into the UO2 lattice enforces a significant alteration in mechanism and oxidation rate. Noticeable changes in mechanism become apparent between 1% and 3% gadolinium content.

Uranium Dioxide, Gadolinium Oxide, Thermal Air Oxi↗

Investigation of thermal aging effects on the tensile properties of Alloy 617 by in-situ synchrotron wide-angle X-ray scattering

The nickel-base Alloy 617 has been considered as the lead candidate structural material for the intermediate heat exchanger (IHX) of the Very-High-Temperature Reactor (VHTR). In order to assess the long-term performance of Alloy 617, thermal aging experiments up to 10,000 h in duration were performed at 1000 degrees C. Subsequently, in-situ synchrotron wide-angle X-ray scattering (WAXS) tensile tests were carried out at ambient temperature. M23C6 carbides were identified as the primary precipitates, while a smaller amount of M6C was also observed. The aging effects were quantified in several aspects: (1) macroscopic tensile properties, (2) volume fraction of the M23C6 Phase, (3) the lattice strain evolution of both the matrix and the M23C6 precipitates, and (4) the dislocation density evolution during plastic deformation. The property-microstructure relationship is described with a focus on the evolution of the M23C6 phase. For aging up to 3000 h, the yield strength (YS) and ultimate tensile strength (UTS) showed little variation, with average values being 454 MPa and 787 MPa, respectively. At 10,000 h, the YS and UTS reduced to 380 MPa and 720 MPa, respectively. The reduction in YS and UTS is mainly due to the coarsening of the M23C6 Precipitates. After long term aging, the volume fraction of the M23C6 phase reached a plateau and its maximum internal stress was reduced, implying that under large internal stresses the carbides were more susceptible to fracture or decohesion from the matrix. Finally, the calculated dislocation densities were in good agreement with transmission electron microscopy (TEM) measurements. The square roots of the dislocation densities and the true stresses displayed typical linear behavior and no significant change was observed in the alloys in different aging conditions.

Alloy 617↗

Nanoparticle Superlattices with Negative Thermal Expansion (NTE) Coefficients

In this work, we report on the assembly of gold nanoparticles grafted with poly(ethylene glycol) (PEG–AuNPs) in aqueous solutions into the face-centered cubic superlattice by synchrotron X-ray scattering. At sufficiently high salt concentrations, the lattice constant decreases with increasing temperature, i.e., it exhibits a negative thermal expansion (NTE) coefficient that is 2–4 orders (in magnitude) larger than previously reported in NTE materials. The generality of the effect is demonstrated with different salts and different PEG chain lengths. Theoretical calculations show that PEG–AuNP becomes more insoluble (with the Flory–Huggins parameter χ > (1/2)) as temperature increases through water dehydration, with a decrease in the volume of the superlattice and an increase in the entropy of the system. Implications on the formation of nanoparticle superlattices and NTE properties are also discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermal Emission Spectroscopy of Single, Isolated Carbon Nanoparticles: Effects of Particle Size, Material, Charge, Excitation Wavelength, and Thermal History

Findings are introduced for thermal emission from individually trapped carbon nanoparticles (NPs) in the temperature range from ~1000 to ~2100 K. We explore the effects on the magnitude and wavelength dependency of the emissivity, ε(λ), of the NP size and charge and of the type of carbon material, including graphite, graphene, diamond, carbon black, and carbon dots. Furthermore, it is found that heating the NPs, particularly to temperatures above ~1900 K, results in significant changes in the emission properties, which is attributed to changes in the distribution of surface and defect sites caused by annealing and sublimation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Intramolecular Noncovalent Interactions Facilitate Thermally Activated Delayed Fluorescence (TADF)

In the conventional molecular design of thermally activated delayed fluorescence (TADF) organic emitters, simultaneously achieving a fast rate of reverse intersystem crossing (RISC) from the triplet to the singlet manifold and a fast rate of radiative decay is a challenging task. A number of recent experimental data, however, point to TADF emitters with intramolecular π-π interactions as a potential pathway to overcome the issue. Here, we report a comprehensive investigation of TADF emitters with intramolecular π…π or lone-pair…π non-covalent interactions. We uncover the impact of those intramolecular non-covalent interactions on the TADF properties. In particular, we find that folded geometries in TADF molecules can trigger lone-pair…π interactions, introduce a n → π* character of the relevant transitions, enhance the singlet-triplet spin-orbit coupling, and ultimately greatly facilitate the RISC process. Furthermore, this work provides a robust foundation for the molecular design of a novel class of highly efficient TADF emitters in which intramolecular non-covalent interactions play a critical function.

36 MATERIALS SCIENCE↗

Nanophotonic Atomic Force Microscope Transducers Enable Chemical Composition and Thermal Conductivity Measurements at the Nanoscale [Nanophotonic AFM Transducers Enable Chemical Composition and Thermal Conductivity Measurements at the Nanoscale]

The atomic force microscope (AFM) offers a rich observation window on the nanoscale, yet many dynamic phenomena are too fast and too weak for direct AFM detection. Integrated cavity-optomechanics is revolutionizing micromechanical sensing; however, it has not yet impacted AFM. Here, we make a groundbreaking advance by fabricating picogram-scale probes integrated with photonic resonators to realize functional AFM detection that achieve high temporal resolution (<10 ns) and picometer vertical displacement uncertainty simultaneously. The ability to capture fast events with high precision is leveraged to measure the thermal conductivity (η), for the first time, concurrently with chemical composition at the nanoscale in photothermal induced resonance experiments. The intrinsic η of metal–organic-framework individual microcrystals, not measurable by macroscale techniques, is obtained with a small measurement uncertainty (8%). The improved sensitivity (50×) increases the measurement throughput 2500-fold and enables chemical composition measurement of molecular monolayer-thin samples. In conclusion, our paradigm-shifting photonic readout for small probes breaks the common trade-off between AFM measurement precision and ability to capture transient events, thus transforming the ability to observe nanoscale dynamics in materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Host-Free Yellow-Green Organic Light-Emitting Diodes with External Quantum Efficiency over 20% Based on a Compound Exhibiting Thermally Activated Delayed Fluorescence

Thermally activated delayed fluorescent (TADF) materials are advantageous as emitters in organic light-emitting diodes (OLEDs) due to their ability to utilize all excited states formed by charge recombination for light emission, potentially leading to 100% internal quantum efficiency. As in conventional fluorescent or phosphorescent OLEDs, TADF emitters are commonly doped at a relatively low concentration in a host matrix. However, increasing evidence suggest that balanced ambipolar transport properties and small aggregation-induced fluorescence quenching allows TADF emitters to be used alone in so-called host-free OLEDs. Here, we report on host-free OLEDs in which the EMLs consist solely of a yellow-green-emitting TADF compound, 5,5'-(2,3,5,6-tetra(carbazol-9-yl)-1,4-phenylene)bis(2-(4-(tert-butyl)phenyl)-1,3,4-oxadiazole), TCZPBOX. Devices with this host-free EML yield a maximum external quantum efficiency (EQE) of 21%, current efficacy (CE) of 73 cd/A, and power efficacy (PE) of 79 lm/W at a luminance of 10 cd/m 2 . At a high luminance of 10,000 cd/m 2 , a high EQE of 13% is maintained. A maximum luminance of 120,000 cd/m2 is reached at an applied voltage of 9.8 V. When TCZPBOX was doped in the host of 2,6-di(carbazol-9-yl)-pyridine (PYD2) at 40 wt. %, the device yielded a maximum EQE of 28%, CE of 94 cd/A, and PE of 100 lm/W at 10 cd/m 2 .

36 MATERIALS SCIENCE↗

Validity of Saha's equation of thermal ionization for negatively charged spherical particles in complex plasmas in thermal equilibrium

The authors have discussed the validity of Saha's equation for the charging of negatively charged spherical particles in a complex plasma in thermal equilibrium, even when the tunneling of the electrons, through the potential energy barrier surrounding the particle is considered. It is seen that the validity requires the probability of tunneling of an electron through the potential energy barrier surrounding the particle to be independent of the direction (inside to outside and vice versa) or in other words the Born's approximation should be valid.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Utilization fo the Satellite Test Assistant Robot (STAR) for Visual and Thermal Analysis for Articles in the Thermal Vacuum Test Environment

An innovative new telerobotic inspection system called STAR has been developed to asist engineers in the visual and thermal analysis fo flight hardware being tested in a simulated space environment. This paper describes the architecture of the STAR mechanical and control systems and discusses some uses of STAR to date.

STAR satellite test assistant robot space simulati↗