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At least 109 records · Page 6

Electrical and Optical Property of Ferroelectric BaTiO3:Eu

We studied various electrical and optical properties of Europium (1 atomic %) incorporated BaTiO3 film on n-Si(100) substrate. The thin film structure was analyzed by X-ray diffraction. Film thickness and optical refractive index were measured with an ellipsometer. P-E hysteresis measurement shows the remnant polarization of 37 micro C/sq cm in BaTiO3:Eu film. C-V measurements on the pure BaTiO3 film show recovery of capacitance across sweeping voltage ranges with a narrow transition zone due to the polarization change. On the other hand, C-V and I-V measurements on the BaTiO3:Eu film show that Europium incorporation increases positively charged states in the BaTiO3 layer such that BaTiO3:Eu/n-Si interface behaves like a leaky p-n junction.

Park, Yeonjoon↗

Detecting Thermal Barrier Coating Delamination Using Visible and Near-Infrared Luminescence from Erbium-Doped Sublayers

Nondestructive diagnostic tools are needed to monitor early stages of delamination progression in thermal barrier coatings (TBCs) because the risk of delamination induced coating failure will compromise engine performance and safety. Previous work has demonstrated that for TBCs composed of yttria-stabilized zirconia (YSZ), luminescence from a buried europium-doped sublayer can be utilized to identify the location of TBC delamination from the substantially higher luminescence intensity observed from the delaminated regions of the TBC. Luminescence measurements from buried europium-doped layers depend on sufficient transmittance of the 532 nm excitation and 606 nm emission wavelengths through the attenuating undoped YSZ overlayer to produce easily detected luminescence. In the present work, improved delamination indication is demonstrated using erbium-doped YSZ sublayers. For visible-wavelength luminescence, the erbium-doped sublayer offers the advantage of a very strong excitation peak at 517 nm that can be conveniently excited a 514 nm Ar ion laser. More importantly, the erbium-doped sublayer also produces near-infrared luminescence at 1550 nm that is effectively excited by a 980 nm laser diode. Both the 980 nm excitation and the 1550 nm emission are transmitted through the TBC with much less attenuation than visible wavelengths and therefore show great promise for delamination monitoring through thicker or more highly scattering TBCs. The application of this approach for both electron beam physical vapor deposited (EB-PVD) and plasma-sprayed TBCs is discussed.

Eldridge, J. I.↗

Delamination-Indicating Thermal Barrier Coatings

The risk of premature failure of thermal barrier coatings (TBCs), typically composed of yttria-stabilized zirconia (YSZ), compromises the reliability of TBCs used to provide thermal protection for turbine engine components. Unfortunately, TBC delamination proceeds well beneath the TBC surface and cannot be monitored by visible inspection. Nondestructive diagnostic tools that could reliably probe the subsurface damage state of TBCs would alleviate the risk of TBC premature failure by indicating when the TBC needs to be replaced before the level of TBC damage threatens engine performance or safety. To meet this need, a new coating design for thermal barrier coatings (TBCs) that are self-indicating for delamination has been successfully implemented by incorporating a europium-doped luminescent sublayer at the base of a TBC composed of YSZ. The luminescent sublayer has the same YSZ composition as the rest of the TBC except for the addition of low-level europium doping and therefore does not alter TBC performance.

Eldridge, Jeffrey I.↗

Toward white light emission from plasmonic-luminescent hybrid nanostructures

We study the light emission of plasmonic-luminescent hybrid nanostructures consisting of Ag nanoparticles (NPs) embedded in europium oxide (EuO X ). The Ag NPs present a bidimensional organization in the nanostructures and they optically behave as oblate spheroids. The photoluminescence (PL) spectral response of the nanostructures evolves from a narrow red emission characteristic of Eu 3+ ions in absence of Ag NPs to a broad blue-green emission band associated with Eu 2+ ions when the layer of Ag NPs is present. This behavior is not related to a change in the Eu 2+ /Eu 3+ ratio, which is verified by compositional analysis. Instead, a detailed investigation of the PL emission of the nanostructures suggests that the coupling of the Ag NPs to the Eu 2+ ions present in the EuO X layer, which manifests itself in an efficient sensitization of these ions, enhances their broad visible emission. In particular, the longitudinal mode of the Ag NPs surface plasmon is considered to be responsible for the efficient energy transfer for the non-normal incidence excitation PL configuration used. Finally, the use of a capping amorphous Al 2 O 3 layer allows improving the robustness of hybrid nanostructures and further enhances their PL emission. These findings provide a new path to actively control the selective excitation of Eu 2+ and Eu 3+ ions via a controlled coupling with the surface plasmon resonance modes of the Ag NPs and points to these nanostructures as promising building blocks for the development of integrable white light sources.

36 MATERIALS SCIENCE↗

On the New Oxyarsenides Eu 5 Zn 2 As 5 O and Eu 5 Cd 2 As 5 O

The new quaternary phases Eu5Zn2As5O and Eu5Cd2As5O have been synthesized by metal flux reactions and their structures have been established through single-crystal X-ray diffraction. Both compounds crystallize in the centrosymmetric space group Cmcm (No. 63, Z = 4; Pearson symbol oC52), with unit cell parameters a = 4.3457(11) Å, b = 20.897(5) Å, c = 13.571(3) Å; and a = 4.4597(9) Å, b = 21.112(4) Å, c = 13.848(3) Å, for Eu5Zn2As5O and Eu5Cd2As5O, respectively. The crystal structures include one-dimensional double-strands of corner-shared MAs4 tetrahedra (M = Zn, Cd) and As–As bonds that connect the tetrahedra to form pentagonal channels. Four of the five Eu atoms fill the space between the pentagonal channels and one Eu atom is contained within the channels. An isolated oxide anion O2– is located in a tetrahedral hole formed by four Eu cations. Applying the valence rules and the Zintl concept to rationalize the chemical bonding in Eu5M2As5O (M = Zn, Cd) reveals that the valence electrons can be counted as follows: 5 × [Eu2+] + 2 × [M2+] + 3 × [As3–] + 2 × [As2–] + O2–, which suggests an electron-deficient configuration. The presumed h+ hole is confirmed by electronic band structure calculations, where a fully optimized bonding will be attained if an additional valence electron is added to move the Fermi level up to a narrow band gap (Eu5Zn2As5O) or pseudo-gap (Eu5Cd2As5O). In order to achieve such a formal charge balance, and hence, narrow-gap semiconducting behavior in Eu5M2As5O (M = Zn, Cd), europium is theorized to be in a mixed-valent Eu2+/ Eu3+ state.

36 MATERIALS SCIENCE↗

Wash Penalty Factors: Insight into the Effects of Water Wash Down of Building Materials for Radionuclide/Nuclear (Rn) Decontamination - 20153

The release of radiological material to the urban environment can have a devastating socio-economic impact. In an urban release scenario, areas around the dispersal epicenter and any areas contaminated via atmospheric deposition may require extensive decontamination. Most recently, our group reported the decontamination efficacy of pressurized water washing of common porous building materials, and compared the penetration depth of the contaminations before and after exposure to pressurized tap water. Here, we continue evaluation of the decontamination efficacy of wash solutions based on potassium (K{sup +}) salt for cesium (Cs), strontium (Sr), and europium (Eu) contaminations on common building surfaces. The surfaces included: the cement used in concrete, the aggregate used in concrete, intact concrete, roadway asphalt, asphalt shingles, and latex paint. We deposited solutions of {sup 137}Cs, {sup 85}Sr, and {sup 152}Eu onto numerous common building materials and exposed these materials to a static bath or low-pressure flow of tap water, 0.1 M potassium chloride (KCl), and 0.5 M KCl. The decontamination efficacy and the depth profile for residual contamination were measured to determine the conditions under which applying a wash solution has benefit compared to physically removing the surface material. To aid in these analyses, we introduced a 'wash penalty factor' to quantify the degree to which contamination migrated into the bulk material by the action of the wash method. On asphalt, 70-80% of the radionuclides were found to be within 0.02 mm of the surface. Cs{sup +} bonded to negative charge sites on the surface of the mineral aggregate (used in concrete) so decontamination was improved by ion exchange with K{sup +}. Sr{sup 2+} is soluble and removed by water, while not bonding to aggregate or demonstrating solubility in the liquid asphalt. Eu{sup 3+} is precipitated and not removed in gentle wash but displays mobility within the pore space that suggests its presence as a colloid. Concrete is more porous than asphalt, and 80% of the radionuclides were within 0.2 mm of the surface for {sup 137}Cs and {sup 152}Eu and 50- 80% for {sup 85}Sr. On concrete, Cs{sup +} bonds similarly to asphalt. Sr{sup 2+} bonds to the cement or precipitates from the alkaline pore water. Eu{sup 3+} sorbs to the cement and then precipitates. In brick, the results for Cs{sup +} and Sr{sup 2+} suggested that diffusion of ions from deeper in the coupon was important. Eu{sup 3+} is removed poorly due to precipitation. We will explain and report example wash penalty factors that vary from 0 to > 1 for the various methods and the implications for deciding when to implement wash down methods. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Advancement of Commercial Intumescent Expanding Foams for Deactivation and Decommissioning in the Nuclear Sector - 20198

Florida International University (FIU), in collaboration with The Department of Energy's Office of Environmental Management (DOE-EM), Savannah River National Laboratory (SRNL), and sites across the Savannah River complex, have identified an operational requirement for a fixative technology that is intended to immobilize and/or isolate residual contamination within a 3-dimensional space. Fixation of radiological contamination can reduce worker risk and mitigate potentially hazardous conditions, however nearly every marketed contamination fixative has been found to be flammable; a significant concern in radiological facilities. Coupled with this, industry fixatives are normally used as a thin coating which can present problems when attempting to stabilize irregular geometry or areas that are difficult to access whilst ensuring full coverage. The technical evaluation and advancement of commercial-off-the-shelf (COTS) polyurethane foams has yielded a down-selected candidate that shows potential in meeting the requirements to support deactivation and decommissioning activities. Several performance criteria have been established and tested to progress the technology readiness level towards an active field demonstration (TRL-7). Such criteria include: mechanical failure limits, adhesive and cohesive properties, thermal/fire resilience, determining thermal behavior, ability to immobilize contamination, and a means of non-destructive evaluation of applications. The test scenario examined was targeted towards an application for decommissioning nuclear pipework, in which the down-selected polyurethane foam would act as a barrier to segregate pipework and mitigate the potential for release during cutting, packaging, and storage operations. Testing carried out at SRNL included: mechanical evaluation of tensile, compressive, and adhesion strength by dynamic mechanical analysis (DMA), as well as thermogravimetric analysis (TGA). FIU examined the foam's fixative properties by utilizing phosphorescent europium-dysprosium doped strontium aluminate powder to investigating the extent to which contamination can be immobilized. FIU has also exploited previous successes in the field of intumescent technologies to assess the down-selected foam's tolerance to an extreme fire scenario, while maintaining the ability to effectively mitigate a contamination release. Parallel to this, extensive thermal investigations were carried out to determine the upper boundary of anticipated heat generation during the curing process as heat generation has the potential to compromise rubber parts of contaminated enclosures. These investigations subsequently yielded a promising method for a non-destructive application evaluation by means of infrared thermography. Utilizing the high sensitivity of modern IR cameras, coupled with the heat generated during the curing process of the polyurethane foam, FIU has been exploring the concept of monitoring the external pipe surface for indications of an irregular or abnormal application, thus informing operational decision making. The testing carried out utilized several current 'best fit' ASTM standards, which serve as helpful guidelines for testing, however, a precise definition of the operational parameters and requirements is still necessary. With continued collaboration with SRNL, FIU aims refine said definitions and develop new standards by which this, and other decommissioning technologies, can be accredited by relevant standards based testing. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Rare Earth and Transition Metal Containing Glasses

Transition metal (TM) and rare earth (RE) ions have been incorporated into many glass systems such as silicate, phosphate, and borosilicate-based oxide glasses, as well as in halide and chalcogenide glasses, that find applications ranging from optical, photonic, and magnetic devices, solid-state battery, to nuclear waste disposal. Understanding the structural role of RE and TM in these glasses can help to develop glass compositions for targeted applications with either high-optical emission efficiency, electrical conductivity, or chemical durability. In this chapter, we first provide a general introduction of the applications and structural features of RE and TM in glasses, then the critical aspects of molecular dynamics (MD) simulations of these glasses such as interatomic potentials, structural analysis tools to study RE and TM ions in glasses and their clustering behaviors, Quantitative Structure–Property Analysis (QSPR), diffusion and dynamic property calculations, and electronic structure calculations to understand electronic defects such as charge trapping and radiation effects are introduced. Three representative case studies are presented: the first one is on MD simulations of erbium- and europium-doped silica and silicate glasses, as well as cerium doped aluminophosphate glasses, that revealed the effect of glass composition on RE ion local structure and clustering behavior. Electronic structure calculations of cerium-doped glass show how the existence of multioxidation states help to mediate radiation-induced damages caused by excited electron–hole pairs was also discussed. The second one focuses on alkali vanadophosphate glasses where the existence of two vanadium oxidation states help to provide electronic conduction in the glasses while alkali ions provide ionic conduction. MD simulations were used to understand vanadium environments and other structural aspects in the phosphate glasses, as well as the ionic transport behaviors of alkali ions. The third case study is on zirconium-containing borosilicate and aluminosilicate glasses that find wide applications in nuclear waste disposal. MD simulations help to provide structural details of zirconium ions that are validated by diffraction and EXAFS spectra. The structural information was used to interpret changes of mechanical properties and chemical durability by using QSPR and other analyses-based MD-generated structure models.

Du, Jincheng↗

Establishment of time‐resolved fluoroimmunoassay of IgG4 based on magnetic microspheres

Abstract Background The abnormal increase in serum IgG4 level is an important clinical symptom of IgG4‐related disease (IgG4‐RD), and the detection of serum IgG4 level is a powerful tool for the diagnosis of IgG4‐RD. This study was conducted to establish a simple and rapid immunoassay for the determination of human serum IgG4 levels. Methods Based on the competition method, a novel immunoassay was established for the determination of human serum IgG4 using a combination of time‐resolved fluoroimmunoassay (TRFIA) and magnetic microspheres. IgG4 was coupled with magnetic microspheres and competed with IgG4 in the samples to bind the Eu 3+ ‐labeled anti‐IgG4 antibody. The immunocomplex was separated and washed in a magnetic field, and the fluorescence counts were measured according to the number of dissociated europium ions. Results The analytical sensitivity of IgG4‐TRFIA based on magnetic microspheres was 0.006 g/L, and the detection range was 0.006–20 g/L under optimal conditions. The precision, recovery, and specificity of this immunoassay were demonstrated to be acceptable. The clinical application of IgG4‐TRFIA based on magnetic microspheres was evaluated and compared with that of immunonephelometry. The results showed that the two detection methods had a good correlation, with a correlation coefficient of .9871. Conclusion IgG4‐TRFIA based on magnetic microspheres has the advantages of high sensitivity, wide detection range, and short analysis time and has the potential to become a useful tool for the diagnosis of IgG4‐RD.

Wu, Qingqing↗

Characterizing the general chelating affinity of serum protein fetuin for lanthanides

Fetuin is an abundant blood protein that participates in multiple biological processes, including the transport and regulation of calcium. Fetuin is also known to have a high affinity for uranium (as the uranyl dioxo cation) and plutonium, thus it has been suggested as one of the main endogenous chelating biomolecules involved in the transport of actinides following an internal uptake event. Nevertheless, no direct measurements of its affinity for f-elements beside these two actinides have been reported. Here, we investigate the interaction between fetuin and trivalent lanthanides, such as samarium, europium, terbium, and dysprosium, by mass spectrometry and fluorescence spectroscopy. In this work, mass spectrometry results indicated that fetuin has four metal binding sites for the metal ions studied. Upon formation, the metal–protein complexes showed luminescence emission as a result of antenna sensitization of the metal ions, whose photophysics were characterized and exploited to perform direct spectrofluorimetric titrations. Furthermore, the thermodynamic constants were calculated for all complexes, confirming the formation of stable complexes with log $β^{\prime}_4$ values between 26 and 27. In characterizing the affinity of the serum protein fetuin for several f-elements, this study expands upon the initial findings focused on uranyl and plutonium, and contributes to a better understanding of the internal distribution and deposition of lanthanides, potentially representative of trivalent actinides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On silica's roles in controlling americium migration in contaminated sediments

Two studies in the early 1980s described the leaching behavior of americium (Am) disposed as part of acidic high-salt processing wastes from the Hanford Site’s Plutonium Finishing Plant to nearby ground sediments. Here these batch leach experiments showed that the Am concentrations followed a linear log [Am] versus pH relationship with a slope of –1. Column leach experiments in the second study, however, did not follow this relationship and only ~30% of the americium desorbed even after extensive column leaching. Here, the 1980s research is re-examined along with previously unpublished information and, in light of recent published work, a plausible mechanism is proposed to explain these phenomena. Amorphous silica in the contaminated sediments is postulated to be the substrate responsible for both the exchangeable Am available for leaching and the retained low-leachable Am made evident in the column leach experiments. The exchangeable Am 3+ in the contaminated sediment leach experiments behaves with pH dependence similar to that observed for uptake onto amorphous silica of sodium (Na + ), calcium (Ca 2+ ), barium (Ba 2+ ), cadmium (Cd 2+ ), uranyl (UO 2 2+ ), ferric (Fe 3+ ), chromic (Cr 3+ ), cupric (Cu 2+ ), plumbous (Pb 2+ ), uranium(IV) (U 4+ ), plutonium(IV) (Pu 4+ ), zirconium (Zr 4+ ), analogue lanthanide (gadolinium, Gd 3+ , europium, Eu 3+ , and lutetium, Lu 3+ ) and curium (Cm 3+ ) ions as well as other studies with Am 3+ . Correspondingly, the residual low-leachable Am 3+ revealed in the column leach experiments is attributed to incorporation of Am 3+ within amorphous silica by dynamic Am 3+ sorption and silica precipitation processes.

58 GEOSCIENCES↗

Distribution of rare earth and other critical elements in lignites from the Eocene Jackson Group, Texas

Coal is increasingly evaluated as a source of rare earth elements (REEs) in the United States to address the overreliance on imported REEs. The objective of this study was to assess the distribution of REEs in lignites from selected mining areas in the Texas Gulf Coastal Plain region. Thirty-one archived lignite and rock samples previously collected by the U.S. Geological Survey were analyzed for their rare earth element and critical mineral content. These include samples from one core (5400 and 5500 lignite horizons) and two opencast lignite mines (Gibbons Creek 3500 and 4500 horizons, and San Miguel horizons A to D) in the Eocene Jackson Group of the Texas Gulf of Mexico Coastal Plain. Some lithologies in the Gibbons Creek 3500 and 4500 lignite-bearing sections have high total rare earth, yttrium (Y), and scandium (Sc) (REYSc) values, up to 7800 ppm (ash basis) REYSc. The lignite lithologies show an enrichment in rare earths, [samarium (Sm) through gadolinium (Gd)]. The basal Gibbons Creek 3500 lignite bench shows a heavy rare earth element enrichment pattern resembling that often seen in peats through high volatile A bituminous coals. The 5500 lignite sequence, overlying the latter lignite sections, shows a light rare earth enrichment. The San Miguel lignite benches have heavy rare earth enrichments with a negative europium (Eu) anomaly.

58 GEOSCIENCES↗

Analysis of chemical stress and the propensity for cracking during the vertical Bridgman growth of BaBrCl:Eu

Computational models are employed to analyze residual chemical stresses arising from compositional variations in europium-doped BaBrCl crystals grown by the vertical Bridgman method. We find that significant chemical stress is produced by radial segregation of Eu in this system. In particular, the distribution of normal stresses is set by the radial concentration gradient, whose changing sign produces surface states in tension or compression. Additionally, crack opening from surface flaws will be promoted or suppressed by tensile or compressive surface stresses, respectively. Thus, crystal growth processing strategies that change the radial dopant concentration gradients are posited to affect the propensity for cracking. For this system, surface stresses are changed from states of tension to compression when the growth rate is increased, thus improving the chances to avoid cracking—a strategy that defies classical wisdom that dictates slower growth to improve outcomes. Similar strategies affecting segregation may prove beneficial to tailor chemical stress fields to reduce cracking in other crystal growth systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystal growth of new high light yield halide perovskite scintillator RbSrI 3

X-ray radiography systems are a key national security technology enabling non-invasive cargo screening. However, the scintillators currently used in these systems have limitations in performance that prompt research for new suitable materials. Here, in this work, crystal growth, physical properties, and optical and scintillation properties of a new halide perovskite scintillator RbSrI 3 were investigated for the first time. The melting point was determined to be 453 °C. Divalent europium and ytterbium were investigated as potential luminescent activators. Light yield and energy resolution of RbSrI 3 :Eu 5 mol% was 78,700 ph/MeV and 2.8 % at 662 keV, and that of RbSrI 3 :Yb 0.5 mol% was 24,000 ph/MeV and 4.9 % at 662 keV.

36 MATERIALS SCIENCE↗

Metal-insulator transition temperature in EuO 1−x films as a function of exposure time in air

Oxygen-deficient Europium monoxide EuO 1-x shows a metal-to-insulator transition near the Curie temperature (T C ). A systematic transport study of EuO 1-x thin films as a function of exposure time in air reveals a gradually decreased T C from 140 K to 70 K as the concentration of the oxygen vacancies decreases, which is accompanied by a drastic increase in the resistance. Here we also find an unusual enhancement of magnetic anisotropy in the transport measurements, which results from the strong spin-orbit coupling at the interface between the film and substrate and possible presence of spin-textures like skyrmions in EuO 1-x .

36 MATERIALS SCIENCE↗

Micro-photoluminescence mapping and Chemometrics for the rapid classification of rare earth materials

This article introduces advancements in chemically mapping rare earth materials using photoluminescence (PL) and chemometrics. By leveraging the high sensitivity and selectivity of PL compared to alternative optical techniques, as well as its compatibility with microscopy, we present enhanced capabilities for noninvasive material screening and characterization. Exemplary PL spectra of samarium(III) and europium(III) in oxide, nitrate, and chloride forms demonstrated the ability to extract detailed chemical information of diverse rare earth particles. Additionally, we introduced efficient PL mapping sequences capable of covering a 9 mm diameter carbon tab within minutes, which highlighted the benefits of rapid, large-area imaging. Furthermore, an integrated approach combining PL mapping with principal component analysis and a random forest classifier enabled the resolution of overlapping spectral peaks from different chemistries and provided accurate material classification. In conclusion, these advancements underscored the versatility and robustness of PL for chemically mapping rare earth materials, with the potential to support applications in mining, energy, environmental monitoring, isotope production and beyond.

Chemometrics↗

Stresses within rare-earth doped yttria-stabilized zirconia thermal barrier coatings from in-situ synchrotron X-ray diffraction at high temperatures

There is a growing interest for smart coatings that can be integrated into turbine engines for in-situ temperature measurements or health monitoring. The addition of rare-earth dopants into standard thermal barrier ceramic top coat materials is used to obtain luminescent coatings that enable spectral measurements, for real-time temperature or health monitoring. The thermomechanical performance and durability of such novel coating compositions in extreme environments still remains to be evaluated. Consequently, the ability to manufacture sensor coatings which present suitable thermal properties needs to be demonstrated. For this study, highly luminescent erbium and europium doped yttria-stabilized zirconia and state-of-the-art yttria-stabilized zirconia coatings manufactured by air plasma spray were characterized to determine the effects of the embedded rareearth dopants on coating internal strain and stress and to quantify and compare their high temperature response using synchrotron X-ray diffraction. In-situ depth-resolved strain measurements were performed at 15 μm intervals along the depth of the coatings to evaluate materials response at key locations, specifically at layer interfaces. In-plane stress was calculated for the coatings and a finite element model was implemented to supplement the results and enable further predictions. The results show that the sensor coatings that were manufactured in this work revealed only minor variations in the strain response of sensor coatings under a typical thermal cycle and especially at temperatures closer to that of gas turbine operating conditions, compared to state-of-the-art coatings. This work demonstrates the viability of manufacturing rare-earth doped yttria-stabilized zirconia coatings that provide beneficial spectroscopic monitoring capabilities while having minimal impact on the thermomechanical response of the thermal barrier coatings.

Air plasma spray↗