Portable Luminescent Sensing Technologies for Economically Critical Metal Ions
TechConnect World Innovation Conference & Exposition 2023
Crawford, Scott↗
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Luminescent group 1A copper halides and uses thereof
High photoluminescence, high stability, inorganic perovskite compounds comprising an alkali metal selected from potassium (K), rubidium (Rb), and cesium (Cs); copper (Cu); and at least one halogen selected from chlorine (Cl), bromine (Br), and iodine (I). The perovskites may be free of lead (Pb). The inorganic perovskite compound may be used in an optoelectronic device. The optoelectronic device optionally contains a phosphor such as a blue-emitting phosphor. The inorganic perovskite compound may be used as an anti-counterfeiting nanotaggant applied on or within an object that susceptible to counterfeiting to enable confirmation of an authentic object.
Saparov, Bayram↗
Fiber Optic Luminescent Sensing of Economically Critical Metals
Pittcon 2023, Philadelphia, PA, March 18-22, 2023
Crawford, Scott↗
Luminescent Sensor Technologies for the Detection of Economically Critical Metals
University of Pittsburgh Engineering Science Program Seminar, Pittsburgh, PA, March 14, 2023
Crawford, Scott↗
Portable Luminescent Sensor Technologies for Economically Critical Metals
Presentation on the development of sensing materials and compact platforms for the photoluminescence-based detection of economically critical metals, including rare earth elements, cobalt, and aluminum. The important of detecting metals that interfere with critical metal processing, such as iron and aluminum, are also discussed. The presented results represent a significant step forward in reducing the economic and time costs associated with the characterization of metals during prospecting and downstream processing.
Crawford, Scott↗
Assessing Lanthanide Trispyrazolylborates as Luminescent Single-Molecule Magnets
Presentation put together by an intern on his PhD work that also includes experiments performed at INL.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
Optical Diagnostics for High-Temperature Thermal Barrier Coatings
Thermal barrier coatings (TBCs) are typically composed of translucent ceramic oxides that provide thermal protection for metallic components exposed to high-temperature environments, such as in jet turbine engines. Taking advantage of the translucent nature of TBCs, optical diagnostics have been developed that can provide an informed assessment of TBC health that will allow mitigating action to be taken before TBC degradation threatens performance or safety. In particular, rare-earth-doped luminescent sublayers have been integrated into the TBC structure to produce luminescence that monitors TBC erosion, delamination, and temperature gradients. Erosion monitoring of TBC-coated specimens is demonstrated by utilizing visible luminescence that is excited from a sublayer that is exposed by erosion. TBC delamination monitoring is achieved in TBCs with a base rare-earth-doped luminescent sublayer by the reflectance-enhanced increase in luminescence produced in regions containing buried delamination cracks. TBC temperature monitoring is demonstrated using the temperature-dependent decay time for luminescence originating from the specific coating depth associated with a rare-earth-doped luminescent sublayer. The design and implementation of these TBCs with integrated luminescent sublayers is discussed, including co-doping strategies to produce more penetrating near-infrared luminescence. It is demonstrated that integration of the rare-earth-doped sublayers is achieved with no reduction in TBC life. In addition, results for multilayer TBCs designed to also perform as radiation barriers are also presented.
Eldridge, Jeffrey I.↗
Cathodoluminescence of shocked quartz at the Cretaceous-Tertiary boundary
Empirical studies have documented an association between rock type and the cathodoluminescence color of constituent quartz grains. Quartz from extrusive igneous sources luminesces uniform pale blue. Quartz from intrusive igneous and high-grade metamorphic rocks generally luminesces darker purple-blue, whereas quartz recrystallized under low-grade metamorphic conditions luminesces reddish-brown. Quartz grains in most sandstones luminesce a heterogeneous mixture of these colors because the grains were derived from a variety of ultimate source rocks. If shocked quartz found at the Cretaceous-Tertiary (K-T) boundary is volcanic in origin, its cathodoluminescence should be predominantly pale blue. Alternatively, quartz grains derived from bolide impact upon, and ejection of, mixed igneous, metamorphic, and sedimentary rocks should luminesce a variety of colors. Grain mounts of sand collected at the K-T boundary horizon from the Clear Creek North site in the Raton Basin, Colorado were examined. Shocked quartz luminesced a variety of colors and very few grains luminesced the pale blue color that is typical of volcanic quartz. It was concluded that the shocked quartz was derived from a petrologically diverse source region without substantial volcanic contribution. Most shocked grains apparently were derived from low-grade metamorphic rocks, with a slightly smaller contribution from high-grade metamorphic and intrusive igneous rocks. Rare quartz grains with brown-luminescing rims reflect a minor addition from detrital sedimentary sources. The apparent relative abundances of intrusive (and rare extrusive) igneous, metamorphic, and sedimentary ultimate source rocks suggested by CL colors of shock-deformed quartz at the K-T boundary is consistent with a crustal/supracrustal origin for the grains.
Owen, Michael R.↗
Method development for compensating temperature effects in pressure sensitive paint measurements
Pressure sensitive luminescent paints (PSP) have recently emerged as a viable technique for aerodynamic pressure measurements. The technique uses a surface coating which contains probe molecules that luminesce when excited by light of an appropriate wavelength. The photoluminescence of these materials is known to be quenched by the presence of molecular oxygen. Since oxygen is a fixed mole fraction of the air, the coating's luminescence intensity varies inversely with air pressure. Digital imaging of the luminescence varying across a coated surface produces a pressure distribution map over that surface. One difficulty encountered with this technique is the temperature effect on the luminescence intensity. Present PSP formulations have significant sensitivity to temperature. At the moment, the most practical way of correcting for temperature effects is to calibrate the paint in place at the operating temperatures by using a few well-placed pressure taps. This study is looking at development of temperature indicating coatings that can be applied and measured concurrently with PSP, and use the temperature measurement to compute the correct pressure. Two methods for this dual paint formulation are proposed. One method will use a coating that consists of temperature sensitive phosphors in a polymer matrix. This is similar in construction to PSP, except that the probe molecules used are selected primarily for their temperature sensitivity. Both organic phosphors (e.g., europium thenoyltrifluoroacetonate, bioprobes) and inorganic phosphors (e.g., Mg4(F)GeO6:Mn, La2O2S:Eu, Radelin Type phosphors, Sylvania Type phosphors) will be evaluated for their temperature sensing potential. The next method will involve a novel coating composing of five membered heterocyclic conducting polymers which are known to show temperature dependent luminescence (e.g., poly(3-alkylthiopene), poly(3-alkylselenophene), poly(3-alkylfuran)). Both methods will involve applying a bottom layer of temperature sensitive coating followed by a top coating of PSP. An oxygen-impermeable polymer can be used as the temperature sensitive coating matrix, or it can be layered in between the coatings to prevent oxygen quenching of the bottom coating's luminescence. The probe molecules of the coatings will be excited by a broad band of light, with the different emissions detected and measured at their distinct wavelengths. Developmental research of these coatings is still in progress; however, preliminary results look very promising.
Demandante, Carlo Greg N.↗
Photoluminescence in Tagging: A Glowing Review
This literature review explores the options of using photoluminescence for tagging uranium fuel and zirconium cladding in order to easily and quickly associate interdicted material to its facility of origin or pathway after loss of institutional control. Photoluminescence is the spontaneous emission of radiation by a substance when excited by interaction with light. The source of photoluminescence can be from organic, inorganic, and organometallic compounds. Each luminophore, or compound responsible for luminescent properties, has individual strengths and weaknesses, depending on the intended use. Many factors can affect the brightness, lifetime, color, and detectability of luminophores, such as humidity, temperature, oxygen availability, noise from radiation–induced luminescence, and the presence of quenching substances like iron. Application of luminescent compound to the surface of an item can be done using paint, dye, thin film, thick film, or electrochemical coating. Several of the application techniques may have secondary functions such as corrosion resistance and detection, heat resistance, protective properties, and more. When considering cladding, there are various successful studies on the application of luminescent coatings on zirconium. However, significant research will be necessary to explore which luminophore and which application technique would best fit the intended use. In order to proceed with this research, a baseline of the natural luminescence of the intended base material (nuclear fuel or cladding) is necessary. While there may be issues with background noise, quenching from the environment, quenching from the substrate, signal to noise weakness, etc. the multitude of options may make photoluminescent tagging an option. In summary, this review has demonstrated that photoluminescence is a potential option to tag nuclear fuel and cladding, but additional paper–studies, testing, and research is required to understand the compatibility of luminescent tags in nuclear reactor environments, manufacturability, and detectability.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Transgenic AEQUORIN reveals organ-specific cytosolic Ca2+ responses to anoxia and Arabidopsis thaliana seedlings
Using the transgenic AEQUORIN system, we showed that the cotyledons and leaves of Arabidopsis thaliana seedlings developed a biphasic luminescence response to anoxia, indicating changes in cytosolic Ca2+ levels. A fast and transient luminescence peak occurred within minutes of anoxia, followed by a second, prolonged luminescence response that lasted 1.5 to 4 h. The Ca2+ channel blockers Gd3+, La3+, and ruthenium red (RR) partially inhibited the first response and promoted a larger and earlier second response, suggesting different origins for these responses. Both Gd3+ and RR also partially inhibited anaerobic induction of alcohol dehydrogenase gene expression. However, although anaerobic alcohol dehydrogenase gene induction occurred in seedlings exposed to water-agar medium and in roots, related luminescence responses were absent. Upon return to normoxia, the luminescence of cotyledons, leaves, and roots dropped quickly, before increasing again in a Gd3+, La3+, ethyleneglycol-bis(beta-aminoethyl ether)-N,N'-tetraacetic acid-, and RR-sensitive fashion.
Non-NASA Center↗
Development of YAG:Dy Thermographic Phosphor Coatings for Turbine Engine Applications
The selection and development of thermographic phosphor coatings were pursued to meet the objective of demonstrating luminescence-decay-based temperature measurements up to 1300C on the surface of a vane in an operating demonstrator turbine engine. To meet this objective, YAG:Dy was selected based on the desirable luminescence performance observed for YAG:Dy powder: (1) excellent temperature sensitivity and intensity at operating turbine engine temperatures, (2) an emission peak at the relatively short wavelength of 456 nm, where the interference from background blackbody radiation is fairly low, and (3) its nearly single exponential decay which makes for a simple, reliable temperature calibration. However, implementation of YAG:Dy for surface temperature measurements required application of YAG:Dy as a coating onto the surface of a superalloy component with a preexisting yttria-stabilized zirconia (YSZ) thermal barrier coating (TBC). An inherent dilemma in producing a YAG:Dy coating is that coating processing is constrained to be performed at temperatures below (less than 1200C) what is considered safe for the superalloy component, much lower than temperatures used to produce the high quality crystalline powder. Therefore, YAG:Dy coatings tend to exhibit lower luminescence performance compared to well prepared YAG:Dy powder, and the luminescence performance of the coating will depend on the method of coating deposition. In this presentation, the luminescence performance of YAG:Dy coatings prepared by the different methods of (1) application of a binder-based YAG:Dy-containing paint, (2) solution precursor plasma spray (SPPS), and (3) electron-beam physical vapor deposition (EB-PVD) and the effect of post-deposition heat treatments will be discussed.
Eldridge, J. I.↗
Real-Time Thermographic-Phosphor-Based Temperature Measurements of Thermal Barrier Coating Surfaces Subjected to a High-Velocity Combustor Burner Environment
Surface temperature measurements were conducted on metallic specimens coated with an yttria-stabilized zirconia (YSZ) thermal barrier coating (TBC) with a YAG:Dy phosphor layer that were subjected to an aggressive high-velocity combustor burner environment. Luminescence-based surface temperature measurements of the same TBC system have previously been demonstrated for specimens subjected to static furnace or laser heating. Surface temperatures were determined from the decay time of the luminescence signal of the YAG:Dy phosphor layer that was excited by a pulsed laser source. However, the furnace and laser heating provides a much more benign environment than that which exists in a turbine engine, where there are additional challenges of a highly radiant background and high velocity gases. As the next step in validating the suitability of luminescence-based temperature measurements for turbine engine environments, new testing was performed where heating was provided by a high-velocity combustor burner rig at Williams International. Real-time surface temperature measurements during burner rig heating were obtained from the decay of the luminescence from the YAG:Dy surface layer. The robustness of several temperature probe designs in the sonic velocity, high radiance flame environment was evaluated. In addition, analysis was performed to show whether the luminescence decay could be satisfactorily extracted from the high radiance background.
Eldridge, Jeffrey I.↗
Single detector laser-induced fluorescence imager and raman spectral instrument
Apparatus include divergence optics removably coupled to receive a probe beam in a first imaging mode to cause the probe beam to diverge before impinging on a first area of a target surface, and to not receive the probe beam in a second imaging mode to cause the probe beam to impinge on a second area of the target surface smaller than the first area, collection optics configured to receive, in response to the probe beam, luminescence light emitted from the first area and spectral light emitted from the second area, and an optical detector coupled to the collection optics, wherein the optical detector includes a luminescence imaging detector portion and a spectral imaging detector portion adjacent to the luminescence imaging detector portion, wherein the luminescence imaging detector portion is configured to receive the luminescence light emitted from the first area and the spectral imaging detector portion is configured to receive the spectral light from the second area.
Gasda, Patrick J.↗
Surface Temperature Measurements from a Stator Vane Doublet in a Turbine Engine Afterburner Flame Using a YAG:Tm Thermographic Phosphor
Luminescence-based surface temperature measurements were obtained from a YAG:Tm-coated stator vane doublet exposed to the afterburner flame of a J85 test engine at University of Tennessee Space Institute (UTSI). The objective of the testing was to demonstrate that reliable surface temperatures based on luminescence decay of a thermographic phosphor producing short-wavelength emission could be obtained from the surface of an actual engine component in a high gas velocity, highly radiative afterburner flame environment. YAG:Tm was selected as the thermographic phosphor for its blue emission at 456 nm (1D23F4 transition) and UV emission at 365 nm (1D23H6 transition) because background thermal radiation is lower at these wavelengths, which are shorter than those of many previously used thermographic phosphors. Luminescence decay measurements were acquired using a probe designed to operate in the afterburner flame environment. The probe was mounted on the sidewall of a high-pressure turbine vane doublet from a Honeywell TECH7000 turbine engine coated with a standard electron-beam physical vapor deposited (EB-PVD) 200-m-thick TBC composed of yttria-stabilized zirconia (YSZ) onto which a 25-m-thick YAG:Tm thermographic phosphor layer was deposited by solution precursor plasma spray (SPPS). Spot temperature measurements were obtained by measuring luminescence decay times at different afterburner power settings and then converting decay time to temperature via calibration curves. Temperature measurements using the decays of the 456 and 365 nm emissions are compared. While successful afterburner environment measurements were obtained to about 1300C with the 456 nm emission, successful temperature measurements using the 365 nm emission were limited to about 1100C due to interference by autofluorescence of probe optics at short decay times.
thermographic phosphor↗
The impact of 2 H 9/2 → 4 I 13/2 emission from Er 3+ ions on ratiometric optical temperature sensing with Yb 3+ /Er 3+ co-doped upconversion materials
Yb 3+ /Er 3+ co-doped upconversion materials are widely used for luminescence intensity ratio (LIR) thermometry, where the relative intensity ratio of the green luminescence transitions ( 2 H 11/2 4 I 15/2 and 4 S 3/2 4 I 15/2 ) of Er 3+ dopant ions changes with temperature. In this work we report on the impact of an additional transition from the 2 H 9/2 level to the intermediate 4 I 13/2 level, which overlaps with the green luminescence normally used for LIR thermometry. The 2 H 9/2 4 I 13/2 emission overlaps extensively with the 4 S 3/2 4 I 15/2 emission and is more sensitive to pump power. The wavelength intervals used to integrate both 2 H 11/2 4 I 15/2 and 4 S 3/2 4 I 15/2 luminescence need be selected carefully in order to achieve accurate temperature readouts.
36 MATERIALS SCIENCE↗
Copper(I) photosensitizer-silica nanoparticle assembly towards enhanced aqueous photoluminescence
Harnessing the luminescence potential of Cu(I) complexes in aqueous media is typically hindered by their poor photostability and altered properties. Here, we report the synthesis, engineering and morphological characterization of a hydrophobic homoleptic copper(I) complex entrapped into silica nanoparticles, Cu-I@SiO 2 (where “Cu-I” designates [Cu(2,9-diiodo-1,10-phenanthroline) 2 ] + ), as a promising stabilisation strategy towards water-compatible, Cu(I) complex-based luminescence. The polyether chain-decorated nano-objects are spherical with an average diameter of ca. 10.8 ± 1.9 nm. Upon dispersion in water, clear solution-like suspensions were obtained. Significantly, the aqueous suspensions photo-luminesce (Φ em = 5×10 -4 ) upon excitation through the Metal-to-Ligand Charge-Transfer transition (MLCT) of the embedded copper(I) complexes. In contrast, the corresponding silica-free molecular complex dissolved in an aqueous environment revealed fully quenched emission. Finally, the use of Cu-I@SiO 2 suspensions as luminescent probes is reported, first by assessing their potential use as electrochemiluminescent probes, and second by monitoring the photoluminescence from Cu-I@SiO 2 in the presence of whole blood.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Spatial profiles of photon chemical potential in near-field thermophotovoltaic cells
Emitted photons stemming from the radiative recombination of electron–hole pairs carry chemical potential in radiative energy converters. This luminescent effect can substantially alter the local net photogeneration in near-field thermophotovoltaic cells. Several assumptions involving the luminescent effect are commonly made in modeling photovoltaic devices; in particular, the photon chemical potential is assumed to be zero or a constant prescribed by the bias voltage. The significance of photon chemical potential depends upon the emitter temperature, the semiconductor properties, and the injection level. Hence, these assumptions are questionable in near-field thermophotovoltaic devices with nanoscale separation distances between the emitter and the cell. In the present work, an iterative solver that combines fluctuational electrodynamics with the drift-diffusion model is developed to tackle the coupled photon and charge transport problem, enabling the determination of the spatial profile of photon chemical potential beyond the detailed balance approach. Here, the difference between the results obtained by allowing the photon chemical potential to vary spatially and by assuming a constant value demonstrates the limitations of the conventional approaches. This study is critically important for performance evaluation of near-field thermophotovoltaic systems with nanoscale vacuum gaps.
30 DIRECT ENERGY CONVERSION↗