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At least 37 records · Page 2

Cryogenic Vibrational Spectroscopy of the Deprotonated Dimer of Phosphoric Acid

Phosphate-containing molecules are ubiquitous in nature, where they play crucial roles in biochemical processes. Further, they are of technical importance, for example, in certain batteries and in fuel cells, where a unique property of phosphoric acid is exploited its exceptionally high proton conductivity. Proton transport in phosphoric acid is known to involve proton shuttling; however, the elementary steps involved are not clear. To elucidate the hydrogen bonding preferences of phosphoric acid, we investigate the dihydrogen phosphate anion as well as the deprotonated dimer of phosphoric acid (H 3 PO 4 ·H 2 PO 4 − ) in the gas phase using infrared action spectroscopy in helium nanodroplets and infrared D 2 -tagging photodissociation spectroscopy, and the experimental spectra are compared to theoretical ones. Theory finds for H 3 PO 4 ·H 2 PO 4 − two different structures that are predicted to be nearly isoenergetic. The comparison to the experimental spectra, however, allows for a clear assignment and structure identification. The resulting structure has an interesting binding motif, which might be of relevance to interactions of phosphoric acid in the condensed phase and which can serve as a benchmark for quantum chemical calculations.

Chemical structure↗

Temperature-dependent x-ray fluorescent response from thermographic phosphors under x-ray excitation

Phosphor thermometry has been successfully applied within several challenging environments. Typically, the thermographic phosphors are excited by an ultraviolet light source, and the temperature-dependent spectral or temporal response is measured. However, this is challenging or impossible in optically thick environments. In addition, emission from other sources (e.g., a flame) may interfere with the optical phosphor emission. Furthermore, a temperature dependent x-ray excitation/emission could alleviate these issues as x-rays could penetrate obscurants with no interference from flame luminosity. In addition, x-ray emission could allow for thermometry within solids while simultaneously x-ray imaging the structural evolution. In this study, select thermographic phosphors were excited via x-ray radiation, and their x-ray emission characteristics were measured at various temperatures. Several of the phosphors showed varying levels of temperature dependence with the strongest sensitivity occurring for YAG:Dy and ZnGa 2 O 4 :Mn. This approach opens a path for less intrusive temperature measurements, particularly in optically opaque multiphase and solid phase combustion environments.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Energy dispersive x-ray diffraction of luminescent powders: A complement to visible phosphor thermometry

Energy-dispersive x-ray diffraction of thermographic phosphors has been explored as a complementary temperature diagnostic to visible phosphor thermometry in environments where the temperature-dependent optical luminescence of the phosphors is occluded. Powder phosphor samples were heated from ambient to 300°C in incremental steps and probed with polychromatic synchrotron x rays; scattered photons were collected at a fixed diffraction angle of 3.9°. Crystal structure, lattice parameters, and coefficients of thermal expansion were calculated from the diffraction data. Finally, of the several phosphors surveyed, YAG:Dy, ZnO:Ga, and GOS:Tb were found to be excellent candidates for diffraction thermometry due to their strong, distinct diffraction peaks that shift in a repeatable and linear manner with temperature.

47 OTHER INSTRUMENTATION↗

Laser discrimination by stimulated emission of a phosphor

A method for discriminating sources of UV, near infrared, and far infrared laser radiation was discovered. This technology is based on the use of a single magnesium sulfide phosphor doubly doped with rare earth ions, which is thermally/optically stimulated to generate colors correlatable to the incident laser radiation. The phosphor, after initial charging by visible light, exhibits green stimulated luminescence when exposed to a near infrared source (Nd: YAG laser). On exposure to far infrared sources (CO2 laser) the phosphor emission changes to orange color. A UV laser produces both an orange red as well as green color. A device using this phosphor is useful for detecting the laser and for discriminating between the near infrared, far infrared, and UV lasers. The technology is also capable of infrared laser diode beam profiling since the radiation source leaves an imprint on the phosphor that can be photographed. Continued development of the technology offers potential for discrimination between even smaller bandwidths within the infrared spectrum, a possible aid to communication or wavemixing devices that need to rapidly identify and process optical signals.

Mathur, V. K.↗

Thermal and Electrical Conductivity Measurements of CDA 510 Phosphor Bronze

Many cryogenic systems use electrical cables containing phosphor bronze wire. While phosphor bronze's electrical and thermal conductivity values have been published, there is significant variation among different phosphor bronze formulations. The James Webb Space Telescope (JWST) will use several phosphor bronze wire harnesses containing a specific formulation (CDA 510, annealed temper). The heat conducted into the JWST instrument stage is dominated by these harnesses, and approximately half of the harness conductance is due to the phosphor bronze wires. Since the JWST radiators are expected to just keep the instruments at their operating temperature with limited cooling margin, it is important to know the thermal conductivity of the actual alloy being used. We describe an experiment which measured the electrical and thermal conductivity of this material between 4 and 295 Kelvin.

Tuttle, James E.↗

Phosphor Ceramic Composite for Tunable Warm White Light

Composite phosphor ceramics for warm white LED lighting were fabricated with K 2 SiF 6 :Mn 4+ (KSF) as both a narrowband red phosphor and a translucent matrix in which yellow-emitting Y 3 Al 5 O 12 :Ce 3+ (YAG) particles were dispersed. The emission spectra of these composites under blue LED excitation were studied as a function of YAG loading and thickness. Warm white light with a color temperature of 2716 K, a high CRI of 92.6, and an R9 of 77.6 was achieved. A modest improvement in the thermal conductivity of the KSF ceramic of up to 9% was observed with the addition of YAG particles. In addition, a simple model was developed for predicting the emission spectra based on several parameters of the composite ceramics and validated with the experimental results. The emission spectrum can be tuned by varying the dopant concentrations, thickness, YAG loading, and YAG particle size. This work demonstrates the utility of KSF/YAG composite phosphor ceramics as a means of producing warm white light, which are potentially suitable for higher-drive applications due to their increased thermal conductivity and reduced droop compared with silicone-dispersed phosphor powders.

36 MATERIALS SCIENCE↗

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↗

Increasing the Stability of Deep Blue Phosphor‐Sensitized OLEDs Using the Polariton‐Enhanced Purcell Effect

Abstract The stability of efficient, deep blue organic light‐emitting diodes (OLEDs) remains a major challenge in the field of organic electronics. Poor device stability originates from the high probability for destructive non‐radiative triplet exciton annihilation events. Phosphor‐sensitized fluorescence (PSF) is proposed to achieve an efficient, deep blue color by energy transfer from phosphors to fluorophores. Recently, the polariton‐enhanced Purcell (PEP) effect is introduced to decrease the triplet radiative lifetime and density, resulting in an increase in blue phosphorescent OLED lifetime. Here, the PEP effect is introduced to enhance the stability of the PSF‐OLEDs. It is shown that the PEP effect increases all radiative decay rates of the phosphors and fluorophores, leading to a reduction in the triplet annihilation events. Using a Pt‐complex phosphor sensitizer and a so‐called multi‐resonance fluorescent emitter in a PEP cavity, a 3.1‐fold lifetime increase is observed at a current density ofJ= 10 mA cm −2 , reduced EQE roll‐off and deep blue color with Commission Internationale de l'Eclairage coordinates of (0.13, 0.09). The PEP effect maximally extends PSF‐OLED lifetimes in devices with the highest triplet‐to‐singlet energy transfer rates. Moreover, this work suggests that the benefits of PEPs apply to all triplet‐based OLEDs.

Chemistry↗

Phosphoric acid pre-treatment to tailor polybenzimidazole membranes for vanadium redox flow batteries

We repot vanadium redox flow batteries (VRFBs) use ion-selective membranes for transporting ionic species while separating the positive and negative electrolytes. In this paper, we report phosphoric acid doped polybenzimidazole (PBI) membranes that yield high ionic selectivity and conductivity in VRFBs. The phosphoric acid pre-treatment swells the PBI matrix irreversibly and increases its sulfuric acid doping in VRFB electrolytes. The pre-treated membranes show comparable area resistance with Nafion-212 with better selectivity towards vanadium ions. A low resistance was obtained with a reduced membrane thickness, which can reduce the overall cost of materials. The VRFB using an optimized phosphoric acid pre-treated PBI membrane demonstrates coulombic, voltage, and energy efficiencies of 99.7, 90.3, and 90.0%, respectively, at 40 mA cm -2 while achieving ~40% higher discharge capacity compared to Nafion-212. Furthermore, the VRFB cell shows excellent cycling stability, i.e., only 6.8% or 0.068% per cycle capacity decay for 100 cycles while maintaining coulombic efficiency at >99.9% (98.5% coulombic efficiency for Nafion-212 with a capacity decay of 0.42% per cycle) proving the effectiveness of pre-treatment of phosphoric acid on PBI membranes.

36 MATERIALS SCIENCE↗

High Temperature Polymer Electrolyte Membrane Fuel Cells with High Phosphoric Acid Retention

Phosphoric acid loss poses immense hurdles for the durability of high-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). Here we report quaternary ammonium-biphosphate ion-pair HT-PEMFCs that do not lose phosphoric acids under normal and accelerated stress conditions. Additionally, our energetics study explains the acid loss behavior of the conventional phosphoric acid-polybenzimidazole (PA-PBI) system by two mechanisms. If PA loss occurs via acid evaporation, the acid loss is constant over time. On the other hand, when water activity in the PA-PBI system is high, exponential decay of PA loss occurs via the water replacement mechanism. Combined 31 P NMR and computational studies show that the proposed ion-pair system has six times higher interaction energy, which allows for containing all PAs in the membrane electrode assemblies under a broad range of operating conditions. In addition, polar interactions between the phosphonic acid ionomer and phosphoric acid explain acid retention in the electrodes of the ion-pair HT-PEMFCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Persistence of phosphor glow in microchannel plate image intensifiers

Image intensifier tubes using microchannel plate amplification stages and phosphor output stages are being increasingly used in various detection applications. In this paper, measurements of the decay times of what are attributed to be the P20 phosphors in various image intensifiers are reported. It is found that the long tail on the decay curve of the phosphor following illumination can be a limitation for certain observations. In addition, the background level of phosphor glow (which is seen by the subsequent detection system as a light signal) continues to build with continuing illumination.

Torr, M. R.↗

Single-Layer, Multicolor Electroluminescent Phosphors

Etching eliminated in producing phosphor layers for displays. New process enables production of single-layer, two-color phosphor layer without etching. Method of construction, beginning with glass substrate with electrode and insulator layers, involves deposition of green phosphor masking with metal mask or photoresist; diffusion or ion implantation of manganese through mask to produce red phosphor and removal of mask.

Robertson, James B.↗

Electrodeposition of Low Stress Nickel Phosphorous Alloys for Precision Component Fabrication

Nickel alloys are favored for electroforming precision components. Nickel phosphorous and nickel cobalt phosphorous are studied in this work. A completely new and innovative electrolytic process eliminates the fumes present in electroless processes and is suitable for electroforming nickel phosphorous and nickel cobalt phosphorous alloys to any desirable thickness, using soluble anodes, without stripping of tanks. Solutions show excellent performance for extended throughput. Properties include, cleaner low temperature operation (40 - 45 C), high Faradaic efficiency, low stress, Rockwell C 52 - 54 hardness and as much as 2000 N per square millimeter tensile strength. Performance is compared to nickel and nickel cobalt electroforming.

Engelhaupt, Darell↗

High Temperature Thermographic Phosphor Coatings Development

For many years, phosphor thermometry has been used for non-contact temperature measurements. A large number of applications have been associated with high temperatures, especially for aerospace systems where blackbody radiation backgrounds are large and in challenging environments, such as vibration, rotation, flame, or noise. These environments restrict the use of more common thermocouples or infrared thermometric techniques. In particular, temperature measurements inside jet turbines, rocket engines, or similar devices are especially amenable to phosphor techniques. Often the fluorescent materials are used as powders, either suspended in binders and applied like paint or applied as high-temperature sprays. Thin coatings that are less than 50 m thick are used on the surfaces of interest. These coatings will quickly assume the same temperature as the surface to which they are applied. The temperature dependence of fluorescent materials is a function of the base matrix atoms and a small quantity of added activator or dopant ions. Often for high temperature applications, the selected materials are refractory and include rare earth ions. Phosphors like Y3Al5O12 (YAG) doped with Eu, Dy, or Tm, Y2O3 doped with Eu, or similar rare earth compounds, will survive high temperatures and can be configured to emit light that changes rapidly in lifetime and intensity. For example, researchers at Oak Ridge National Laboratory recently observed fluorescence from YAG:Dy and YAG:Tm at temperatures above 1400 C. One of the biggest challenges is to locate a binder material that can withstand tremendous variations in temperature in an adverse aerospace environment. This poster will provide an overview into our attempt to utilize phosphors for thermometry purposes. Emphasis will be placed on the use of selected binder materials that can withstand high temperatures. This research was completed for the National Aeronautics and Space Administration's Glenn Research Center in Cleveland, Ohio.

Goedeke, Shawn↗

Surface Temperature Measurements from a Stator Vane Doublet in a Turbine Engine Afterburner Flame using Ultra-Bright Cr-Doped GdAlO3 Thermographic Phosphor

Luminescence-based surface temperature measurements from an ultra-bright Cr-doped GdAlO3 perovskite (GAP:Cr) coating were successfully conducted on an air-film-cooled 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 at UTSI was to demonstrate that reliable thermal barrier coating (TBC) surface temperatures based on luminescence decay of a thermographic phosphor could be obtained from the surface of an actual engine component in an aggressive afterburner flame environment and to address the challenges of a highly radiant background and high velocity gases. A high-pressure turbine vane doublet from a Honeywell TECH7000 turbine engine was 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 GAP:Cr thermographic phosphor layer was deposited by EB-PVD. The ultra-bright broadband luminescence from the GAP:Cr thermographic phosphor is shown to offer the advantage of over an order-of-magnitude greater emission intensity compared to rare-earth-doped phosphors in the engine test environment. This higher emission intensity was shown to be very desirable for overcoming the necessarily restricted probe light collection solid angle and for achieving high signal-to-background levels. Luminescence-decay-based surface temperature measurements varied from 500 to over 1000C depending on engine operating conditions and level of air film cooling.

Eldridge, Jeffrey I.↗

Systems and methods for fluoride ceramic phosphors for LED lighting

The present disclosure relates to a lighting component which may comprise a light emitting diode (LED) or laser diode (LD) for generating at least one of blue light or ultraviolet light. A fluoride phosphor matrix may be included, which may be consolidated into a phosphor ceramic structure including at least one of a transparent fluoride ceramic structure or a translucent fluoride ceramic structure, and positioned adjacent to the LED or LD. The phosphor ceramic structure generates at least one of red or orange light when irradiated by the light emitted from the LED or LD. The phosphor ceramic structure exhibits reduced thermal quenching relative to a fluoride particulate structure irradiated by the LED or LD.

Cherepy, Nerine↗

Thermographic phosphor digital image correlation

The invention advances the ratio method of phosphor thermography using two machine vision cameras for full-field temperature measurements of a solid surface. As an example, algorithms from digital image correlation (DIC) can be used to determine the stereoscopic imaging system intrinsic and extrinsic parameters, and accurately register material points on the sample to subpixel locations in each image with 0.07 px or better accuracy. A phosphor calibration sample fabricated using aerosol deposition can be used for in situ determination of the temperature-versus-intensity ratio relationship. The full calibration methodology and several improvements on two-color phosphor thermography open the door for full-field temperature measurements in dynamic tests with deforming test specimens. In particular, thermographic phosphors can be combined with stereo digital image correlation in a novel diagnostic, TP+DIC, to measure time-resolved full-field surface strains and temperatures simultaneously, thereby enabling testing in combined thermo-mechanical environments.

Winters, Caroline↗

Advances in phosphor two-color ratio method thermography for full-field surface temperature measurements

We report thermographic phosphors can be employed for optical sensing of surface, gas phase, and bulk material temperatures through different strategies including the time-decay method, time-integrated method, and frequency-domain method. We focus on the time-integrated method, also known as the ratio method, as it can be more practical in many situations. This work advances the ratio method using two machine vision cameras with CMOS detectors for full-field temperature measurements of a solid surface. A phosphor calibration coupon is fabricated using aerosol deposition and employed for in situ determination of the temperature-versus-intensity ratio relationship. Algorithms from digital image correlation are employed to determine the stereoscopic imaging system intrinsic and extrinsic parameters, and accurately register material points on the sample to subpixel locations in each image with 0.07 px or better accuracy. Detector nonlinearity is carefully characterized and corrected. Temperature-dependent, spatial non-uniformity of the full-field intensity ratio—posited to be caused by a blue-shift effect of the bandpass filter for non-collimated light and/or a wavelength-dependent transmission efficiency of the lens—is assessed and treated for cases where a standard flat-field correction fails to correct the non-uniformity. In sum, pixel-wise calibration curves relating the computed intensity ratio to temperature in the range of T = 300–430 K are generated, with an embedded error of less than 3 K. This work offers a full calibration methodology and several improvements on two-color phosphor thermography, opening the door for full-field temperature measurements in dynamic tests with deforming test articles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗