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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

Local structure and structural rigidity of the green phosphor β-SiAlON:Eu{sup 2+}

Eu{sup 2+} inserted in β-Si{sub 3−x}Al{sub x}O{sub x}N{sub 4−x} is a material that shows exceptional promise as a green-emitting phosphor. Synchrotron X-ray and neutron scattering, in conjunction with first-principles calculations and Eu L{sub 3} X-ray absorption measurements, yield a consistent picture of the composition, and the favorable position for Eu{sup 2+} substitution in the crystal structure. The Debye temperature Θ{sub D}, which is a proxy for structural rigidity relating to effectiveness as a phosphor, is very high for the starting β-Si{sub 3}N{sub 4} framework and is determined to decrease only slightly for the small amounts of Al{sup 3+} and O{sup 2−} co-substitution that are required for charge balance associated with Eu{sup 2+} insertion.

36 MATERIALS SCIENCE↗

Role of Silica Support in Phosphoric Acid Catalyzed Production of p -Xylene from 2,5-Dimethylfuran and Ethylene

p-Xylene is a commodity chemical of industrial importance for terephthalic acid production, for which renewable sourcing from naturally abundant lignocellulosic biomass is highly desired. Previous work demonstrated that phosphoric acid stabilized on siliceous zeolite supports (e.g., P-BEA, P-SPP) exhibits high selectivity toward p-xylene (>97%) from 2,5-dimethylfuran (DMF) and ethylene. However, the effect of the support and the contribution of heterogeneous versus homogeneous phosphoric acid on the observed catalytic behavior in the solvated reaction system have not been addressed. Here, we determine the phosphoric acid catalytic activity for DMF conversion and its selectivity to p-xylene when it is supported on a silica support as well as in the absence of a support. Specifically, phosphoric acid catalysis was studied in three different scenarios: (1) phosphoric acid was added in the liquid reaction mixture in the absence of any solid support, (2) phosphoric acid was added in the liquid reaction mixture along with inert silica support including siliceous zeolite (i.e., allowing for phosphoric acid–support assembly to proceed in the reaction mixture), and (3) phosphoric acid was first impregnated on the siliceous zeolite support and then the preassembled supported phosphoric acid catalyst was added in the liquid reaction mixture. We found that the reaction rate and selectivity to p-xylene are different in the above scenarios reflecting the effect of the solid support on the catalytic performance of phosphoric acid. In scenario 1, a low concentration of phosphoric acid (1.7 mM) in the absence of any solid support exhibited high selectivity to p-xylene (80% selectivity to p-xylene at 60% conversion of DMF), which decreased with increasing acid concentration. The selectivity to p-xylene and activity of phosphoric acid significantly increased by adding a silica support into the reaction system (scenario 2). Furthermore, this improvement was attributed to phosphoric acid partial association with the surface of the silica support under the reaction conditions (in situ catalyst assembly). Phosphoric acid predeposited on siliceous zeolite supports (e.g., P-BEA, P-SPP) synthesized via impregnation prior to the reaction (scenario 3) catalyzed the reaction heterogeneously without noticeable leaching and exhibited the highest activity and selectivity to p-xylene, suggesting an important role of the silica support and the need to ensure that phosphoric acid acts as a heterogeneous catalyst in order to accomplish selective conversion of DMF to p-xylene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phosphor-converted white light emitting diodes having narrow-band green phosphors

In one aspect, a phosphor converted white light LED comprising a narrow green phosphor rather than a conventional broad green phosphor may simultaneously exhibit high R9, and high Luminance Efficacy of Radiation, optionally without use of a deep red phosphor to maintain desired red color rendering. In another aspect, a phosphor converted white light LED comprising a narrow green phosphor rather than a conventional broad green phosphor may provide an emission spectrum exhibiting a significant dip in the yellow region of the spectrum and thereby provide high red-green contrast without use of a filter. The yellow dip may be shallower than in conventional devices, and the device may therefore be brighter, while maintaining desired CRI and R9.

36 MATERIALS SCIENCE↗

The effect of Tb{sup +3} on α-Sr{sub 2}P{sub 2}O{sub 7} phosphor for green LED phosphor application

A series of Tb{sup +3} activated α-Sr{sub 2}P{sub 2}O{sub 7} (Strontium Pyrophosphate) phosphors were synthesized by high temperature combustion synthesis method. The structural analysis has been done by x-ray diffraction and FTIR (Fourier Transform Infrared Spectrum). The results obtained in structural characterization indicate that the doping concentration did not affect the crystal phase and structure of the phosphors. X-ray diffraction pattern reveals that the all samples were consistence with the JCPDS card No. 24-1011. The phosphor was excited at 232 nm wavelength, very intense PL green emission peak have been observed at 545 nm. This illustrates, that the phosphors could be efficiently excited because of the charge transfer band of the host as well as the energy transfer process occurred between host (Sr{sub 2}P{sub 2}O{sub 7}) and activator (Tb{sup +3}). By increasing the doping concentration of Tb{sup +3}, the intensity of 545 nm emission peak has been increased predominantly and it suggest that the phosphor prepared has very good application in green LED phosphor.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Technoeconomic Assessment of Phosphoric Acid and Rare Earth Element Recovery from Phosphoric Acid Sludge

Sustainability faces many challenges, including the availability of materials necessary for technological advancement. Rare earth elements (REEs), for example, are key materials for several manufacturing industries that can unlock renewable energy and sustainable development. In this study, a decanter centrifuge has been employed to successfully separated phosphoric acid and REE-containing particles from phosphoric acid sludge with concentrations ranging from 1000 to 2200 ppm REEs. Operating efficiently with up to 35 wt.% solids, the centrifuge was demonstrated to achieve approximately 95% phosphoric acid recovery and 90% REE recovery in a single pass, eliminating the need for additional processing steps. This breakthrough supports a proposed rare earth oxide (REO) recovery process integrating phosphoric acid (PA), elemental phosphorus (P4), and REO into two potential pathways: PA-REO and PA-P4-REO. These processes aim to reintroduce recovered phosphoric acid into the main product to significantly increase output and revenue. Post-separation, phosphorus-rich particles can be converted to P4, while REE-containing solids undergo further treatment including acid leaching, extraction/stripping, precipitation, and calcination to produce a marketable REO material. Technoeconomic analysis indicates promising profitability, with the PA-REO process showing a delta net present value (ΔNPV) of USD 441.8 million over a 12-year period and expected return within a year of construction, while the PA-P4-REO process yields a ΔNPV of USD 178.7 million over a 12-year return period. Both pathways offer robust financial prospects and demonstrate the feasibility of commercial-scale REO recovery from phosphoric acid sludge, offering an economically feasible approach to produce REEs for future sustainable development challenges related to sustainability.

36 MATERIALS SCIENCE↗

The Influence of Phosphor and Binder Chemistry on the Aging Characteristics of Remote Phosphor Products

The influence of phosphor and binder layer chemistries on the lumen maintenance and color stability of remote phosphor disks were examined using wet high-temperature operational lifetime testing (WHTOL). As part of the experimental matrix, two different correlated color temperature (CCT) values, 2700 K and 5000 K, were studied and each had a different binder chemistry. The 2700 K samples used a urethane binder whereas the 5000 K samples used an acrylate binder. Experimental conditions were chosen to enable study of the binder and phosphor chemistries and to minimize photo-oxidation of the polycarbonate substrate. Under the more severe WHTOL conditions of 85°C and 85% relative humidity (RH), absorption in the binder layer significantly reduced luminous flux and produced a blue color shift. The milder WHTOL conditions of 75°C and 75% RH, resulted in chemical changes in the binder layer that may alter its index of refraction. As a result, lumen maintenance remained high, but a slight yellow shift was found. The aging of remote phosphor products provides insights into the impact of materials on the performance of phosphors in an LED lighting system.

Davis, Lynn↗

Continuous recovery of phosphoric acid and Rare-Earths containing particles from phosphoric acid sludge using a decanter centrifuge

Recovery of rare earth elements (REEs) from various industrial and natural streams currently draws significant attention in efforts to meet the demands of the manufacturing industry. Among many industrial byproducts and waste streams, phosphoric acid sludge could be one of the most economically feasible resources for the recovery of REEs because solid particles in the sludge contain relatively concentrated REEs, up to 3,000 ppm, while the liquid component of the sludge is valuable phosphoric acid (P 2 O 5 ) that can be recovered and returned to the main product. Due to high viscosity and large solids content (e.g., 30–40 %), however, this byproduct stream requires multistep separation and purification processes. In this study, a single-step process involving a continuous-flow decanter centrifuge (CFDC) was employed to investigate its feasibility for continuous solid/liquid separation from real phosphoric acid sludge. High centrifugal forces generated from up to 1500 G gravity acceleration separate solid particles from the sludge, generating a liquid-rich stream and a solids-rich stream at the exit of the CFDC. A single pass of phosphoric-acid sludge through the CFDC yielded 95 % liquid recovery and 90 % recovery of REEs-containing solids from 20 to 34 wt% solids-containing sludge. Finally, a reduced order model developed for the CFDC operation showed good agreement with experimental data, and preliminary technoeconomic analysis revealed potential process feasibility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solid-state actinide acid phosphites from phosphorous acid melts

The reaction of UO{sub 3} and H{sub 3}PO{sub 3} at 100 °C and subsequent reaction with dimethylformamide (DMF) produces crystals of the compound (NH{sub 2}(CH{sub 3}){sub 2})[UO{sub 2}(HPO{sub 2}OH)(HPO{sub 3})]. This compound crystallizes in space group P2{sub 1}/n and consists of layers of uranyl pentagonal bipyramids that share equatorial vertices with phosphite units, separated by dimethylammonium. In contrast, the reaction of phosphorous acid and actinide oxides at 210 °C produces a viscous syrup. Subsequent dilution in solvents and use of standard solution-state methods results in the crystallization of two polymorphs of the actinide acid phosphites An(HPO{sub 2}OH){sub 4} (An=U, Th) and of the mixed acid phosphite–phosphite U(HPO{sub 3})(HPO{sub 2}OH){sub 2}(H{sub 2}O)·2(H{sub 2}O). α- and β-An(HPO{sub 2}OH){sub 4} crystallize in space groups C2/c and P2{sub 1}/n, respectively, and comprise a three-dimensional network of An{sup 4+} cations in square antiprismatic coordination corner-sharing with protonated phosphite units, whereas U(HPO{sub 3})(HPO{sub 2}OH){sub 2}(H{sub 2}O){sub 2}·(H{sub 2}O) crystallizes in a layered structure in space group Pbca that is composed of An{sup 4+} cations in square antiprismatic coordination corner-sharing with protonated phosphites and water ligands. We discuss our findings in using solid inorganic reagents to produce a solution-workable precursor from which solid-state compounds can be crystallized. - Graphical abstract: Reaction of UO{sub 3} and H{sub 3}PO{sub 3} at 100 °C and subsequent reaction with DMF produces crystals of (NH{sub 2}(CH{sub 3}){sub 2})[UO{sub 2}(HPO{sub 2}OH)(HPO{sub 3})] with a layered structure. Reaction of phosphorous acid and actinide oxides at 210 °C produces a viscous syrup and further solution-state reactions result in the crystallization of the actinide acid phosphites An(HPO{sub 2}OH){sub 4} (An=U, Th), with a three-dimensional network structure, and the mixed acid phosphite–phosphite U(HPO{sub 3})(HPO{sub 2}OH){sub 2}(H{sub 2}O){sub 2}·(H{sub 2}O) with a layered structure. - Highlights: • U(VI), U(IV) and Th(IV) phosphites were synthesized by solution-state methods. • A new uranyl phosphite structure is based upon uranyl phosphite anionic sheets. • New U and Th phosphites have framework structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Monolithic translucent BaMgAl 10 O 17 :Eu 2+ phosphors for laser-driven solid state lighting

With high power light emitting diodes and laser diodes being explored for white light generation and visible light communication, thermally robust encapsulation schemes for color-converting inorganic phosphors are essential. In the current work, the canonical blue-emitting phosphor, high purity Eu-doped BaMgAl 10 O 17 , has been prepared using microwave-assisted heating (25 min) and densified into translucent ceramic phosphor monoliths using spark plasma sintering (30 min). Lastly, the resulting translucent ceramic monoliths convert UV laser light to blue light with the same efficiency as the starting powder and provide superior thermal management in comparison with silicone encapsulation.

36 MATERIALS SCIENCE↗

Novel Transparent Phosphor Conversion Matrix with High Thermal Conductivity for Next Generation Phosphor-Converted LED-based Solid State Lighting

The low thermal conductivity of state-of-the-art polymer encapsulants (k ~ 0.15 Wm-1K-1) limits the efficiency and power density of current phosphor conversion light emitting diodes (pc-LEDs). The technical objective of this project was to demonstrate synthesis and processing schemes for the fabrication of polymer hybrid encapsulants with a thermal conductivity exceeding k = 0.4 Wm-1K-1 for LED applications. The ‘hybrid polymer’ approach encompasses the dispersion of high thermal conductivity particle fillers (zinc oxide, ZnO as well as the alpha-polymorph of alumina, Al2O3) within a polysiloxane matrix (poly(dimethylsiloxane), PDMS as well as poly(phenyl methyl siloxane), PPMS) to increase the thermal conductivity while maintaining optical transparency and photothermal stability at levels consistent with LED applications. To accomplish this goal, a novel synthesis method for the fabrication of nanosized ZnO particles was developed and a novel surface chemistry was established to modify the surface of zinc oxide particle fillers and thus to enable their dispersion in poly(dimethyl siloxane) (PDMS) matrix polymers. Molecular dynamics and Mie simulations were used to optimize ligand structure and to enable the concurrent mixing of particles in PDMS/PPMS embedding media while also minimizing the thermal boundary resistance as well as optical scattering of particle fillers. Using this approach the synthesis of PDMS/ZnO hybrid encapsulants exhibiting a thermal conductivity of 0.64 Wm-1K-1 and optical transparency > 0.7 mm-1 was demonstrated. A forming process based on micromolding was developed to demonstrate the forming of particle filled PDMS into film and lens shapes. Photothermal stability testing revealed stability of the materials for approximately 4000 min when exposed to blue light LED (450 nm, 30 W/cm2). One postgraduate and seven graduate students were supported by the project. The research performed within this project led to fifteen publications in peer-reviewed journals and one patent application. The grant stimulated a multi-investigator research collaborations among seven investigators at Carnegie Mellon University to address the challenge of encapsulants in pc-LED applications. The grant also catalyzed the future collaboration between researchers at Carnegie Mellon University and OSRAM Sylvania to address challenges associated with the use if polymers in LED applications.

36 MATERIALS SCIENCE↗

Europium-doped aluminum oxide phosphors as indicators for frontal polymerization dynamics

In this study, we present an inexpensive and practical method that allows the monitoring and visualization of front polymerization, propagation, and dynamics. Commercially available europium-doped aluminum oxide powders were combined with video imaging to visualize free-radical propagating polymer fronts. In order to demonstrate the applicability of this method, frontal copolymerization reactions of propoxylated glycerin triacrylate (EB53), pentaerythritol triacrylate (PETA), and pentaerythritol tetra-acrylate (PETEA) with 1,1-Bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane (Luperox 231®) as an initiator were studied and compared to the results obtained by IR imaging. Systems exhibiting higher filler loading, higher EB53 content, and less acrylated monomers showed a marked decrease in front velocity, while those with more acrylated monomers and higher crosslinking density showed a marked increase in front velocity. Finally, in order to show the potential of the imaging technique, we studied fronts propagating in planar and spherical geometries.

36 MATERIALS SCIENCE↗