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At least 163 records · Page 9

Electrocatalyst advances for hydrogen oxidation in phosphoric acid fuel cells

The important considerations that presently exist for achieving commercial acceptance of fuel cells are centered on cost (which translates to efficiency) and lifetime. This paper addresses the questions of electrocatalyst utilization within porous electrode structures and the preparation of low-cost noble metal electrocatalyst combinations with extreme dispersions of the metal. Now that electrocatalyst particles can be prepared with dimensions of 10 A, either singly or in alloy combinations, a very large percentage of the noble metal atoms in a crystallite are available for reaction. The cost savings for such electrocatalysts in the present commercially driven environment are considerable.

Stonehart, P.↗

Assessment and comparison of 100-MW coal gasification phosphoric acid fuel cell power plants

One of the advantages of fuel cell (FC) power plants is fuel versatility. With changes only in the fuel processor, the power plant will be able to accept a variety of fuels. This study was performed to design process diagrams, evaluate performance, and to estimate cost of 100 MW coal gasifier (CG)/phosphoric acid fuel cell (PAFC) power plant systems utilizing coal, which is the largest single potential source of alternate hydrocarbon liquids and gases in the United States, as the fuel. Results of this study will identify the most promising integrated CG/PAFC design and its near-optimal operating conditions. The comparison is based on the performance and cost of electricity which is calculated under consistent financial assumptions.

Lu, Cheng-Yi↗

Mixed anhydrides (phosphoric-carboxyl) are also formed in the esterification of 5'-amp with n-acetylaminoacyl imidazolides - Implications regarding the origin of protein synthesis

Procedure for the formation of aminoacyl esters of monoribonucleotides with aminoacyl imidazolides were first reported by Gottikh et al. (1970) and summarized in 1970. This reaction has been widely used by us and numbers of other workers as a convenient means of preparing aminoacyl esters of nucleotides. We have previously reported that, under conditions of excess imidazolide, large amounts of bis 2', 3' esters are formed in addition to the monoesters. However, to our knowledge, no one has reported that in addition to the esters, relatively large amounts of the mixed anhydride, with the amino acid carboxyl attached to the phosphate, are also formed at short reaction times. We report here on the relative amounts of anhydride and esters formed in this reaction of racemic mixtures of eleven N-acetyl amino acid imidazolides with 5'-AMP and discuss the relevance of the findings to the origin of protein synthesis.

Wickramasinghe, Nalinie S. M. D.↗

Lithium-Ion Electrolytes Containing Phosphorous-Based, Flame-Retardant Additives

Future NASA missions aimed at exploring Mars, the Moon, and the outer planets require rechargeable batteries that can operate over a wide temperature range (-60 to +60 C) to satisfy the requirements of various applications. In addition, many of these applications will require improved safety, due to their use by humans. Currently, the state-of-the-art lithium-ion (Li-ion) system has been demonstrated to operate over a wide range of temperatures (-40 to +40 C); however, abuse conditions can often lead to cell rupture and fire. The nature of the electrolyte can greatly affect the propensity of the cell/battery to catch fire, given the flammability of the organic solvents used within. Li-ion electrolytes have been developed that contain a flame-retardant additive in conjunction with fluorinated co-solvents to provide a safe system with a wide operating temperature range. Previous work incorporated fluorinated esters into multi-component electrolyte formulations, which were demonstrated to cover a temperature range from 60 to +60 C. This work was described in Fluoroester Co-Solvents for Low-Temperature Li+ Cells (NPO-44626), NASA Tech Briefs, Vol. 33, No. 9 (September 2009), p. 37; and Optimized Li-Ion Electrolytes Con tain ing Fluorinated Ester Co-Solvents (NPO-45824), NASA Tech Briefs, Vol. 34, No. 3 (March 2010), p. 48. Other previous work improved the safety characteristics of the electrolytes by adding flame-retardant additives such as triphenyl phosphate (TPhPh), tri-butyl phosphate (TBuPh), triethyl phosphate (TEtPh), and bis(2,2,2-trifluoroethyl) methyl phosphonate (TFMPo). The current work involves further investigation of other types of flame-retardant additives, including tris(2,2,2-trifluoroethyl) phosphate, tris(2,2,2-trifluoroethyl) phosphite, triphenylphosphite, diethyl ethylphosphonate, and diethyl phenylphosphonate added to an electrolyte composition intended for wide operating temperatures. In general, many of the formulations investigated in this study displayed good performance over a wide temperature range, good cycle life characteristics, and are expected to have improved safety characteristics, such as low flammability. Of the electrolytes studied, 1.0 M LiPF6 in EC+EMC+DEP (20:75:5 v/v %) and 1.0 M LiPF6 in EC+EMC+DPP (20:75:5 v/v %) displayed the best operation at low temperatures, whereas the electrolyte containing triphenylphosphite displayed the best cycle life performance compared to the baseline solution. It is anticipated that further improvements can be made to the life characteristics with the incorporation of a SET promoters (such as VC, vinylene carbonate), which will likely inhibit the decomposition of the flame-retardant additives.

Smart, Marshall C.↗

Depth-Penetrating Luminescence Thermography of Thermal- Barrier Coatings

A thermographic method has been developed for measuring temperatures at predetermined depths within dielectric material layers . especially thermal-barrier coatings. This method will help satisfy a need for noncontact measurement of through-the-thickness temperature gradients for evaluating the effectiveness of thermal- barrier coatings designed to prevent overheating of turbine blades, combustor liners, and other engine parts. Heretofore, thermography has been limited to measurement of surface and near-surface temperatures. In the thermographic method that is the immediate predecessor of the present method, a thermographic phosphor is applied to the outer surface of a thermal barrier coating, luminescence in the phosphor is excited by illuminating the phosphor at a suitable wavelength, and either the time dependence of the intensity of luminescence or the intensities of luminescence spectral lines is measured. Then an emissivity-independent surface-temperature value is computed by use of either the known temperature dependence of the luminescence decay time or the known temperature dependence of ratios between intensities of selected luminescence spectral lines. Until now, depth-penetrating measurements have not been possible because light of the wavelengths needed to excite phosphors could not penetrate thermal-barrier coating materials to useful depths. In the present method as in the method described above, one exploits the temperature dependence of luminescence decay time. In this case, the phosphor is incorporated into the thermal-barrier coat at the depth at which temperature is to be measured. To be suitable for use in this method, a phosphor must (1) exhibit a temperature dependence of luminescence decay time in the desired range, (2) be thermochemically compatible with the thermal-barrier coating, and (3) exhibit at least a minor excitation spectral peak and an emission spectral peak, both peaks being at wavelengths at which the thermal-barrier coating is transparent or at least translucent. Conventional thermographic phosphors are not suitable because they are most efficiently excited by ultraviolet light, which does not penetrate thermal- barrier coating materials. (Typical thermal-barrier coating materials include or consist of various formulations of yttria-stabilized zirconia.) Only a small fraction of phosphor candidates have significant excitation at wavelengths long enough (>500 nm) for sufficient penetration of thermal-barrier coatings. One suitable phosphor material . yttria doped with europium (Y2O3:Eu) . has a minor excitation peak at 532 nm and an emission peak at 611 nm. In experiments, this material was incorporated beneath a 100-microns-thick thermal-barrier coating and subjected to excitation and measurement by the luminescence-decay-time technique. These experiments were found to yield reliable temperature values up to 1,100 C. At the time of reporting the information for this article, a search for suitable phosphors other than (Y2O3:Eu) was continuing.

Eldridge, Jeffrey↗

Heterovalent Substitution of K 2 SrP 2 O 7 :Cr 3+ to Achieve Anti-Thermal-Quenching Broadband Near-Infrared Luminescence

Broadband near-infrared (NIR) light sources based on phosphor-converted light-emitting diodes are highly desirable for biochemical analysis and medical diagnosis applications. However, thermal quenching remains a demanding challenge for developing efficient NIR phosphors. Herein, we report the enhancement of both quantum efficiency and thermal stability in Cr 3+ -activated K 2 SrP 2 O 7 phosphors through a heterovalent substitution strategy by replacing Sr 2+ with Al 3+ in K 2 Sr 1–x Al x P 2 O 7 (0.05 ≤ x ≤ 0.2) to obtain optimized broadband NIR emission. Structural modulation via Al 3+ substitution leads to the optimized composition, K 2 Sr 0.88 Al 0.1 P 2 O 7 :0.02Cr 3+ , which emits across a broad NIR range of 650–1100 nm peaking at 807 nm with a full width at half-maximum of ∼130 nm under 448 nm excitation. Remarkably, its emission intensity at 150 °C remains 120% of the initial value at room temperature, demonstrating a rare antithermal-quenching behavior. Temperature-dependent XRD studies further reveal that Al 3+ substitution effectively suppresses lattice expansion at elevated temperatures, indicating enhanced lattice stability under thermal excitation. Detailed structural and spectral analyses show that the substitution enhances local site symmetry, reduces electron–phonon coupling, increases thermally induced absorption probability, and fortifies energetic barriers against nonradiative transitions. These synergistic effects collectively endow this NIR phosphor with a superior thermal stability. Furthermore, NIR light-emitting diodes fabricated with this phosphor exhibit strong potential for applications in information identification, nondestructive detection, and night vision technologies. This study demonstrates a local structure engineering strategy for designing thermally robust Cr 3+ -activated NIR phosphors, offering valuable insights into material discovery and NIR spectroscopy device development.

Cr3+↗

Radiation sensitive area detection device and method

A radiation sensitive area detection device for use in conjunction with an X ray, ultraviolet or other radiation source is provided which comprises a phosphor containing film which releases a stored diffraction pattern image in response to incoming light or other electromagnetic wave. A light source such as a helium-neon laser, an optical fiber capable of directing light from the laser source onto the phosphor film and also capable of channelling the fluoresced light from the phosphor film to an integrating sphere which directs the light to a signal processing means including a light receiving means such as a photomultiplier tube. The signal processing means allows translation of the fluoresced light in order to detect the original pattern caused by the diffraction of the radiation by the original sample. The optical fiber is retained directly in front of the phosphor screen by a thin metal holder which moves up and down across the phosphor screen and which features a replaceable pinhole which allows easy adjustment of the resolution of the light projected onto the phosphor film. The device produces near real time images with high spatial resolution and without the distortion that accompanies prior art devices employing photomultiplier tubes. A method is also provided for carrying out radiation area detection using the device of the invention.

Carter, Daniel C.↗

Single layer multi-color luminescent display and method of making

The invention is a multi-color luminescent display comprising an insulator substrate and a single layer of host material, which may be a phosphor deposited thereon that hosts one or more different impurities, therein forming a pattern of selected and distinctly colored phosphors such as blue, green, and red phosphors in a single layer of host material. Transparent electrical conductor means may be provided for subjecting selected portions of the pattern of colored phosphors to an electric field, thereby forming a multi-color, single layer electroluminescent display. A method of forming a multi-color luminescent display includes the steps of depositing on an insulator substrate a single layer of host material, which itself may be a phosphor, with the properties to host varying quantities of different impurities and introducing one or more of said different impurities into selected areas of the said single layer of host material by thermal diffusion or ion implantation to form a pattern of phosphors of different colors in the said single layer of host material.

Robertson, James B.↗

Achieving Multimodal and Multicolor Luminescence in LaAlO 3 :Pr 3+ , Gd 3+ via Trap Engineering and Energy Transfer

Achieving multimodal luminescence within a single phosphor is vital for multifunctional applications but remains challenging due to complex color tuning and trap engineering. In this study, we report Pr 3+ and Gd 3+ co‐doped LaAlO 3 (LAO:PG) phosphors, designed through careful modulation of multilevel traps and Pr 3+ → Gd 3+ energy transfer dynamics. These materials exhibit diverse luminescence modes, including down‐conversion luminescence (DCL), up‐conversion luminescence (UCL), persistent luminescence (PersL), optically stimulated luminescence (OSL), and thermally stimulated luminescence (TSL) across a wide spectral range. Unlike previously studied Pr 3+ ‐doped LAO, the co‐doped LAO:PG shows DCL in both UV‐visible and NIR regions and displays ultraviolet‐C UCL under visible excitation. Notably, we observe, for the first time, PersL lasting several minutes in these phosphors—an improvement over the non‐PersL behavior of Pr 3+ ‐only doped LAO. Additionally, the LAO:PG phosphors exhibit strong OSL response. TSL analysis reveals five distinct trap levels linked to these properties. Density functional theory calculations further correlate intrinsic defects to these traps, supporting a proposed mechanism for the observed multimodal luminescence. These findings highlight LAO:PG as a promising platform for developing advanced phosphors with integrated luminescence modes, paving the way for future applications in data storage, phototherapy, and anti‐counterfeiting technologies.

Chemistry↗

A method of making a single layer multi-color luminescent display

The invention is a method of forming a multi-color luminescent display including the steps of depositing on an insulator substrate a smooth single layer of host material which itself may be a phosphor with the properties to host varying quantities of different impurities and introducing one or more of said different impurities into selected areas of the single layer of host material via an appropriately positioned mask as by thermal diffusion or ion-implantation to form a pattern of phosphors of different colors in the single layer of host material such that the top surface of the host layer remains smooth. Red phosphors are formed by adding impurities selected from the group consisting of Sm, SmF3, Eu, EuF3, and ZnS:MnTbF3 to a ZnS host; green phosphors by adding impurities selected from the group consisting of Tb and TbF3 to a ZnS host; and blue phosphors by adding impurities selected from the group consisting of Tm, Al, Ag, and Mg to a ZnS host.

Robertson, James B.↗

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.↗

Temperature Sensing Above 1000 C Using Cr-Doped GdAlO3 Spin-Allowed Broadband Luminescence

Cr-doped GdAlO3 (Cr:GdAlO3) is shown to produce remarkably high-intensity spin-allowed broadband luminescence with sufficiently long decay times to make effective luminescence-decay-time based temperature measurements above 1000 C. This phosphor is therefore an attractive alternative to the much lower luminescence intensity rare-earth-doped thermographic phosphors that are typically utilized at these elevated temperatures. In particular, Cr:GdAlO3 will be preferred over rare-earth-doped phosphors, such as Dy:YAG, at temperatures up to 1200 C for intensity-starved situations when the much lower emission intensity from rare-earth-doped phosphors is insufficient for accurate temperature measurements in the presence of significant radiation background. While transition-metal-doped phosphors such as Cr:Al2O3 (ruby) are known to exhibit high luminescence intensity at low dopant concentrations, quenching due to nonradiative decay pathways competing with the (sup 2)E to (sup 4)A(sub 2) radiative transition (R line) has typically restricted their use for temperature sensing to below 600 C. Thermal quenching of the broadband (sup 4)T(sub 2) to (sup 4)A(sub 2) radiative transition from Cr:GdAlO3, however, is delayed until much higher temperatures (above 1000 C). This spin-allowed broadband emission persists to high temperatures because the lower-lying (sup 2)E energy level acts as a reservoir to thermally populate the higher shorter-lived (sup 4)T(sub 2) energy level and because the activation energy for nonradiative crossover relaxation from the (sup 4)T(sub 2) level to the (sup 4)A(sub 2) ground state is high. The strong crystal field associated with the tight bonding of the AlO6 octahedra in the GdAlO3 perovskite structure is responsible for this behavior.

Eldridge, Jeffrey I.↗

Biobased Flame Retardants Towards Sustainable Building Materials with Low Embodied Carbon

Incorporation of fire retardants in different types of products is one of the essential steps in the material production process to minimize fire risk and meet fire safety requirements. A variety of commonly used flame retardants based on halogen, mineral, and other compounds has gained popularity due to their efficient flame-retardant behaviors. However, especially in the case of halides, there are numerous toxicity related issues and environmental pollution effects that have urged the building sector to deviate from their use and focus on the development of non-toxic alternatives. Therefore, to enhance the safety of flame retardants, the synthesis of flame retardants from waste feedstocks using phosphorous chemistry with a dual flame-retardant mechanism has been established. A range of waste feedstocks that include cardanol, vanillin, and gallic acids has been converted into a series of flame retardants using a one-step approach by incorporating phosphorous moieties into their structures. The established pathways allow to develop a range of flame-retardant materials by converting waste feedstocks into phosphorous-based materials with inherent flame retardancy. The introduction of abundant aromatic structures from biobased feedstocks enables high charring capabilities in materials in which these biobased flame retardants have been incorporated, increasing their char yields which significantly enhances the flame suppressing properties of the designed materials. Studies show that inclusion of phosphoric moieties into structures allows the displacement of flame enhancing radicals, by releasing non-flammable and non-toxic gases, therefore inhibiting the spread of fire in the gas phase. The resulting biobased flame retardants have been incorporated in wood substrates, foam insulation, and hemp fibers where the results show that only 1-5% of loading of biobased flame retardant suppressed the flame completely. This study represents a novel approach for the development of flame retardants with high performance while utilizing waste feedstocks as a source for their design.

Demchuk, Zoriana [ORNL] (ORCID:0000000326292235)↗

The chemical control of soluble phosphorus in the Amazon estuary

The role of sediments in controlling concentrations of soluble phosphorous in the Amazon estuary is examined. The efflux of phosphorous through the estuary is calculated using data collected on field excursions in December 1982 and May 1983, and laboratory mixing experiments. It is observed that soluble phosphorus was released from bottom sediments at a rate of 0.2 micro-M/day, when in seawater and deionizd water mixtures. The relation between release rates and salinity and sediment concentrations is studied. A one-dimensional dispersion model was developed to estimate phosphate inputs to the estuary. The model predicted total fluxes of soluble inorganic phosphorous of 15 x 10 to the 6th mole/day for December 1982 and 27 x 10 to the 6th mole/day for May 1983; the predictions correlate with field observations. It is noted that phosphorous removal is between 0 and 4 ppt at a rate of 0.044 + or - 0.01 micron-M/ppt per day and the annual mean input of phophorous from Amazon to outer-estuary is 23 x 10 to the 6th moles/day.

Fox, L. E.↗

Single layer multi-color luminescent display

The invention is a multi-color luminescent display comprising an insulator substrate and a single layer of host material which may be a phosphor deposited thereon that hosts one or more differential impurities, therein forming a pattern of selected and distinctly colored phosphors such as blue, green, and red phosphors in a single layer of host material. Transparent electrical conductor means may be provided for subjecting selected portions of the pattern of colored phosphors to an electric field thereby forming a multi-color, single layer electroluminescent display.

Robertson, James B.↗