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At least 253 records · Page 14

A Synthetic Pathway for Producing Carbon Dots for Detecting Iron Ions Using a Fiber Optic Spectrometer

Iron detection is of growing importance in the critical minerals sector, where unwanted iron ions are typically removed during the processing of target critical metals. The ideal sensor should utilize inexpensive, scalable materials along with a low-cost, robust, and easy-to-use analysis platform. Here, we demonstrate a simple acid–base synthesis of luminescent iron-responsive carbon dots by reacting ethanolamine, phosphoric acid, and m-phenylenediamine. The carbon dots exhibit selective, iron-specific emission quenching, with the ability to detect part-per-billion levels of iron ions even in 0.1 M HCl. After benchmarking the purified materials using a commercial spectrometer, a “low-cost” process is demonstrated in which carbon dots with minimal purification are coupled with a portable fiber-optic spectrometer for analyzing iron content. Carbon dot-coated paper strips are also evaluated as another convenient platform for iron analysis. Taken together, the sensing material and platforms demonstrated here are well-suited for detecting trace quantities of iron in environmentally relevant conditions, with potential applications in tracking iron removal processes during critical mineral production as one exciting area of interest.

acid mine draining↗

Improved low temperature performance of lithium ion cells with quaternary carbonate-based electrolytes

In order to enable future missions involving the exploration of the surface of Mars with Landers and Rovers, NASA desires long life, high energy density rechargeable batteries which can operate well at very low temperature (down to 40(deg)C). Lithium-ion technology has been identified as being the most promising chemistry, due to high gravimetric and volumetric energy densities, as well as, long life characteristics. However, the state-of-art (SOA) technology is not sufficient to meet the needs of many applications that require excellent low temperature capabilities. To further improve this technology, work at JF'L has been focused upon developing electrolytes that result in lithium-ion cells with wider temperature ranges of operation. These efforts have led to the identification of a number of ternary and quaternary, all carbonate-based electrolytes that have been demonstrated to result in improved low temperature performance in experimental three-electrode MCMB carbon/LiNio.sCoo.zOz cells. A number of electrochemical characterization techniques were performed on these cells (i.e., Tafel polarization measurements, linear polarization measurements, and electrochemical impedance spectroscopy (EIS)) to further enhance our understanding of the performance limitations at low temperature. The most promising electrolyte formulations, namely 1 .O M LiPF6EC+DEC+DMC+EMC (1 : 1: 1 :2 v/v) and 1 .O M LiPF6 EC+DEC+DMC+EMC (1 : 1 : 1 :3 v/v), were incorporated into SAFT prototype DD-size (9 Ahr) lithium- cells for evaluation. A number of electrical tests were performed on these cells, including rate characterization as a function of temperature, cycle life characterization at different temperatures, as well as, many mission specific characterization test to determine their viability to enable future missions to Mars. Excellent performance was observed with the prototype DD-size cells over a wide temperature range (-50 to 4OoC), with high specific energy being delivered at very low temperatures (i.e, over 95 WHrKg being delivered at 40(deg)C using a C/10 discharge rate).

Li-ion low temperature electrolytes↗

Lignite-Derived Carbon Materials for Lithium-Ion Battery Anodes

This project involved collaboration between the University of North Dakota (UND) College of Engineering & Mines, Clean Republic, LLC (CR), and the North American Coal Corporation (NACoal) to develop advanced LIBs anodes from lignite-derived carbon materials. The overall goal of the project was to develop advanced anode materials for LIBs from lignite-derived carbon feedstocks.

01 COAL, LIGNITE, AND PEAT↗

The chemistry of hydrocarbon ions in the Jovian ionosphere

We have modeled the chemistry of hydrocarbon ions in the jovian ionosphere. We find that a layer of hydrocarbon ions is formed in the altitude range 300-400 km above the ammonia cloud tops, due largely to direct ionization of hydrocarbons by photons in the wings of the H2 absorption lines in the 912- to 1100-A region that penetrate to below the methane homopause. We have explicitly included in the model 156 ion-neutral reactions involving hydrocaron ions with up to two carbon atoms. Larger hydrocarbon ions are included as two pseudoions, C3Hn(+) and C4Hn(+). The model shows that 15 reactions of H(+), CH3(+), CH5(+), C2H3(+), C2H5(+), and C2H6(+) with hydrocarbon neutrals are the major processes that are responsible for the production and growth of C1-, C2- and C3- or C4-ions in the hydrocarbon ion layer. The model also shows that ions initially produced in the hydrocarbon ion layer are converted into hydrocarbon ions with more than two carbon atoms with very little loss by recombination. It is likely that successive hydrocarbon ion-neutral reactions continue to produce even larger hydrocarbon ions, so the terminal ions probably have more than three or four carbon atoms. In the auroral regions, the chemistry of hydrocarbon ions may modify the densities of neutral hydrocarbons, especially C2H2 in the upper mesosphere, and may play a major role in the production of polar haze particles.

Kim, Y. H.↗

Facile, low-energy routes for the production of hydrated calcium and magnesium salts from alkaline industrial wastes

Divalent ions are extracted from solids by leaching to form a divalent ion-containing solution. The divalent ion-containing solution is subjected to concentration to form a concentrated divalent ion-containing solution. Precipitation of a divalent ion hydroxide salt is induced from the concentrated divalent ion-containing solution. In other cases, the concentrated divalent ion-containing solution is exposed to carbon dioxide to induce precipitation of a divalent ion carbonate salt.

Sant, Gaurav N.↗

Ca-Rich Carbonate Melts: A Regular-Solution Model, with Applications to Carbonatite Magma + Vapor Equilibria and Carbonate Lavas on Venus

A thermochemical model of the activities of species in carbonate-rich melts would be useful in quantifying chemical equilibria between carbonatite magmas and vapors and in extrapolating liquidus equilibria to unexplored PTX. A regular-solution model of Ca-rich carbonate melts is developed here, using the fact that they are ionic liquids, and can be treated (to a first approximation) as interpenetrating regular solutions of cations and of anions. Thermochemical data on systems of alkali metal cations with carbonate and other anions are drawn from the literature; data on systems with alkaline earth (and other) cations and carbonate (and other) anions are derived here from liquidus phase equilibria. The model is validated in that all available data (at 1 kbar) are consistent with single values for the melting temperature and heat of fusion for calcite, and all liquidi are consistent with the liquids acting as regular solutions. At 1 kbar, the metastable congruent melting temperature of calcite (CaCO3) is inferred to be 1596 K, with (Delta)bar-H(sub fus)(calcite) = 31.5 +/- 1 kJ/mol. Regular solution interaction parameters (W) for Ca(2+) and alkali metal cations are in the range -3 to -12 kJ/sq mol; W for Ca(2+)-Ba(2+) is approximately -11 kJ/sq mol; W for Ca(2+)-Mg(2+) is approximately -40 kJ/sq mol, and W for Ca(2+)-La(3+) is approximately +85 kJ/sq mol. Solutions of carbonate and most anions (including OH(-), F(-), and SO4(2-)) are nearly ideal, with W between 0(ideal) and -2.5 kJ/sq mol. The interaction of carbonate and phosphate ions is strongly nonideal, which is consistent with the suggestion of carbonate-phosphate liquid immiscibility. Interaction of carbonate and sulfide ions is also nonideal and suggestive of carbonate-sulfide liquid immiscibility. Solution of H2O, for all but the most H2O-rich compositions, can be modeled as a disproportionation to hydronium (H3O(+)) and hydroxyl (OH(-)) ions with W for Ca(2+)-H3O(+) (approximately) equals 33 kJ/sq mol. The regular-solution model of carbonate melts can be applied to problems of carbonatite magma + vapor equilibria and of extrapolating liquidus equilibria to unstudied systems. Calculations on one carbonatite (the Husereau dike, Oka complex, Quebec, Canada) show that the anion solution of its magma contained an OH mole fraction of (approximately) 0.07, although the vapor in equilibrium with the magma had P(H2O) = 8.5 x P(CO2). F in carbonatite systems is calculated to be strongly partitioned into the magma (as F(-)) relative to coexisting vapor. In the Husereau carbonatite magma, the anion solution contained an F(-) mole fraction of (approximately) 6 x 10(exp -5).

Treiman, Allan H.↗

Mixed-Polarity Copolymers Based on Ethylene Oxide and Cyclic Carbonate: Insights into Li-Ion Solvation and Conductivity

Here, this study investigates the relationship between polarity and ionic conductivity in random and block copolymer electrolytes comprising highly flexible oligo(ethylene oxide) methyl ether methacrylate (OEM) and highly polar but glassy glycerol carbonate methacrylate (GCMA) monomers, blended with either lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or lithium triflate. Interestingly, the high polarity of GCMA did not significantly enhance ionic dissociation, and the random copolymers (POEM-r-PGCMA) showed similar or lower ionic conductivities than the POEM homopolymer. Further analysis revealed that Li + only interacts with OEM and its counterion, not with GCMA. The less-intermixed and weakly phase-separated block copolymer (POEM-b-PGCMA) exhibited even lower conductivities than the random copolymer. Our results suggest that Li + solvation occurs only in the POEM-rich phase and that the larger PGCMA regions, depleted of Li + , disrupt long-range ion transport. These findings provide valuable insights into the design of polymer electrolytes and how segmental mobility and functional groups with contrasting polarities affect ion transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical State of Surface Oxygen on Carbon and Its Effects on the Capacity of the Carbon Anode in a Lithium-Ion Battery Investigated

In a lithium-ion battery, the lithium-storage capacity of the carbon anode is greatly affected by a surface layer formed during the first half cycle of lithium insertion and release into and out of the carbon anode. The formation of this solid-electrolyte interface, in turn, is affected by the chemistry of the carbon surface. A study at the NASA Glenn Research Center examined the cause-and-effect relations. Information obtained from this research could contribute in designing a high-capacity lithium-ion battery and, therefore, small, powerful spacecraft. In one test, three types of surfaces were examined: (1) a surface with low oxygen content (1.5 at.%) and a high concentration of active sites, (2) a surface with 4.5 at.% -OH or -OC type oxygen, and (3) a surface with 6.5 at.% O=C type oxygen. The samples were made from the same precursor and had similar bulk properties. They were tested under a constant current of 10 mA/g in half cells that used lithium metal as the counter electrode and 0.5 M lithium iodide in 50/50 (vol%) ethylene carbonate and dimethyl carbonate as the electrolyte. For the first cycle of the electrochemical test, the graph describes the voltage of the carbon anode versus the lithium metal as a function of the capacity (amount of lithium insertion or release). From these data, it can be observed that the surface with low oxygen and a high concentration of active sites could result in a high irreversible capacity. Such a high irreversible capacity could be prevented if the active sites were allowed to react with oxygen in air, producing -OH or -OC type oxygen. The O=C type oxygen, on the other hand, could greatly reduce the capacity of lithium intercalation and, therefore, needs to be avoided during battery fabrication.

Hung, Ching-Cheh↗

Use of accelerated helium-3 ions for determining oxygen and carbon impurities in some pure materials

Methods are developed for the determination of O impurity in Be and Si carbide and concurrent determination of C and O impurities in Si and W by irradiation with accelerated He-3 ions and subsequent activity measurements of C-11 and F-18 formed from C and O with the aid of a gamma-gamma coincidence spectrometer. Techniques for determining O in Ge and Ga arsenide with radiochemical separation of F-18 are also described.

Aleksandrova, G. I.↗

Carbon and nitrogen lines in the spectra of Wolf-Rayet stars

The one-representative-point radiative transfer theory of Castor and van Blerkom (1970) is used to predict the relative energies in emission lines of the ions of carbon and nitrogen in Wolf-Rayet atmospheres for a wide range of parameters. The predicted ratios are compared with observed relative energies of lines in the visible and ultraviolet spectral ranges of six Wolf-Rayet stars. It is found that the lower levels of C II, C III, N III, and N IV are strongly overpopulated relative to their populations in LTE. The differences between WC and WN spectra appear to be due chiefly to a difference in electron temperature in the line-emitting regions. The typical volume of stars studied is estimated to be in the range of 10 to the 41st to 10 to the 44th cu cm. Possible ways in which the line-emitting regions may be arranged around the star are discussed, noting that the high-temperature line-emitting plasma may lie in a thin annular disk approximately 10 to the 15th cm from the star.

Bhatia, A. K.↗

Conceptual Design of the Nuclear Electronic Xenon Ion System (NEXIS)

In support of the NEXIS program, Aerojet-Redmond Operations, with review and input from the JPL and Boeing, has completed the design for a development model (DM) discharge chamber assembly and main discharge cathode assembly. These efforts along with the work by JPL to develop the carbon-carbon-composite ion optics assembly have resulted in a complete ion engine design. The goal of the NEXIS program is to significantly advance the current state of the art by developing an ion engine capable of operating at an input power of 20kW, an Isp of 7500 sec and have a total xenon through put capability of 2000 kg. In this paper we will describe the methodology used to design the discharge chamber and cathode assemblies and describe the resulting final design. Specifics will include the concepts used for the mounting of the ion optics along with the concepts used for the gimbal mounts. In addition, we will present results of a vibrational analysis showing how the engine will respond to a typical Delta IV heavy vibration spectrum.

ion truster↗

Inhomogeneous distribution of lithium and electrolyte in aged Li-ion cylindrical cells

Carbonate-based electrolytes in Li-ion batteries exhibit long range order in a frozen state, which enables their non-destructive analysis by diffraction methods. In the current study the spatial distribution of lithium and electrolyte inside the graphite anode was determined in cycled Li-ion cells using monochromatic spatially-resolved neutron diffraction measurements at 150 K. The results indicate a loss of lithium and electrolyte and their non-uniform distribution in the graphite anode in aged Li-ion cells. The observed lithium and electrolyte losses are directly correlated with two electrochemical performance degradation mechanisms, which are responsible for the cell capacity fade.

18650-type↗

Direct Synthesis of Layer-Tunable and Transfer-Free Graphene on Device-Compatible Substrates Using Ion Implantation Toward Versatile Applications

Direct synthesis of layer-tunable and transfer-free graphene on technologically important substrates is highly valued for various electronics and device applications. State of the art in the field is currently a two-step process: a high-quality graphene layer synthesis on metal substrate through chemical vapor deposition (CVD) followed by delicate layer transfer onto device-relevant substrates. Here, we report a novel synthesis approach combining ion implantation for a precise graphene layer control and dual-metal smart Janus substrate for a diffusion-limiting graphene formation to directly synthesize large area, high quality, and layer-tunable graphene films on arbitrary substrates without the post-synthesis layer transfer process. Carbon (C) ion implantation was performed on Cu–Ni film deposited on a variety of device-relevant substrates. A well-controlled number of layers of graphene, primarily monolayer and bilayer, is precisely controlled by the equivalent fluence of the implanted C-atoms (1 monolayer ~4 × 10 15 C-atoms/cm 2 ). Upon thermal annealing to promote Cu-Ni alloying, the pre-implanted C-atoms in the Ni layer are pushed toward the Ni/substrate interface by the top Cu layer due to the poor C-solubility in Cu. As a result, the expelled C-atoms precipitate into a graphene structure at the interface facilitated by the Cu-like alloy catalysis. After removing the alloyed Cu-like surface layer, the layer-tunable graphene on the desired substrate is directly realized. The layer-selectivity, high quality, and uniformity of the graphene films are not only confirmed with detailed characterizations using a suite of surface analysis techniques but more importantly are successfully demonstrated by the excellent properties and performance of several devices directly fabricated from these graphene films. Molecular dynamics (MD) simulations using the reactive force field (ReaxFF) were performed to elucidate the graphene formation mechanisms in this novel synthesis approach. With the wide use of ion implantation technology in the microelectronics industry, this novel graphene synthesis approach with precise layer-tunability and transfer-free processing has the promise to advance efficient graphene-device manufacturing and expedite their versatile applications in many fields.

36 MATERIALS SCIENCE↗

Transport of Sputtered Carbon During Ground-Based Life Testing of Ion Thrusters

High voltage, high power electron bombardment ion thrusters needed for deep space missions will be required to be operated for long durations in space as well as during ground laboratory life testing. Carbon based ion optics are being considered for such thrusters. The sputter deposition of carbon and arc vaporized carbon flakes from long duration operation of ion thrusters can result in deposition on insulating surfaces, causing them to become conducting. Because the sticking coefficient is less than one, secondary deposition needs to be considered to assure that shorting of critical components does not occur. The sticking coefficient for sputtered carbon and arc vaporized carbon is measured as well as directional ejection distribution data for carbon that does not stick upon first impact.

Marker, Colin L.↗

Is a pyrene-like molecular ion the cause of the 4,430-angstroms diffuse interstellar absorption band?

The diffuse interstellar bands (DIBs), ubiquitous absorption features in astronomical spectra, have been known since early this century and now number more than a hundred. Ranging from 4,400 angstroms to the near infrared, they differ markedly in depth, width and shape, making the concept of a single carrier unlikely. Whether they are due to gas or grains is not settled, but recent results suggest that the DIB carriers are quite separate from the grains that cause visual extinction. Among molecular candidates the polycyclic aromatic hydrocarbons (PAHs) have been proposed as the possible carriers of some of the DIBs, and we present here laboratory measurements of the optical spectrum of the pyrene cation C16H10+ in neon and argon matrices. The strongest absorption feature falls at 4,435 +/- 5 angstroms in the argon matrix and 4,395 +/- 5 angstroms in the neon matrix, both close to the strong 4,430-angstroms DIB. If this or a related pyrene-like species is responsible for this particular band, it must account for 0.2% of all cosmic carbon. The ion also shows an intense but puzzling broad continuum, extending from the ultraviolet to the visible, similar to what is seen in the naphthalene cation and perhaps therefore a common feature of all PAH cations. This may provide an explanation of how PAHs convert a large fraction of interstellar radiation from ultraviolet and visible wavelengths down to the infrared.

NASA Center ARC↗