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At least 37 records · Page 2

Superconducting films of MgB 2 via ion beam mixing of Mg/B multilayers

The growth of smooth superconducting MgB 2 films in a non-epitaxial regime is challenging. Here, we study the formation of superconducting MgB 2 films by solid-phase reactive inter-diffusion of sputter-deposited Mg/B multilayers, employing ion beam mixing to disperse the multilayers prior to thermal annealing. The multilayers are intermixed by room-temperature bombardment with 500 keV Xe ions to doses up to 4 × 10 16 cm –2 , followed by thermal annealing to form MgB 2 . Results show that such an intermixing step leads to a dramatic reduction in surface roughness of superconducting films. However, lattice defects produced by ion bombardment reduce the critical superconducting transition temperature, an effect which scales monotonically with ion dose. The critical temperature can be recovered by an additional defect annealing step at $700\ ^{\circ}{\rm C}$.

36 MATERIALS SCIENCE↗

Synergistic effects of W–Ta alloys exposed to various ELM-like fusion events

Abstract Recently tungsten alloys have shown capabilities in suppressing morphological changes when exposed to harsh fusion conditions. Morphological changes due to He + and D + ions at high temperatures (1000–2000 K) can lead to easier erosion and sputtering of tungten (W) particles towards quenching the fusion plasma. This study investigated W–3Ta alloy as potential plasma facing materials (PFMs) exposed to different edge-localized mode (ELM)-like energies and ion loadings. Performance of W–3Ta has been tested as a function of ELM-like energies (0.6–1.5 GW m −2 ) and varying He + and D + ion concentrations (100% He + , 50% He + :50% D + ,10% He + :90% D + (similar ELM-like reactor condition), and 100% D + ions). Early-stage fuzz formation and surface pores were observed during 100% He + ion irradiation and mixed ion loadings but not observed during 100% D + ion loadings. Pores decreased in quantity and increased in size with increasing transient heat loading. Grain boundaries acted as trapping sites of helium and deuterium atoms during dual beam ion irradiations, as observed through increased pore size along the grain boundary. Qualitative erosion estimates were measured using witness plates. Increased erosion was observed with increasing D + ion concentration, which is attributed to D supersaturation in the near surface region affecting thermal and mechanical properties. More erosion was observed for W–3Ta samples compared to pure W, evident through large (>10 µ m) cracks on the surface, and an increase in W metal x-ray photoelectron spectroscopy peaks under similar loading conditions. The slight enhancement in erosion is attributed to the slightly decreased thermal properties, ∼10% thermal diffusivity drop, of W–3Ta at high temperatures. The damage threshold was impacted by ion loading, where distinct cracking was observed for 100% He + at a lower heat loading. This matrix study using reactor-like loading supports the need for extensive studies on future W alloy PFMs before selecting one as an alternative.

Physics↗

Analysis of Supercritical-Extracted Chelated Metal Ions From Mixed Organic-Inorganic Samples

Organic and inorganic contaminants of an environmental sample are analyzed by the same GC-MS instrument by adding an oxidizing agent to the sample to oxidize metal or metal compounds to form metal ions. The metal ions are converted to chelate complexes and the chelate complexes are extracted into a supercritical fluid such as CO2. The metal chelate extract after flowing through a restrictor tube is directly injected into the ionization chamber of a mass spectrometer, preferably containing a refractory metal filament such as rhenium to fragment the complex to release metal ions which are detected. This provides a fast, economical method for the analysis of metal contaminants in a sample and can be automated. An organic extract of the sample in conventional or supercritical fluid solvents can be detected in the same mass spectrometer, preferably after separation in a supercritical fluid chromatograph.

Sinha, Mahadeva P.↗

Ion-beam-induced atomic mixing

Calculations based on the diffusion model are presented of atomic mixing by ion bombardment. This mixing is assumed to have its basis, as does sputtering, in the collision cascades generated by the primary beam. Sharp interfaces within a target are seen to be smoothed by ion bombardment. Mixing may place fundamental limits on the resolution of ion microprobes.

Haff, P. K.↗

Neutral oxygen and sulfur densities in the Io torus

Ultraviolet spectra (1150-1750 A) of the Io torus, obtained using a rocket-borne telescope and spectrometer in May 1981, show emissions of neutral sulfur and neutral oxygen, as well as ionic emissions of S II, S III, and S IV. The emissions are observed almost 180 deg from the location of the satellite Io and imply the existence of an extended neutral atomic cloud associated with the torus. In the present work, neutral densities and ion mixing ratios are derived by modeling the observations using torus electron temperature and density profiles proportional to those at the time of the Voyager 1 encounter. The model includes the effects of photoexcitation, which can be considerable if the neutral cloud is large enough. At the time of the observation, substantial densities of neutral oxygen and neutral sulfur are found in regions of the torus far from Io. These lower limits on the neutral densities are compared to theoretical models of the neutral source, and the ion mixing ratios are compared to IUE observations of the torus obtained over a period of 5 yr. Arguments that tend to rule out Europa as the source of the neutral emission are also presented.

Skinner, T. E.↗

High-Current Light-Ion Cyclotron for Applications in Nuclear Security and Radioisotope Production

In this article, we propose the conceptual design, with supporting beam dynamics results, of a normal conducting, separated-sector cyclotron with a strong-focusing field gradient designed to accelerate light ions with a charge-to-mass ratio of 1/2 up to 15–20 MeV/u. The design can support a host of applications for therapy, radiobiology, material science, and instrumentation development. The light-ion species, which can include a mixed ion beam, can be dynamically chosen to provide a range of characteristic signals appropriate for specific material identification such as special nuclear materials. A conservative baseline concept is presented which has been optimized for radioisotope production of alpha emitters and theranostic radiopharmaceuticals. The modular design is also demonstrated to be scalable in gross physical parameters by a factor of 2–3, thereby reducing the size, weight, and power requirements (SWaP) and enabling near-term security applications.

07 ISOTOPE AND RADIATION SOURCES↗

Long-term stability of the Io high-temperature plasma torus

The short wavelength camera of the International Ultraviolet Explorer satellite was used to measure S II 1256, S III 1199, semiforbidden S III 1729, and semiforbidden S IV 1406 emission from the high-temperature region of the Io plasma torus. Observations over a period of five years (1979-1984) indicate that the Io plasma parameters have relatively small variations, particularly in the case of the mixing ratio for the dominant constituent S(++), and electron temperature. A simple three-dimensional model of the plasma torus was used to obtain the ion mixing ratios and the plasma density for each observation. The results are compared with Voyager 1 data for mixing ratio (ion density divided by electron density); ionization balance; and plasma density. The results of the comparison are discussed in detail.

Moos, H. W.↗

Overview of Large Helical Device experiments of basic plasma physics for solving crucial issues in reaching burning plasma conditions

Recently, experiments on basic plasma physics issues for solving future problems in fusion energy have been performed on a Large Helical Device. There are several problems to be solved in future devices for fusion energy. Emerging issues in burning plasma are: alpha-channeling (ion heating by alpha particles), turbulence and transport in electron dominant heating helium ash exhaust, reduction of the divertor heat load. To solve these problems, understanding the basic plasma physics of (1) wave–particle interaction through (inverse) Landau damping, (2) characteristics of electron-scale (high-k) turbulence, (3) ion mixing and the isotope effect, and (4) turbulence spreading and detachment, is necessary. This overview discusses the experimental studies on these issues and turbulent transport in multi-ion plasma and other issues in the appendix.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

The Role of Side Chains and Hydration on Mixed Charge Transport in n ‐Type Polymer Films

Abstract Introducing ethylene glycol (EG) side chains to a conjugated polymer backbone is a well‐established synthetic strategy for designing organic mixed ion‐electron conductors (OMIECs). However, the impact that film swelling has on mixed conduction properties has yet to be scoped, particularly for electron‐transporting (n‐type) OMIECs. Here, the authors investigate the effect of the length of branched EG chains on mixed charge transport ofn‐type OMIECs based on a naphthalene‐1,4,5,8‐tetracarboxylic‐diimide‐bithiophene backbone. Atomic force microscopy (AFM), grazing‐incidence wide‐angle X‐ray scattering (GIWAXS), and scanning tunneling microscopy (STM) are used to establish the similarities between the common‐backbone films in dry conditions. Electrochemical quartz crystal microbalance with dissipation monitoring (EQCM‐D) and in situ GIWAXS measurements reveal stark changes in film swelling properties and microstructure during electrochemical doping, depending on the side chain length. It is found that even in the loss of the crystallite content upon contact with the aqueous electrolyte, the films can effectively transport charges and that it is rather the high water content that harms the electronic interconnectivity within the OMIEC films. These results highlight the importance of controlling water uptake in the films to impede charge transport inn‐type electrochemical devices.

Chemistry↗

Direct Observation of Defect‐Aided Structural Evolution in a Nickel‐Rich Layered Cathode

Abstract Ni‐rich LiNi 1− x − y Mn x Co y O 2 (NMC) layered compounds are the dominant cathode for lithium ion batteries. The role of crystallographic defects on structure evolution and performance degradation during electrochemical cycling is not yet fully understood. Here, we investigated the structural evolution of a Ni‐rich NMC cathode in a solid‐state cell by in situ transmission electron microscopy. Antiphase boundary (APB) and twin boundary (TB) separating layered phases played an important role on phase change. Upon Li depletion, the APB extended across the layered structure, while Li/transition metal (TM) ion mixing in the layered phases was detected to induce the rock‐salt phase formation along the coherent TB. According to DFT calculations, Li/TM mixing and phase transition were aided by the low diffusion barriers of TM ions at planar defects. This work reveals the dynamical scenario of secondary phase evolution, helping unveil the origin of performance fading in Ni‐rich NMC.

Li, Shuang↗

Direct observation of defect-aided structural evolution in Ni-rich layered cathode

Ni-rich LiNi 1-x-y Mn x Co y O 2 (NMC) layered compounds have become the dominated cathode for lithium ion batteries. The role of crystallographic defects on their structure evolution and consequent performance degradation during electrochemical cycling is not yet fully understood. In this work, we investigated the structural evolution of Ni-rich NMC cathode in a solid-state cell via in-situ transmission electron microscopy. We identified antiphase boundary (APB) and twin boundary (TB) separating layered phases played an important role on phase change. Upon the lithium depletion, the APB extends across the layered structure, while Li/transition metal (TM) ion mixing in the layered phases is detected to induce the rock-salt phase formation along the coherent TB. According to DFT calculations, Li/TM mixing and phase transition are aided by the low diffusion barriers of TM ions at planar defects. Finally, this work reveals the dynamical scenario of secondary phase evolution, which helps to unveil the origin of performance fading in Ni-rich NMC.

25 ENERGY STORAGE↗

Ion diffusion coefficients in poly(3-alkylthiophenes) for energy conversion and biosensing: role of side-chain length and microstructure

Conductive polymers are promising materials as active elements for energy storage and conversion devices due to mixed ion–electron conduction. The ion diffusion coefficient is a relative measure of the efficacy of ion transport, allowing for comparison between materials and electrochemical conditions. In this work, diffusion coefficients of hexafluorophosphate (PF6–) counterions in poly(3-alkylthiophene) (P3AT) materials are measured as a function of both side-chain length and microstructure using electrochemical impedance spectroscopy (EIS). For semi-crystalline films, the diffusion coefficient is found to be anomalous and nearly independent of applied electrochemical potential. Here, the anomalous behavior of diffusion indicates that spin casting yields compact films with an enthalpic barrier to ion transport, attributed to ionic trapping. Diffusion coefficient values ~10 –11 cm 2 s –1 were measured for all films, indicating interchain spacing, in the absence of strong intermolecular interactions with the electrolyte, is not a viable design strategy to control ion transport. For the prototypical system of poly(3-hexylthiophene), we observe almost no potential dependence in ion transport for regioregular and regiorandom films of comparable molecular weight, with both exhibiting anomalous diffusion. Alternatively, changing the microstructure of poly(3-hexylthiophene) to a mostly amorphous, ion-imprinted structure yields ~500× increase in the diffusion coefficient to ~2 × 10 –8 cm 2 s –1 at 0.8 V vs. Ag/Ag + with behavior closer to ordinary diffusion. Collectively, these results indicate new insight into ion transport in conductive polymers, where ionic trapping effects can be mitigated through electrodeposition protocols over post-synthesis processing (i.e. spin coating).

14 SOLAR ENERGY↗

Selectivity of Electrochemical Ion Insertion into Manganese Dioxide Polymorphs

The ion insertion redox chemistry of manganese dioxide has diverse applications in energy storage, catalysis, and chemical separations. Unique properties derive from the assembly of Mn–O octahedra into polymorphic structures that can host protons and nonprotonic cations in interstitial sites. Despite many reports on individual ion-polymorph couples, much less is known about the selectivity of electrochemical ion insertion in MnO 2 . In this work, we use density functional theory to holistically compare the electrochemistry of A x MnO 2 (where A = H + , Li + , Na + , K + , Mg 2+ , Ca 2+ , Zn 2+ , Al 3+ ) in aqueous and nonaqueous electrolytes. We develop an efficient computational scheme demonstrating that Hubbard-U correction has a greater impact on calculating accurate redox energetics than choice of exchange-correlation functional. Using PBE+U, we find that for nonprotonic cations, ion selectivity depends on the oxygen coordination environments inside a polymorph. When H + is present, however, the driving force to form hydroxyl bonds is usually stronger. In aqueous electrolytes, only three ion-polymorph pairs are thermodynamically stable within water’s voltage stability window (Na + and K + in α-MnO 2 , and Li + in λ-MnO 2 ), with all other ion insertion being metastable. We find Al 3+ may insert into the δ, R, and λ polymorphs across the full 2-electron redox of MnO 2 at high voltage; however, electrolytes for multivalent ions must be designed to impede the formation of insoluble precipitates and facilitate cation desolvation. We also show that small ions coinsert with water in α-MnO 2 to achieve greater coordination by oxygen, while solvation energies and kinetic effects dictate water coinsertion in δ-MnO 2 . Finally, taken together, these findings explain reports of mixed ion insertion mechanisms in aqueous electrolytes and highlight promising design strategies for safe, high energy density electrochemical energy storage, desalination batteries, and electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Redesign of the Extravehicular Mobility Unit Airlock Cooling Loop Recovery Assembly

During EVA (Extravehicular Activity) 23 aboard the ISS (International Space Station) on 07/16/2013 an episode of water in the EMU (Extravehicular Mobility Unit) helmet occurred, necessitating a termination of the EVA (Extravehicular Activity) shortly after it began. The root cause of the failure was determined to be ground-processing short-comings of the ALCLR (Airlock Cooling Loop Recovery) Ion Beds which led to various levels of contaminants being introduced into the Ion Beds before they left the ground. The Ion Beds were thereafter used to scrub the failed EMU cooling water loop on-orbit during routine scrubbing operations. The root cause investigation identified several areas for improvement of the ALCLR Assembly which have since been initiated. Enhanced washing techniques for the ALCLR Ion Bed have been developed and implemented. On-orbit cooling water conductivity and pH analysis capability to allow the astronauts to monitor proper operation of the ALCLR Ion Bed during scrubbing operation is being investigation. A simplified means to acquire on-orbit EMU cooling water samples have been designed. Finally, an inherently cleaner organic adsorbent to replace the current lignite-based activated carbon, and a non-separable replacement for the separable mixed ion exchange resin are undergoing evaluation. These efforts are undertaken to enhance the performance and reduce the risk associated with operations to ensure the long-term health of the EMU cooling water circuit.

Steele, John↗

Redesign of the Extravehicular Mobility Unit Airlock Cooling Loop Recovery Assembly

During EVA (Extravehicular Activity) 23 aboard the ISS (International Space Station) on 07/16/2013 an episode of water in the EMU (Extravehicular Mobility Unit) helmet occurred, necessitating a termination of the EVA (Extravehicular Activity) shortly after it began. The root cause of the failure was determined to be ground-processing short-comings of the ALCLR (Airlock Cooling Loop Recovery) Ion Beds which led to various levels of contaminants being introduced into the Ion Beds before they left the ground. The Ion Beds were thereafter used to scrub the failed EMU cooling water loop on-orbit during routine scrubbing operations. The root cause investigation identified several areas for improvement of the ALCLR Assembly which have since been initiated. Enhanced washing techniques for the ALCLR Ion Bed have been developed and implemented. On-orbit cooling water conductivity and pH analysis capability to allow the astronauts to monitor proper operation of the ALCLR Ion Bed during scrubbing operation is being investigated. A simplified means to acquire on-orbit EMU cooling water samples has been designed. Finally, an inherently cleaner organic adsorbent to replace the current lignite-based activated carbon, and a non-separable replacement for the separable mixed ion exchange resin are undergoing evaluation. These efforts are undertaken to enhance the performance and reduce the risk associated with operations to ensure the long-term health of the EMU cooling water circuit.

Steele, John↗

Temperature Effects on Interdiffusion of Al and U-Mo under Irradiation

A high-energy Xe ion irradiation experiment was conducted to investigate the temperature dependence of interdiffusion in bilayer Al-UMo samples under irradiation. The amount of interdiffusion achieved at a fixed dose with the increase of temperature showed a clear transition at 175 degrees C (with an estimated error in the range of ± 10 degrees C) from temperature-independent to temperature-dependent behavior. The activation energy derived from the curve of interdiffusion quantity vs. irradiation temperature is 0.77 ± 0.16 eV. This information has been utilized to understand the temperature effect on the interdiffusion process that occurred at the interfaces of U-Mo particles and the Al matrix in U-Mo/Al dispersion fuels, whose magnitude significantly impacts the fuel's performance. Although this temperature effect was deemed important, it cannot be examined directly using in-pile irradiation data, as fuel temperatures cannot be measured in reactor irradiation and are highly correlated with fission rate and thermal conductivity evolution. To connect the knowledge accumulated from ion irradiation with in-pile irradiation data, simulation of a full-sized U-Mo/Al dispersion fuel plate irradiated in the FUTURE test in the BR2 reactor was performed with the Dispersion Analysis Research Tool (DART), a dispersion fuel performance code. DART is equipped with an interaction or interdiffusion layer (IL) growth correlation formulated to describe the temperature dependence of ion mixing results. The agreement between calculated and measured fuel meat constituent volume fractions and swelling data demonstrated that the temperature effect on in-pile Al-UMo interdiffusion is well captured with the correlation. In this case, the fitted activation energy is 0.70 eV. Considering the uncertainties associated with the ion irradiation data, the activation energy obtained from in-pile data fitting is in accord with that from ion irradiation results.

36 MATERIALS SCIENCE↗