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At least 613 records · Page 34

Biomimetic composite architecture achieves ultrahigh rate capability and cycling life of sodium ion battery cathodes

Sodium ion batteries are an emerging candidate to replace lithium ion batteries in large-scale electrical energy storage systems due to the abundance and widespread distribution of sodium. Despite the growing interest, the development of high-performance sodium cathode materials remains a challenge. In particular, polyanionic compounds are considered as a strong cathode candidate owing to their better cycling stability, a flatter voltage profile, and stronger thermal stability compared to other cathode materials. Here, we report the rational design of a biomimetic bone-inspired polyanionic Na3V2(PO4)3-reduced graphene oxide composite (BI-NVP) cathode that achieves ultrahigh rate charging and ultralong cycling life in a sodium ion battery. At a charging rate of 1 C, BI-NVP delivers 97% of its theoretical capacity and is able to retain a voltage plateau even at the ultra-high rate of 200 C. It also shows long cycling life with capacity retention of 91% after 10 000 cycles at 50 C. The sodium ion battery cells with a BI-NVP cathode and Na metal anode were able to deliver a maximum specific energy of 350 W h kg−1 and maximum specific power of 154 kW kg−1. In situ and postmortem analyses of cycled BI-NVP (including by Raman and XRD spectra) HRTEM, and STEM-EELS, indicate highly reversible dilation–contraction, negligible electrode pulverization, and a stable NVP-reduced graphene oxide layer interface. The results presented here provide a rational and biomimetic material design for the electrode architecture for ultrahigh power and ultralong cyclability of the sodium ion battery full cells when paired with a sodium metal anode.

25 ENERGY STORAGE↗

Epitaxial SrTiO 3 films with dielectric constants exceeding 25,000

Significance Semiconductor interfaces are among the most important in use in modern technology. The properties they exhibit can either enable or disable the characteristics of the materials they connect for functional performance. While much is known about important junctions involving conventional semiconductors such as Si and GaAs, there are several unsolved mysteries surrounding interfaces between oxide semiconductors. Here we resolve a long-standing issue concerning the measurement of anomalously low dielectric constants in SrTiO 3 films with record high electron mobilities. We show that the junction between doped and undoped SrTiO 3 required to make dielectric constant measurements masks the dielectric properties of the undoped film. Through modeling, we extract the latter and show that it is much higher than previously measured.

36 MATERIALS SCIENCE↗

FEBIP for functional nanolithography of 2D nanomaterials

Lithographic patterning on emerging nanomaterials is one of essential ingredients for the development of new functional nanomaterial and device systems. Focused electron beam induced processing (FEBIP) in combination with an on-demand reconfigurable precursor injection system enables the highest resolution and controllability of nanolithography on two-dimensional (2D) nanomaterials. FEBIP allows for localized atomic-to-nanoscale engineering of nanomaterials and devices in a multi-mode format including geometrical patterning, functionalization/defect formation/doping, metal/metal oxide deposition, interface fusion and activation, active channel cleaning. This chapter discusses the scientific bases and showcases the state-of-the-art FEBIP technologies with a specific focus on functional lithography of 2D nanomaterials and provides future prospects of FEBIP technologies to address real industrial needs for the development of high-performance, next-generation functional devices.

2D materials, nanolithography, focused electron be↗

Role of Oxygen on Chemical Segregation in Uncapped Ge 2 Sb 2 Te 5 Thin Films on Silicon Nitride

Germanium antimony telluride has been the most used and studied phase-change material for electronic memory due to its suitable crystallization temperature, amorphous to crystalline resistance contrast, and stability of the amorphous phase. In this paper, the segregation of Ge in a Ge 2 Sb 2 Te 5 film of 30 nm thickness during heating inside the transmission electron microscope was observed and characterized. Furthermore, Ge 2 Sb 2 Te 5 film was deposited using sputtering on a Protochips Fusion holder and left uncapped in atmosphere for about four months. Oxygen incorporated within the film played a significant role in the chemical segregation observed which resulted in amorphous Ge-O island boundaries and Sb and Te rich crystalline domains. Such composition changes can occur when the phase-change material interfaces insulating oxide layers in an integrated device and can significantly impact its electrical and thermal properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Neutron irradiation effects on the corrosion of Zircaloy-4 in a pressurized water reactor environment - 2016-0085

Long-time Advanced Test Reactor (ATR) corrosion weight-gain data from non-fueled α-processed Zircaloy-4 cladding coupons are presented herein. The data were generated in pressurized loops that simulated pressurized water reactor (PWR) chemistry, temperature, and neutron flux conditions. High neutron flux and high-fluence post-transition corrosion rates were accelerated over out-of-flux post-transition corrosion rates by more than 40 times at 270 deg. C and more than 30 times at 310 deg. C We conclude in large part that the acceleration was caused by irradiation-induced changes to the base metal. The effect that irradiation has on the base metal and its effect on corrosion has been shown in the past to be carried over into post-irradiation tests in autoclave environments, but its impact was shown in this study to be accentuated in the in-reactor environment, in which sustained corrosion accelerations were much greater than observed in the postirradiation tests (in non-irradiation environments). This suggests some aspect of the radiation environment potentially acts synergistically with the corrosion film formed from the irradiation-damaged base metal to further accelerate in-reactor corrosion rates. We also present results from detailed microstructural examinations of thick (more than 25 μm) oxide films formed on α-processed Zircaloy-4 grown in a 360 deg. C autoclave and in the reactor. The examinations consisted of optical microscopy, field emission gun scanning electron microscopy, focused ion beam microscopy, analytical electron microscopy, and X-ray diffraction, with a focus on the evolution of the microstructure of the intermetallic precipitates in the oxide films during exposure to autoclave water or to the corroding environment under neutron irradiation. The film microstructure suggests that the water environment was closer to the oxide-metal interface in the films grown in the reactor than in the autoclave-grown corrosion films examined, but it was not obvious from the microstructural examinations how the radiation environment facilitated that effect. (authors)

36 MATERIALS SCIENCE↗

Fabrication of Position Controlled Si/SiGe Quantum Dots for Integrated Optical Sources and Beyond

Recent work done at the University of Florida (UF) revealed a tremendously enhanced germanium diffusion process along silicon/silicon dioxide interfaces during oxidizing anneals, allowing for the controlled formation of Si quantum wires. This project seeks to further explore this unusual germanium behavior during oxidation for the purpose of forming unique and useful nano and quantum structures. Specifically, we propose here to demonstrate for the first time that this phenomenon can be extended to realize OD Si nanostructures through the oxidation of axially heterostructured vertical Si/SiGe pillars. Such structures could be of great interest for applications in integrated optoelectronics, beyond Moore's Law computing, and quantum computing.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A General Overview of Cathodic Protection in Reinforced Concrete

Corrosion of reinforcement steel in concrete is a prevalent issue in infrastructures worldwide, with the direct costs of repair estimated to be $1 trillion annually. Treatment options are complicated by the concrete’s role in the corrosion process. Ordinary, modern-day cement is so alkaline that it maintains a thick passive layer on the steel surface, reducing corrosion to inconsequential rates. However, environmental contaminants in the form of carbon dioxide or chlorides may cause a breakdown in the passive layer, exposing the steel surface to corrosion. Galvanic cells will be free to form due to potential differences along the rebar, and anode sites will create dissolved iron ions that cannot travel far through the still concrete. Thus, rust products will accumulate directly onto the steel/concrete interface. Iron oxides have a much higher volume relative to steel, and even a miniscule amount of rust can produce enough volumetric stress to cause cracking, spalling and delamination of the surrounding concrete, increasing the risk of structural failure. Safeguards and inhibiting technology exist to limit the chances of corrosion initiation by either species, but cracking of the concrete cover and gradual accumulation of contaminants means that corrosion is unavoidable in certain environments and will initiate, given enough time.

36 MATERIALS SCIENCE↗

Tunneling in thin MOS structures

Recent results on tunneling in thin MOS structures are described. Thermally grown SiO2 films in the thickness range of 22-40 A have been shown to be effectively uniform on an atomic scale and exhibit an extremely abrupt oxide-silicon interface. Resonant reflections are observed at this interface for Fowler-Nordheim tunneling and are shown to agree with the exact theory for a trapezoidal barrier. Tunneling at lower fields is consistent with elastic tunneling into the silicon direct conduction band and, at still lower fields, inelastic tunneling into the indirect conduction band. Approximate dispersion relations are obtained over portions of the silicon-dioxide energy gap and conduction band.

Maserjian, J.↗

Limiting process in shallow junction solar cells

In extending the violet and nonreflective cell technology to lower resistivities, several processes limiting output power were encountered. The most important was the dark diffusion current due to recombination at the front grid contacts. After removal of this problem by reduction of the silicon metal contact area (to 0.14 percent of the total area), the electric field enhanced junction recombination current J sub r was the main limitation. Alteration of the diffusion profile to reduce the junction field is shown to be an effective means of influencing J sub r. The remaining problems are the bulk recombination in the n+ layer and the surface recombination at the oxide-silicon interface; both of these problems are aggravated by band-narrowing resulting from heavy doping in the diffused layer. Experimental evidence for the main limitations is shown, where increased diffusion temperature is seen to reduce both the influence of the front grid contacts and the junction electric field by increasing the junction depth. The potential for further significant improvement in efficiency appears to be high.

Meulenberg, A.↗

Photoemission measurements of interface barrier energies for tunnel oxides on silicon

Internal photoemission measurements of the Si/SiO2 and Al/SiO2 barrier heights on oxides of tunneling thickness (43-56 A) are compared with measurements on thick oxides (310 A and greater) and the barrier heights are found to be the same. The results suggest that substantially thinner oxides, grown by the same method, can be characterized by the same barrier heights. Limits to the experimental technique posed by photovoltaic and displacement currents, and transport of hot carriers in the tunnel oxide are discussed.

Dressendorfer, P. V.↗

To Produce Nutrients for Plant Growth

On July 1, 1979 a new research program entitled "Development of a Prototype Experiment for Treating CELSS and PCELSS Wastes to Produce Nutrients for Plant Growth" was undertaken by the Massachusetts Institute of Technology and the Georgia Institute of Technology under grant from the National Aeronautics and Space Administration's Ames Research Center. The program was designed to be completed over a five-year period, with the work divided into two phases. Phase I covers approximately two years and involves the development of necessary facilities, chemical methodologies and models to allow meaningful experiments during Phase II, which will involve interfacing waste oxidation with plant growth. Homogeneous samples of freeze-dried human feces and urine have been prepared to assure comparability of results among various CELSS waste treatment research groups. A model of food processing wastes within a PCELSS was developed, and an initial batch of waste was prepared. An automated gas chromatographic system to analyze oxidizer effluents was designed and is operational. A state-of-the-art quantitative elemental analysis capability, built around inductively coupled plasma emission spectroscopy and atomic absorption spectroscopy using electrothermal atomization, has been demonstrated. A continuous flow wet oxidation system was constructed and is now operational.

Michael Modell↗

An X-ray diffraction study of titanium oxidation

Titanium specimens of commercial purity were exposed at 1100 to 1400 F to laboratory air for times up to 100 hours. The extent of substrate contamination by interstitial oxygen was was determined by a new X-ray diffraction analysis involving transformation of X-ray diffraction intensity bands. The oxygen solid-solubility at the oxide-metal interfaces and its variation with time at temperature were also determined. Diffusion coefficients are deduced from the oxygen depth profiles.

Wiedemann, K. E.↗

Electrical characterization of plasma-grown oxides on gallium arsenide

Plasma-grown GaAs oxides and their interfaces have been characterized by measuring the electrical properties of metal-oxide-semiconductor capacitors and of Schottky junctions. The current transport mechanism in the oxide at high electrical field was found to be Frankel-Poole emission, with an electron trap center at 0.47 eV below the conduction band of the oxide. The interface-state density, evaluated from capacitance and conductance measurements, exhibits a U-shaped interface-state continuum extending over the entire band gap. Two discrete deep states with high concentration are superimposed on this continuum at 0.40 and 0.70 eV below the conduction band. The results obtained from measurements on Schottky junctions have excluded the possibility that these two deep states originate from plasma damage. Possible origins of these states are discussed in this paper.

Hshieh, F. I.↗

Microstructural aspects of zirconia thermal barrier coatings

Various combination of plasma-sprayed bond coatings and zirconia ceramic coatings on a nickel-based superalloy substrate were tested by static thermal exposure at 1200 C and cyclic thermal exposure to 1000 C. The bond coats were based on Ni-Cr-Al alloys with additions of rare earth elements and Si. The ceramic coats were various ZrO2-Y2O3 compositions, of which the optimum was found to be ZrO2-8.9 wt percent Y2O3. Microstructural analysis showed that resistance to cracking during thermal exposure is strongly related to deleterious phase changes. Zones depleted of Al formed at the bond coat/ceramic coat interface due to oxidation and at the bond coat/substrate interface due to interdiffusion, leading eventually to breakdown of the bond coat. The 8.9 percent Y2O3 coating performed best because the as-sprayed metastable tetragonal phase converted slowly into the low-Y2O3 tetragonal plus high-Y2O3 cubic-phase mixture, so that the deleterious monoclinic phase was inhibited from forming. Failure appeared to start with the formation of circumferential cracks in the zirconia, probably due to compressive stresses during cooling, followed by the formation of radial cracks due to tensile stresses during heating. Cracks appeared to initiate at the Al2O3 scale/bond coat interface and propagate through the zirconia coating. Comparisons were made with the behavior of bulk ZrO2-Y2O3 and the relationship between the microstructure of the tetragonal phase and the phase diagram. A separate investigation was also made of the ZrO2-Al2O3 interface.

Mitchell, T. E.↗

Effect of 0.1 at. pct Zirconium on the cyclic oxidation resistance of beta-NiAl

The effect of 0.1 at. pct Zr on the cyclic oxidation of hipped beta-NiAl was studied. Oxidation testing was performed in static air at 1100-1200 C, using 1-hr exposure cycles for test times up to 3000 hr. The weight change versus time data were modeled with the COSP computer program to analyze and predict cyclic-oxidation behavior. Zr additions significantly change the nature of the scale-spalling process during cooling, so that the oxide spalls near the oxide-air interface at a relatively low depth within the scale. Without Zr, the predominantly alpha-Al2O3 scale tends to spall randomly to bare metal at relatively high effective-scale-loss rates, particularly at 1150 C and 1200 C. This leads to higher rates of Al consumption for the Zr-free aluminide and much earlier depletion of Al, leading to eventual breakaway (i.e., failure).

Barrett, Charles A.↗