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At least 667 records · Page 37

Low Temperature Flux Growth of 2H-SiC and Beta-Gallium Oxide

We present brief overview of our study on the low temperature flux growth of two very important novel wide bandgap materials 2H-SiC and Beta-gallium oxide (Beta-Ga2O3). We have synthesized and grown 5 millimeter to 1 centimeter size single crystals of Beta-gallium oxide (Beta-Ga2O3). We used a flux and semi wet method to grow transparent good quality crystals. In the semi-wet method Ga2O3 was synthesized with starting gallium nitrate solution and urea as a nucleation agent. In the flux method we used tin and other metallic flux. This crystal was placed in an alumina crucible and temperature was raised above 1050 degrees Centigrade. After a time period of thirty hours, we observed prismatic and needle shaped crystals of gallium oxide. Scanning electron microscopic studies showed step growth morphology. Crystal was polished to measure the properties. Bandgap was measured 4.7electronvolts using the optical absorption curve. Another wide bandgap hexagonal 2H-SiC was grown by using Si-Al eutectic flux in the graphite crucible. We used slight AlN also as the impurity in the flux. The temperature was raised up to 1050 degrees Centigrade and slowly cooled to 850 degrees Centigrade. Preliminary characterization results of this material are also reported.

Singh, N. B.↗

Measurement of Sn and In Solidification Undercooling and Lattice Expansion Using in situ x-ray diffraction

Undercooling of low melting point metals, Sn and In, on graphite, Cu, and Au-coated Cu surfaces is examined using an in-situ x-ray diffraction technique. Undercoolings of up to 56.1 C were observed for Sn solidified on graphite, which is a non-wetting substrate, while lower undercoolings were observed for Sn of 17.3 C on Au/Ni/Cu and 10.5 C on Cu surfaces. Indium behaved quite differently, showing undercoolings of less than 4 C on all three substrates. In addition, lattice expansion/contraction behavior of Sn, In and intermetallic compounds (IMCs) that formed during the reaction of Sn with the Au/Ni/Cu surface were measured. Results showed anisotropic and non-linear expansion of both Sn and In, with a contraction, rather than expansion, of the basal planes of In during heating. The principal IMC that formed between Sn and the Au/Ni/Cu surface was characterized as CuSn and had an average expansion coefficient of 13.6x10-6/ C, which is less than that of Sn or Cu.

36 MATERIALS SCIENCE↗

A facile approach to prepare graphene via solvothermal reduction of graphite oxide

Highlights: • Graphene was prepared via a novel and facile solvothermal reduction method for graphite oxide. • Most of the oxygen functional groups of graphite oxide were removed. • The reduced graphene oxide obtained was featured with bilayer nanosheets. - Abstract: In this work, a facile reduction strategy is reported for the fabrication of graphene. Graphite oxide (GO) is reduced via a novel solvothermal reaction in a mixed solution of acetone and sodium hypochlorite (NaClO). The structure, surface chemistry, morphology and thermal stability of the as-prepared reduced graphene oxide (RGO) are characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, transmission electron microscopy (TEM), atomic force microscopy (AFM), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The results indicate that most of the oxygenated groups in GO are effectively removed in this solvothermal reaction. The novel reduction method provides a simple, cost-effective and efficient strategy for the fabrication of graphene.

36 MATERIALS SCIENCE↗

On the preparation of TiAl alloy by direct reduction of the oxide mixtures in calcium chloride melt

In recent years, TiAl-based intermetallic alloys are being increasingly considered for application in areas such as (i) automobile/transport sector (passenger cars, trucks and ships) (ii) aerospace industry (jet engines and High Speed Civil Transport propulsion system) and (iii) industrial gas turbines. These materials offer excellent (i) high temperature properties (at higher than 6000C) (ii) mechanical strength and (iii) resistance to corrosion and as a result have raised renewed interest. The combination of these properties make them possible replacement materials for traditional nickel-based super-alloys, which are nearly as twice as dense (than TiAl based alloys). Since the microstructures of these intermetallic alloys affect, to a significant extent, their ultimate performance, further improvements (by way of alteration/modification of these microstructures), have been the subject matter of intense research investigations. It has now been established that the presence of alloy additives, such as niobium, tantalum, manganese, boron, chromium, silicon, nickel and yttrium etc, in specific quantities, impart marked improvement to the properties, viz. fatigue strength, fracture toughness, oxidation resistance and room temperature ductility, of these alloys. From a number of possible alloy compositions, {gamma}-TiAl and Ti-Al-Nb-Cr have, of late, emerged as two promising engineering alloys/materials. . The conventional fabrication process of these alloys include steps such as melting, forging and heat treatment/annealing of the alloy compositions. However, an electrochemical process offers an attractive proposition to prepare these alloys, directly from the mixture of the respective oxides, in just one step. The experimental approach, in this new process, was, therefore, to try to electrochemically reduce the (mixed) oxide pellet to an alloy phase. The removal of oxygen, from the (mixed) oxide pellet, was effected by polarizing the oxide pellet against a graphite electrode in a pool of molten calcium chloride at a temperature of 9000C. The dominant mechanism of the oxygen removal was the ionization of oxygen followed by its subsequent discharge, as CO2/CO, at the anode surface. The removal of oxygen from the oxide mixture helped form the alloy in situ. The presentation shall cover the detailed experimental results pertaining to the preparation, evaluation and characterization of Ti-47Al-2Nb-2Cr (atom%) alloy.

36 MATERIALS SCIENCE↗

Real-Time Observation of Nanoscale Kink Band Mediated Plasticity in Ion-Irradiated Graphite: An In Situ TEM Study

Graphite IG-110 is a synthetic polycrystalline material used as a neutron moderator in reactors. Graphite is inherently brittle and is known to exhibit a further increase in brittleness due to radiation damage at room temperature. To understand the irradiation effects on pre-existing defects and their overall influence on external load, micropillar compression tests were performed using in situ nanoindentation in the Transmission Electron Microscopy (TEM) for both pristine and ion-irradiated samples. While pristine specimens showed brittle and subsequent catastrophic failure, the 2.8 MeV Au2+ ion (fluence of 4.378 × 1014 cm−2) irradiated specimens sustained extensive plasticity at room temperature without failure. In situ TEM characterization showed nucleation of nanoscale kink band structures at numerous sites, where the localized plasticity appeared to close the defects and cracks while allowing large average strain. We propose that compressive mechanical stress due to dimensional change during ion irradiation transforms buckled basal layers in graphite into kink bands. The externally applied load during the micropillar tests proliferates the nucleation and motion of kink bands to accommodate the large plastic strain. The inherent non-uniformity of graphite microstructure promotes such strain localization, making kink bands the predominant mechanism behind unprecedented toughness in an otherwise brittle material.

36 MATERIALS SCIENCE↗

Radiometric characterization of a high temperature blackbody in the visible and near infrared

At the Physikalisch-Technische Bundesanstalt the radiance temperature in the range from 962 °C to 3000 °C is disseminated by applying a high temperature blackbody (HTBB) with a directly heated pyrolytic graphite cavity. The thermodynamic radiance temperature of the HTBB was measured in the temperature range from 1000 °C to 3000 °C by applying almost simultaneously absolutely calibrated silicon photodiode based filter radiometers with centre wavelengths at 476 nm, 676 nm, 800 nm, 900 nm and 1000 nm and InGaAs photodiode based filter radiometers with centre wavelengths at 1300 nm, 1550 nm and 1595 nm. The results demonstrate that, expressed in terms of irradiance, within an uncertainty of 0.1 % (k=1) in a broad wavelength range the thermodynamic radiance temperature of the HTBB is wavelength independent in the investigated temperature interval.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Preparation and characterization of microwave absorbing composite materials with GSs or FeCo/GS composites

Highlights: • It is found that adding GSs or FeCo/GSs composite into the sample SiC/NR can greatly increase RL and the absorbing peak shifts to low-frequency with increasing the adding amount. • The optimum adding amount of GSs is 2%. The sample GS-200-2% possesses the lowest RL value of −31.27 dB at 7.6 GHz. • The optimum adding amount of FeCo/GSs composite is 3%. The sample AGS-450-3% possesses the lowest RL value of −20.67 dB at 7.8 GHz. - Abstract: This study mainly explored the synthesis method of graphene sheets (GSs) and FeCo/graphene sheet (FeCo/GS) composites and evaluated the microwave absorbing characteristics of composite materials containing GSs or FeCo/GS composites. First, graphite oxide (GO) was synthesized by the modified Hummers method. The synthesized GO was further used to synthesize GSs and FeCo/GS composites. Afterward, GSs or FeCo/GS composites were mixed with silicon carbide (SiC) and natural rubber (NR) to prepare microwave absorbing materials with thicknesses of 2 mm. Finally, identification and characterization of these samples were performed by XRD, FE-SEM, TEM, TGA, ESCA, RS, AFM and VNA. GSs were synthesized successfully at a low annealing temperature of 200 °C, and their thicknesses were between 0.848 nm and 2.115 nm, which corresponds to 2–6 stacked layers of graphene. FeCo/GS composites were also synthesized successfully at three different annealing temperatures. The nanoparticles of metals and metal oxides were well-dispersed on the surfaces of and the spaces between GSs. It was found that adding GSs or FeCo/GS composites into the SiC/NR sample can greatly increase reflection loss (RL) and that the absorbing peak shifts to lower frequencies as the concentration of added particles increases. The optimum concentration of added GSs was 2 wt.%. The GS-200-2% sample possessed the lowest RL value of −31.27 dB at 7.6 GHz. The optimum concentration of added FeCo/GS composites was 3 wt.%. The AGS-450-3% sample possessed the lowest RL value of −20.67 dB at 7.8 GHz.

36 MATERIALS SCIENCE↗

Resolving Graphite‐Electrolyte Interphase of Lithium‐Ion Batteries using Air‐Tight Ambient Mass Spectrometry

Abstract The formation of a stable solid electrolyte interphase (SEI) at graphite electrode is necessary for lithium‐ion batteries (LIB) to prevent excessive degradation of electrolytes. Until now, the exact organic composition of SEI has not been decisively determined with lithium ethylene mono‐carbonate (LEMC) being one of the debated components. An air‐tight ambient mass spectrometry (MS) platform is developed to directly characterize the air‐sensitive organic components present in SEI. Ionization occurs via a solvent‐free field‐induced process at atmospheric pressure. Our experimental data, based on tandem MS analysis, revealed LEMC to be the major organic component in SEI. This result resolves a long‐standing mystery surrounding the composition of native SEI in LIB, where no trace of the other debated compound, lithium ethylene dicarbonate, was detected. The energetics of fragmentation of LEMC and the corresponding stabilities of various ionic species detected during the air‐tight ambient MS analysis were calculated using density functional theory (DFT). Our findings confirmed favorable protonation energies and suggested the molecular structures for many of the detected species. Solvent (i. e., ethylene carbonate)‐induced stabilization effects observed during the ionization process were also confirmed by DFT. The reported study encourages the routine use of ambient mass spectrometry to characterize both anodic and cathodic electrodes of all battery types as well as to study other air‐sensitive materials in their native state.

25 ENERGY STORAGE↗

Catalytic propane dehydrogenation over In₂O₃–Ga₂O₃ mixed oxides

We have investigated the catalytic performance of novel In₂O₃–Ga₂O₃ mixed oxides synthesized by the alcoholic-coprecipitation method for propane dehydrogenation (PDH). Reactivity measurements reveal that the activities of In₂O₃–Ga₂O₃ catalysts are 1–3-fold (on an active metal basis) and 12–28-fold (on a surface area basis) higher than an In₂O₃–Al₂O₃ catalyst in terms of C₃H₈ conversion. The structure, composition, and surface properties of the In₂O₃–Ga₂O₃ catalysts are thoroughly characterized. NH₃-TPD shows that the binary oxide system generates more acid sites than the corresponding single-component catalysts. Raman spectroscopy suggests that catalysts that produce coke of a more graphitic nature suppress cracking reactions, leading to higher C₃H₆ selectivity. Lower reaction temperature also leads to higher C₃H₆ selectivity by slowing down the rate of side reactions. XRD, XPS, and XANES measurements, strongly suggest that metallic indium and In₂O₃ clusters are formed on the catalyst surface during the reaction. The agglomeration of In₂O₃ domains and formation of a metallic indium phase are found to be irreversible under O₂ or H₂ treatment conditions used here, and may be responsible for loss of activity with increasing time on stream.

Tan, Shuai↗

Linking spout fluidization hydrodynamics to pyrolytic carbon deposition characteristics in a fluidized bed chemical vapor deposition reactor

Spout fluidized bed chemical vapor deposition (SFB-CVD) is the dominant method for producing pyrolytic carbon (PyC) coatings on tristructural-isotropic (TRISO) fuel particles, yet the relationship between gas injector design, fluidization hydrodynamics, and resulting coating quality remains poorly quantified. Here, in this work, three spout fluidized bed (SFB) nozzle geometries were designed and fabricated to empirically investigate how injector-driven changes in particle circulation influence PyC deposition. The geometries were first evaluated in a room temperature fluidization apparatus using time-resolved particle image velocimetry, which highlighted distinct differences in particle velocity fields, circulation pathways, and overall fluidization quality. Graphite versions of each injector geometry were subsequently implemented in a laboratory-scale SFB-CVD reactor to deposit PyC onto surrogate fuel kernels under similar conditions. Post-deposition characterization included particle morphology, coating thickness, porosity distribution, optical anisotropy, and microindentation mechanical testing. Overall, the results show clear differences in coating microstructure as a function of changing injector geometry, despite mechanical testing indicating comparable elastic modulus values across all coatings. This study provides one of the first fully experimental, quantitative mappings between SFB nozzle geometry, fluidization hydrodynamics, and resulting PyC coating structure. The framework established here supports rational injector design and offers a pathway toward improved coating control in future pilot- and production-scale TRISO fuel fabrication systems.

Coated particle fuel↗

First-principles study of adsorption–desorption kinetics of aqueous V 2+ /V 3+ redox species on graphite in a vanadium redox flow battery

Vanadium redox flow batteries (VRFBs) represent a promising solution to grid-scale energy storage, and understanding the reactivity of electrode materials is crucial for improving the power density of VRFBs. However, atomistic details about the interactions between vanadium ions and electrode surfaces in aqueous electrolytes are still lacking. Here, we examine the reactivity of the basal (0001) and edge (11[2 with combining macron]0) graphite facets with water and aqueous V2+/V3+ redox species at 300 K employing Car–Parrinello molecular dynamics (CPMD) coupled with metadynamics simulations. The results suggest that the edge surface is characterized by the formation of ketonic C[double bond, length as m-dash]O functional groups due to complete water dissociation into the H/O/H configuration with surface O atoms serving as active sites for adsorption of V2+/V3+ species. The formation of V–O bonds at the surface should significantly improve the kinetics of electron transfer at the edge sites, which is not the case for the basal surface, in agreement with the experimentally hypothesized mechanism.

Jiang, Zhen↗

Nondestructive evaluation of composites by optical time domain reflectometry in imbedded optical fibers

The use of imbedded optical fibers to obtain dynamic two-dimensional dynamic-strain measurements by optical time-domain reflectometry (OTDR) in laminated composites is described. The fundamental principles of OTDR are reviewed, and the basic parameters resolution and dynamic range are defined. Results of OTDR measurements on 30-cm square plates of 0/90/90/0-deg graphite epoxy composite with type 1506 optical fibers imbedded in a serpentine pattern between (and parallel to the reinforcing fibers of) the 90-deg plates are presented in graphs and briefly characterized. It is estimated that processing the OTDR data with simple techniques could permit strain detection of the order 0.00001 at sampling rates as high as 1/ms.

Claus, R. O.↗

Electrochemical and anticorrosion behaviors of hybrid functionalized graphite nano-platelets/tripolyphosphate in epoxy-coated carbon steel

Highlights: • FGNP was combined with TPP to obtain a hybrid nano-particle. • TEM image showed uniform distribution of the hybrid nanoparticles in epoxy coating. • FGNP is a substrate for linking of TPP anions by hydrogen bonding. • FGNP as an accelerator, provides rapid iron phosphate passive film formation. • The hybrid nano-particle can provide long-term corrosion protection. - Abstract: Functionalized graphite nano-platelets (FGNP) were combined with tripolyphosphate (TPP) to gain a hybrid nano-particle (FGNP-TPP) with homogenous dispersion in epoxy, resulting in an excellent anti-corrosion coating for carbon steel substrate. Characterization analyses of the hybrid nano-particle were performed by FT-IR, SEM, XRD and TEM. TPP was linked to FGNP nano-particles by hydrogen bondings. Different epoxy coatings formulated with 1 wt.% of FGNP, FGNP-TPP and TPP were evaluated. Electrochemical investigations, salt spray and pull-off tests showed that the hybrid nano-particle can provide long-term corrosion protection compared to FGNP and TPP due to synergistic effect between FGNP as an accelerator and TPP as a corrosion inhibitor to produce a uniform and stable iron-phosphate passive film with high surface coverage.

36 MATERIALS SCIENCE↗

Effect of temperature on silicon-based anodes for lithium-ion batteries

Silicon is considered a promising anode candidate to replace graphite in lithium-ion (Li-ion) batteries for electric vehicle (EV) applications, given its high capacity (approximately 10 times higher than graphite) and, consequently, the higher energy density it can provide. However, to ensure that silicon can be used in EVs, it is necessary to determine whether it can withstand the temperature changes that an EV can experience. For this purpose, we evaluate the electrochemical performance of silicon-graphite (Si-Gr) half-cells at 4 different temperatures and explore the effect of adding fluoroethylene carbonate (FEC) to the electrolyte. We observe that cells cycled without FEC are temperature-sensitive; that is, the specific capacity, cyclability, and coulombic efficiency of Si-Gr vary as a function of the temperature applied. Conversely, the presence of FEC in the cell stabilizes the electrochemical behavior of Si-Gr, diminishing its sensitivity to temperature and providing similar reversible capacity, coulombic efficiency, and cycle-life. In this manuscript, we provide an explanation of the reasons causing this phenomenon along with other side effects of temperature, as proved by several characterization techniques.

25 ENERGY STORAGE↗

In situ deposition of hydroxyapatite on graphene nanosheets

Graphical abstract: A facile chemical precipitation method is reported for effective in situ deposition of hydroxyapatite on graphene nanosheets. Prior to grafting of hydroxyapatite, chemically modified graphene nanosheets were obtained by the reduction of graphene oxide in presence of ethylenediamine. Display Omitted Highlights: ► It is a facile and effective method for deposition of HA on GR nanosheets. ► It avoids the use of harmful reducing agents like hydrazine, NaBH{sub 4} etc. ► GR nanosheets were produced using bio-compatible, ethylenediamine. ► The graphitic structure of synthesized GR nanosheets was high ordered. ► The ratio of Ca to P in HA was 1.64, which is close to ratio in natural bone. -- Abstract: Graphene nanosheets were effectively functionalized by in situ deposition of hydroxyapatite through a facile chemical precipitation method. Prior to grafting of hydroxyapatite, chemically modified graphene nanosheets were obtained by the reduction of graphene oxide in presence of ethylenediamine. The resulting hydroxyapatite functionalized graphene nanosheets were characterized by attenuated total reflection IR spectroscopy, X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, X-ray energy dispersive spectroscopy, Raman spectroscopy and thermogravimetric analysis. These characterization techniques revealed the successful grafting of hydroxyapatite over well exfoliated graphene nanosheets without destroying their structure.

36 MATERIALS SCIENCE↗

Importance of gas heating in capacitively coupled radiofrequency plasma-assisted synthesis of carbon nanomaterials

In pursuit of diamond nanoparticles, a capacitively-coupled radio frequency flow-through plasma reactor was operated with methane-argon gas mixtures. Signatures of the final product obtained microscopically and spectroscopically indicated that the product was an amorphous form of graphite. This result was consistent irrespective of combinations of the macroscopic reactor settings. To explain the observed synthesis output, measurements of C 2 and gas properties were carried out by laser-induced fluorescence and optical emission spectroscopy. Strikingly, the results indicated a strong gas temperature gradient of 100 K per mm from the center of the reactor to the wall. Based on additional plasma imaging, a model of hot constricted region (filamentation region) was then formulated. It illustrated that, while the hot constricted region was present, the bulk of the gas was not hot enough to facilitate diamond sp 3 formation: characterized by much lower reaction rates, when compared to sp 2 , sp 3 formation kinetics are expected to become exponentially slow. This result was further confirmed by experiments under identical conditions but with a H 2 /CH 4 mixture, where no output material was detected: if graphitic sp 2 formation was expected as the main output material from the methane feedstock, atomic hydrogen would then be expected to etch it away in situ, such that the net production of that sp 2 -hybridized solid material is nearly a zero. Finally, the crucial importance of gas heating was corroborated by replacing RF with microwave source whereby facile sp 3 production was attained with H 2 /CH 4 gas mixture.

36 MATERIALS SCIENCE↗

EBS Report - LANL Experimental update of buffer/backfill at elevated P,T

The Used Fuel Disposition campaign is presently investigating various generic repository options for disposal of used fuel. Of interest are the disposal of high heat load canisters (up to 300 °C), which may allow for a reduced repository footprint. The focus of this experimental work is to increase our understanding on the stability of bentonite barriers under different geochemical and mineralogical conditions other than what has been previously investigated. Experiments were performed at 150 – 160 bars at temperatures up to 300 °C for five to six weeks. Unprocessed Wyoming bentonite was saturated with a K-Ca-Na-Cl-rich water at a 9:1 water:rock ratio. Experiments contained various steel plates or Cu-foil and were buffered to low Eh conditions using magnetite and metallic iron. Other experiments for international EBS research included mixed buffers and a heated bentonite with 20 wt. % free moisture for LBNL. The mixed buffer experiments (bentonite-graphite, bentonite-quartz sand) were conducted to investigate potential mineralogic/petrologic changes to mixed buffer systems proposed by the German nuclear repository program. Reaction products associated with the international EBS research were characterized by LANL with thermal-mechanical properties to be characterized by LBNL. The pH, K + , and Ca 2+ concentrations dropped, while SiO 2(aq) , Na + , and SO 4 2- concentrations increased throughout the experiments. The alkali and alkaline earth metals aqueous concentrations appear to be buffered via the montmorillonite and clinoptilolite exchange reactions. Illite or illite/smectite mixed-layer formation is significantly retarded in the closed system due to Na+ and SiO2(aq) accumulation and limited K + supply. Precursor clinoptilolite underwent extensive dissolution during the six week, 300 °C experiments subsequently producing a high-silicon analcime in addition to authigenic silica phases. Analcime and feldspar formation partially sequesters aqueous Al 3+ , thereby potentially inhibiting illitization. Associated with the zeolite alteration is a ~ 17 % volume decrease (assuming quartz formation) that translates into ~ 2% volume loss in the bulk bentonite. Pyrite decomposition is first observed at ~210 °C, generating available H 2 S (aq,g) that reacts with metal plates or evolves as a gas. The copper rapidly degrades in the presence of H 2 S (aq,g) , resulting in the formation of a chalcocite crust on the copper. A layer of Fe-saponite (or rarely, chlorite) forms at the steel bentonite interface, potentially acting as a passivating agent to retard further metal corrosion. Zeolite mineralogy alteration, metal-bentonite interface reactions, and illitization retardation under these experimental repository conditions are important considerations for the long-term stability evaluation of a used fuel repository.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Space processing of composite materials

Materials and processes for the testing of aluminum-base fiber and particle composites, and of metal foams under extended-time low-g conditions were investigated. A wetting and dispersion technique was developed, based on the theory that under the absence of a gas phase all solids are wetted by liquids. The process is characterized by a high vacuum environment and a high temperature cycle. Successful wetting and dispersion experiments were carried out with sapphire fibers, whiskers and particles, and with fibers of silicon carbide, pyrolytic graphite and tungsten. The developed process and facilities permit the preparation of a precomposite which serves as sample material for flight experiments. Low-g processing consists then merely in the uniform redistribution of the reinforcements during a melting cycle. For the preparation of metal foams, gas generation by means of a thermally decomposing compound was found most adaptable to flight experiments. For flight experiments, the use of compacted mixture of the component materials limits low-g processing to a simple melt cycle.

Steurer, W. H.↗