A carbon/tin nanomaterial, consisting of predominantly Sn-filled carbon nanotubes and nanoparticles, is prepared by molten salt electrochemistry, using electrodes of graphite and an electrolyte of LiCl salt containing a small admixture of SnCl2. The C/Sn hybrid material generated is incorporated into the active anode material of a lithium ion battery and tested with regard to storage capacity and cycling behavior. The results demonstrate that the C/Sn material has favorable properties, in terms of energy density and in particular long-term stability, that exceed those of the individual components alone. The initial irreversible capacity of the material is somewhat larger than that of conventional battery graphite which is due to its unique nanostructure. Overall the results would indicate the suitability of this material for use in the anodes of lithium ion batteries with high rate capability.
We report a novel, active-active-inactive-type tin-antimony-copper alloy with dendritic morphology electrodeposited on 3D interconnected microporous copper foam (~70 μm pore diameter) as a promising high specific capacity anode for Li-ion batteries. The multiphase composition, SnSb and Cu6Sn5 “reactant” intermetallics embedded in Sn “matrix,” alleviates the volumetric stress generated during cycling by lithiating at different step potentials (0.84, 0.66, 0.57, 0.42, 0.39, and 0.38 to 0.33 V vs Li/Li+). Copper foam successfully acts as a stress buffer preventing both pulverization and delamination. This combination of properties in tin-antimony-copper anode on copper foam results in 2nd cycle discharge capacity of 723 mAh/g, superior rate capability, and stable cycle retention with a capacity loss of 16 pct in the last 70 cycles at a rate of 400 mA/g (0.5 C) while preserving its structural integrity in comparison to tin-antimony-copper anode deposited on a planar copper foil as a current collector.
The environmental degradation of intermediate heat exchanger (IHX) materials in impure helium has been identified as an area with major ramifications on the design of very high-temperature reactors (VHTR). It has been reported that in some helium environments, non-ductile failure is a significant failure mode for Alloy 617 with long-term elevated-temperature service. Non-ductile failure of intermediate exchangers can result in catastrophic consequences; unfortunately, the knowledge of creep crack initiation and creep crack growth (CCG) in candidate alloys is limited. Current codes and code cases for the candidate alloys do not provide specific guidelines for effects of impure helium on the high-temperature behavior. The work reported here explores creep crack growth characterization of Alloy 617 and Alloy 800H at elevated temperatures in air and in impure helium environments, providing information on the reliability of these alloys in VHTR for long-term service. Alloy 617 was found to exhibit superior CCG resistance compared to Alloy 800H. For Alloy 617 tested at 973 K (700 °C), a notable increase in the resistance to crack growth was measured in air compared to that measured in the helium environment; CCG results for Alloy 800H suggest that air and helium environments produce similar behavior. Testing of grain boundary-engineered (GBE) Alloy 617 samples revealed that, although the technique produces superior mechanical properties in many respects, the GBE samples exhibited inferior resistance to creep crack growth compared to the other Alloy 617 samples tested under similar conditions. Grain size is noted as a confounding factor in creep crack growth resistance.
Friction stir welding of an aluminum-containing oxide dispersion-strengthened steel causes significant oxide particle growth visible at both the nano- and microscales. Quantitative stereology of scanning electron images, small-angle X-ray scattering, energy-dispersive X-ray spectroscopy, and atom-probe tomography is used to quantify the degree of particle coarsening as a function of welding parameters. Results show the dispersed oxides are significantly coarsened in the stir zone due to a proposed combination of agglomeration, Ostwald ripening, and phase transformation within the Al2O3-Y2O3 system. This oxide particle coarsening effectively removes all strengthening contribution of the original oxide particles, as confirmed by uniaxial tensile tests and microhardness measurements.
The reaction of SiF4 gas with aluminum (Al) was studied at temperatures ranging from room temperature to 1723 K (1450 °C). Although thermochemical estimates indicate that reactions throughout the temperature range should be thermodynamically favorable, we found that no reaction takes place appreciably until Al is heated to around 1473 K (1200 °C). The reaction products consist of fine powders of Si, Al, and AlF3. Some of the reaction products were transported away from the reaction zone by strong convection currents resulting from the exothermic reaction. Even at approximately 1673 K (1400 °C), the reaction rate is slow and a significant amount of Al remains unreacted. When NaF powders were used to line the graphite reactor, NaAlF4, AlF3, and Si powders were observed on the upper cooler walls of the reactor, and Si whiskers were formed just above the Al-Si alloy globule on the bottom of the crucible. We found evidence of the formation of AlF and SiF2 vapor species in the reaction zone, which then disproportionated along the cooler walls of the reactor, generating powders of Al and Si and regenerating condensable AlF3 and SiF4 gas, respectively.
Boron removal processes are crucial to make the metallurgical route for silicon refining for solar cells competitive and thus reduce the cost of solar energy. The rate-limiting step was investigated in silicon purification processes for boron removal based on gas blowing, to gain better understanding that should help to improve the design of such processes. We calculate the boron concentration in the off-gas that corresponds to chemical equilibrium between the gas and silicon. The real concentration in the off-gas ranges between 9 and 30 pct of this theoretical value calculated using Gibbs free energies reported in literature. Purification experiments with varying temperature and hydrogen concentration were done to evaluate whether limited chemical reaction rates induce deviation from chemical equilibrium. The experiments and data from literature show that the chemical reactions at the surface of the melt are close to chemical equilibrium, thus the purification rate is limited by mass transfer in the gas phase near the interface. Based on this, recommendations for the design of a gas blowing purification process are given.
This study provides a comparison between environmental impacts of the recovery of platinum group metals (PGMs) from the end-of-life catalytic converters by hydrometallurgical and pyrometallurgical methods. A gate to grave life cycle assessment of a typical three-way catalytic converter manufactured for an Australian passenger car was carried out using GaBi professional environmental package. Recovery rates, as well as qualities, quantities, losses, and fugitive emissions for all materials and elements used in both methods were calculated based on the developed flowsheets. A life cycle impact assessment was then made by carrying out a mass balance calculation. Inventory data show that the hydrometallurgical route for recycling of the platinum group metals out of catalytic converter scrap has lower impacts on the environment compared with the pyrometallurgical method. In terms of emission effects, the hydrometallurgical process was found to be highly advantageous since it causes insignificant emissions to air, sea water, and fresh water. It is also found that the hydrometallurgical route performs comparatively superior in terms of acidification, eutrophication, fossil depletion, and human toxicity. The obtained results are applicable only to the Australian setting.
The low thermal conductivity of oxide nuclear fuels is a performance-limiting parameter. Enhancing this property may provide a contribution toward establishing accident-tolerant fuel forms. In this study, the thermal conductivity of UO2 was increased through the fabrication of ceramic-ceramic composite forms with UO2 containing a continuous BeO matrix. Fuel with a higher thermal conductivity will have reduced thermal gradients and lower centerline temperatures in the fuel pin. Lower operational temperatures will reduce fission gas release and reduce fuel restructuring. Additions of BeO were made to UO2 fuel pellets in 2.5, 5, 7.5, and 10 vol pct concentrations with the goals of establishing reliable lab-scale processing procedures, minimizing porosity, and maximizing thermal conductivity. The microstructure was characterized with electron probe microanalysis, and the thermal properties were assessed by light flash analysis and differential scanning calorimetry. Reliable, high-density samples were prepared using compaction pressure between 200 and 225 MPa and sintering times between 4 and 6 hours. It was found that the thermal conductivity of UO2 improved approximately 10 pct for each 1 vol pct BeO added over the measured temperature range 298.15 K to 523.15 K (25 °C to 250 °C) with the maximum observed improvement being \(\sim \)100 pct, or doubled, at 10 vol pct BeO.
In the carbon looping combustion process the oxygen carrier is regenerated through oxidation in air; this process has been simulated by the oxidation of dense synthetic magnetite for selected temperatures and times. The oxidation of magnetite in air is shown to occur through the formation of dense hematite layers on the particle surface. This dense hematite forms through lath type shear transformations or solid-state diffusion through the product layer. Cyclic reduction in CO-CO2/oxidation in air of hematite single crystals has been carried out under controlled laboratory conditions at 1173 K (900 °C). It has been shown that the initial reduction step is critical to determining the product microstructure, which consists of gas pore dendrites in the magnetite matrix with blocky hematite formed on the pore surfaces. The progressive growth of the magnetite layer with the application of subsequent cycles appears to continue until no original hematite remains, after which physical disintegration of the particles takes place.
Iron oxides have been identified as promising materials for use as oxygen carriers in chemical looping combustion technologies as there are abundant resources available in the form of ore and in industrial wastes. The isothermal reduction of hematite (Fe2O3) in the fuel reactor and the subsequent oxidation of magnetite (Fe3O4) in air are the principal reactions of interest for these applications. Experimental investigations have been carried out to characterize the microstructural changes taking place as a result of the reduction reactions for a range of CO/CO2 gas compositions at temperatures between 1073 K and 1373 K (800 °C and 1100 °C). It has been shown that magnetite spinel is formed directly from hematite under these conditions and that porous magnetite or dense platelet or “lath” type morphologies can be formed depending on gas composition and reaction temperature. The conditions for the lath/pore transition are established. Dendritic gas pores are formed during the creation of the porous magnetite. This morphology allows continuous contact between the gas reactant and reaction interface and results in high reduction reaction rates.
Sb-Se-Sn ternary alloys are promising chalcogenide materials. The liquidus projection and 673.2 K (400 °C) isothermal section of the Sb-Se-Sn ternary system are determined. Numerous Sb-Se-Sn alloys are prepared, and their primary solidification phases are examined. In addition to the three terminal phases, (Sb), (Se) and (Sn), there are Sb2Sn3, SbSn, SnSe, SnSe2, Sb2Se3, Sn2Sb9Se9, and SnSb2Se4 phases. In addition, there are two miscibility gaps along the Sb-Se and Se-Sn and sides. There are ten invariant reactions in the Sb-Se-Sn ternary system, and seven of them are experimentally determined in this study. The lowest reaction temperature of determined invariant reaction is L + SbSn = (Sn) + SnSe at 515.4 K ± 5 K (242.2 °C ± 5 °C). There are nine tie-triangles, which are Liquid + SbSn + SnSe, SbSn + SnSe + (Sb), SnSe + (Sb) + Sn2Sb9Se9, (Sb) + Sb2Se3 + Sn2Sb9Se9, SnSe + Sn2Sb9Se9 + SnSb2Se4, Sb2Se3 + Sn2Sb9Se9 + SnSb2Se4, SnSe + SnSe2 + SnSb2Se4, SnSe2 + SnSb2Se4 + Sb2Se3, and SnSe2 + Sb2Se3 + Liquid in the 673.2 K (400 °C) isothermal section of the Sb-Se-Sn ternary system.
This study assesses the impact of low-dose and low-temperature irradiation on the properties of cubic silicon carbide (3C-SiC). 3C-SiC was irradiated with Kr ions to different fluences at 420 K (147 °C). Raman spectroscopy was used to investigate the impact of irradiation-induced defects on vibrational modes and time-domain thermoreflectance (TDTR) was used to measure thermal conductivity. We observe a noticeable reduction in thermal conductivity with increasing fluence. Analysis of Raman spectra reveals the longitudinal optical (LO) and transverse optical (TO) modes with noticeable peak broadening of LO mode with increasing dosage. We also notice a decrease of ratio of peak intensities of LO and TO modes in irradiated samples. We observe a correlation between the thermal conductivity reduction and the decrease in the peak intensity ratio and attribute this to the accumulation of charged vacancy defects.
A critical evaluation and thermodynamic modeling for thermodynamic properties of all oxide phases and phase diagrams in the Fe–Mn–O system are presented. Optimized Gibbs energy parameters for the thermodynamic models of the oxide phases were obtained which reproduce all available and reliable experimental data within error limits from 298K to above the liquidus temperatures at all compositions covering from known oxide phases, and oxygen partial pressure from metal saturation to 0.21bar. The optimized thermodynamic properties and phase diagrams are believed to be the best estimates presently available. Two spinel phases (cubic and tetragonal) were modeled using Compound Energy Formalism (CEF) with the use of physically meaningful parameters. The present Fe–Mn spinel solutions can be integrated into a larger spinel solution database, which has been already developed. The database of the model parameters can be used along with a software for Gibbs energy minimization in order to calculate any type of phase diagram section and thermodynamic properties.
A general computational alloy design approach, based on thermodynamics and thermokinetics and coupled with a genetic algorithm optimization routine, was applied to the design of novel creep martensitic resistant steels. The optimal alloy suggested by the model has a high density of barely coarsening MX carbonitride precipitates. The model yielded precise values for the concentrations of the 10 alloying elements considered. The model alloy was produced on a 10 kg lab scale. Samples of the new alloy of one of the best commercial martensitic steels on the market P92 were subjected to a high aging temperature of 923 K (650 °C) for times up to 1000 hours. The microstructure of the new alloy in the as-produced state as well as after 1000 hours exposure has all the intended features as predicted by the model. The coarsening rate of the MX rate carbonitrides was substantially lower than that of the precipitates in the P92 steel. The very low coarsening rate explains the superior hardness at very long exposure times.
Aerosol deposition is a thick-film deposition process that can produce layers up to several hundred micrometers thick with densities greater than 95 pct of the theoretical value. The primary advantage of aerosol deposition is that the deposition takes place entirely at room temperature, thereby enabling film growth in material systems with disparate melting temperatures. We show representative characterization results of yttrium iron garnet thick films deposited onto a 〈111〉 gadolinium gallium garnet substrate by aerosol deposition using scanning electron microscopy, X-ray diffraction, profilometry, vibrating sample magnetometry, and ferromagnetic resonance. To further elucidate the effect of density and grain size on the magnetic properties, we perform post-deposition annealing of the films to study the effect on the structural and magnetic properties of the films. Our results indicate that our system can successfully deposit dense, thick yttrium iron garnet films and that with moderate annealing the films can achieve a ferromagnetic resonance linewidth comparable to that reported for polycrystalline films deposited by other higher temperature growth techniques.
This study looks at the energy intensity of the steel industry and the greenhouse gas intensity involved with the production of steel. Using several sources of steel production data and the corresponding energy sources used provides a time-series analysis of the greenhouse gas (GHG) and energy intensity from 1990 to 2014. The impact of the steel economy with the gross domestic product (GDP) provides indirect importance of the general manufacturing sector within Korea and in particular the steel industry. Beyond 2008, the shift in excess materials production and significant increase in total imports have led to an imbalance in the Korean steel market and continue to inhibit the growth of the domestic steel market. The forecast of the GHG and energy intensity along with the steel production up to 2030 is provided using the auto regressive integrated moving average analysis.
A code named OSCAR-Na has been developed to calculate the mass transfer of corrosion products in the primary circuit of sodium fast reactors (SFR). It is based on a solution/precipitation model, including diffusion in the steel (enhanced under irradiation), diffusion through the sodium boundary layer, equilibrium concentration of each element, and velocity of the interface (bulk corrosion or deposition). The code uses a numerical method for solving the diffusion equation in the steel and the complete mass balance in sodium for all elements. Corrosion and deposition rates are mainly determined by the iron equilibrium concentration in sodium and its oxygen-enhanced dissolution rate. All parameters of the model have been assessed from a literature review, but iron solubility had to be adjusted. A simplified primary system description of PHENIX French SFR was able to assess the correct amounts and profiles of contamination on heat exchanger surfaces for the main radionuclides.
The magnetic properties of non-oriented electrical steels are determined by a combination of several metallurgical variables, including crystal orientation, misorientation (the orientation difference between two crystal orientations), and the amount of residual stress associated with plastic deformation. These variables are influenced by cold rolling and annealing. In order to study these relationships, samples in the semi-processed condition were subjected to an additional cold roll and a subsequent annealing at different temperatures, and then characterized using electron backscatter diffraction and nanoindentation. The process routing for these samples was not intended to be representative of real-world manufacturing; the purpose was to produce a spread in the metallurgical variables being investigated. Although some trends were observed involving orientation and misorientation, when present, deformation observed close to grain boundaries appeared to be the most influential variable on the magnetic properties.
Some of the Heusler-phases ( XY 2 Z and XYZ ) are known to have large homogeneity ranges which can be useful for tuning material properties. In this work, we have revised the isothermal section of the Ti-Co-Sn system at 973 K (700 °C). A total of 29 ternary compositions, mostly in the regions TiCo 2− x Sn for 0 ≤ x ≤ 1 and Ti 1+ y Co 2 Sn 1− y for 0 ≤ y ≤ 1, were prepared by arc-melting, then ball-milled and annealed. The resulting annealed powder samples were studied by applying the Rietveld method to X-ray and neutron powder diffraction data. Half-Heusler TiCoSn was not observed. The Heusler phase observed in TiCo 2− x Sn has compositions ranging from TiCo 1.52 Sn to TiCo 2 Sn and has the half-Heusler structure where the excess of Co is located on the semi-filled tetrahedral site 4 d (¾, ¾, ¾) in the space group F -43 m . At 1273 K (1000 °C), this solid solubility is expanded from TiCo 2 Sn to TiCo with full solid solubility where Ti is gradually replacing Sn (Ti 1+ y Co 2 Sn 1− y for 0 ≤ y ≤ 1), while at 973 K (700 °C) there is a small solubility gap for 0.0 ≤ y ≤ 0.2.
Drying rates of lignite particle groups in superheated steam are evaluated using a single-particle model developed for Australian lignite. Size distributions of the particles are assumed to obey the Rosin–Rammler equation with the maximum particle diameters defined as 100, 50, and 6 mm. The results show the drying rate of a lignite group depends strongly on the maximum particle size, and removal of large particles prior to drying is shown to be effective to reduce the drying time. The calculation model is available for simulations of drying behaviors of lignite in various dryers when an appropriate heat transfer coefficient is given. This study simulates the drying of particles smaller than 6 mm using a heat transfer coefficient in a fluidized bed dryer reported elsewhere. The required drying time estimated from the calculation is comparable to the processing time reported in an actual fluidized bed dryer, supporting the validity of the calculation model.
