Turbulent natural convection in a porous square cavity computed with a macroscopic κ–ε model

Detailed numerical computations for laminar and turbulent natural convection within a square cavity filled with a fluid saturated porous medium are presented. Heated vertical walls are maintained at constant but different temperatures, while horizontal surfaces are kept insulated. The macroscopic κ–ε turbulence model with wall function is used to handle turbulent flows in porous media. In this work, the turbulence model is first switched off and the laminar branch of the solution is found when increasing the Rayleigh number, Ra_m. Computations covered the range 10 < Ra_m < 10⁶ and 10⁻⁷ < Da  < 10⁻¹⁰ and made use of the finite volume method. Subsequently, the turbulence model is included and calculations start at high Ra_m, merging to the laminar branch for a reducing Ra_m and for Ra_m less than a certain critical Rayleigh number, Ra_cr. This convergence of results as Ra_m decreases can be seen as a characterization of the laminarization phenomenon. For Ra_m values less than around 10⁴, both laminar and turbulent flow solutions merge, indicating that such critical value for Ra_m was reached. Results further indicate that when the parameters porosity, Pr, conductivity ratio between the fluid and the solid matrix and the Ra_m are kept fixed, the lower the Darcy number, the higher the average Nusselt number at the hot wall.     

Modified APEX reactor as a fusion breeder

An advanced fusion reactor project, called APEX, with improved effectiveness has been developed using a protective flowing liquid wall for tritium breeding and energy transfer. In the modified APEX concept, the flowing molten salt wall is composed of Flibe as the main constituent with increased mole fractions of heavy metal salt (ThF₄ or UF₄) for both fissile and fusile breeding purposes and to increase the energy multiplication. Neutron transport calculations are conducted with the help of the SCALE4.3 SYSTEM by solving the Boltzmann transport equation with the code XSDRNPM. By preserving a self sufficient tritium breeding ratio (TBR > 1.05) for a mole fraction up to 6% of ThF₄ or 12% of UF₄, the modified APEX reactor can produce up to ∼2800 kg of ²³³U/year or ∼4950 kg of ²³⁹Pu/year, assuming the same baseline fusion power production of 4000 MW_th, as in the original APEX concept. With 6% ThF₄ or 12% UF₄ in the coolant, the total energy output will increase to 5560 MW_th or 8440 MW_th, respectively. For a plant operation period of 30 full power years, the atomic displacement and helium production rates remain well below the presumable limits. The additional benefits of fissionable metal salt in the flowing liquid in a fusion reactor can be summarized as breeding of high quality fissile fuel for external reactors and increase of total plant power output.     

Entropy generation due to conjugate natural convection in enclosures bounded by vertical solid walls with different thicknesses

Entropy generation due to conjugate natural convection heat transfer and fluid flow has been studied inside an enclosure with bounded by two solid massive walls from vertical sides at different thicknesses. Enclosure is differentially heated from vertical walls and horizontal walls are adiabatic. Governing equations which are written in streamfunction-vorticity form solved by finite difference technique for the governing parameters as Rayleigh number, 10³ ≤ Ra ≤ 10⁶, length ratio of solid walls as ₁ (for left vertical wall) and ₂ (for right vertical wall) and thermal conductivity ratio of solid to fluid (k), 1 ≤ k ≤ 10. Entropy generation contours due to fluid friction and heat transfer irreversibility, isotherms, streamlines, Nusselt numbers and velocity profiles were obtained. It is found that entropy generation increases with increasing of thermal conductivity ratio and thicknesses of the walls. Entropy generation due to heat transfer is more significant than that of fluid flow irreversibility for all values of thickness of the solid vertical walls.     

Electrochemical and structural characteristics of metal oxide-coated lithium manganese oxide (spinel type): Part I. In the range of 2.5–4.2 V

The electrochemical and structural characteristics of the metal oxide-coated spinel were investigated in the range of 2.5–4.2 V. Metal oxide coating on commercial spinel powder (LiMn_2−xM_xO₄, M=Zr, Nikki, Japan) was carried out using the sol–gel method. Al₂O₃/(PtO_x or CuO_x)-coated spinel exhibited improved cyclability compared to bare spinel. Impedance analysis results indicated that electrochemical resistance value was not consistent with cycle performance. The improved cycle performance of metal oxide-coated spinel may be due to formation of a new Li₂Mn₄O₉, Li₂MnO₃ phase, which is expected to have stability to phase transition (Jahn–Teller distortion).     

Synthesis and electrochemical studies of the 4 V cathode, Li(Ni2/3Mn1/3)O2

Layered Li(Ni_2/3Mn_1/3)O₂ compounds are prepared by freeze-drying, mixed carbonate and molten salt methods at high temperature. The phases are characterized by X-ray diffraction, Rietveld refinement, and other methods. Electrochemical properties are studied versus Li-metal by charge–discharge cycling and cyclic voltammetry (CV). The compound prepared by the carbonate route shows a stable capacity of 145 (±3) mAh g⁻¹ up to 100 cycles in the range 2.5–4.3 V at 22 mA g⁻¹. In the range 2.5–4.4 V at 22 mA g⁻¹, the compound prepared by molten salt method has a stable capacity of 135 (±3) mAh g⁻¹ up to 50 cycles and retains 96% of this value after 100 cycles. Capacity-fading is observed in all the compounds when cycled in the range 2.5–4.5 V. All the compounds display a clear redox process at 3.65–4.0 V that corresponds to the Ni^2+/3+–Ni^3+/4+ couple.     

Thermal cycling of transition joints between modified 9Cr–1Mo steel and Alloy 800 for steam generator application

The effect of accelerated thermal cycling on a joint between modified 9Cr–1Mo steel (Grade 91) and Alloy 800 welded with Inconel¹ 82 and 182 filler material is discussed. This is part of a trimetallic transition joint involving Grade 91–Alloy 800–316LN austenitic stainless steel for steam generator application. It has been shown that, during thermal cycling following the typical post-weld tempering treatment at 760 °C for 2 h, no carbon diffusion occurs from the ferritic steel towards the weld metal. There is, in fact, a hardness increase at the ferritic steel/weld metal interface which is probably a result of work hardening. Carbon migration sets in only after unusually long post-weld heat treatments for 20 and 50 h at 760 °C followed by thermal cycling. Significantly, even under the most severe thermal cycling test conditions imposed, no cracking or oxide notching could be detected, thus demonstrating the superior performance potential of modified 9Cr–1Mo steel as part of a trimetallic configuration.     

Effect of salt concentration on poly (vinyl chloride)/poly (acrylonitrile) based hybrid polymer electrolytes

Hybrid, solid polymer electrolyte films consisting of poly (vinyl chloride) (PVC), poly (acrylonitrile) (PAN) and, propylene carbonate (PC) with different concentrations of LiClO₄ are prepared by means of a using solvent-casting technique. The structure and complex formation are studied by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. The temperature dependence of the ionic conductivities of the polymer films is explained in terms of a free volume model. The conductivities of PVC–PAN–LiClO₄–PC complexes are determined at different salt concentrations. The highest ionic conductivity (8.35 × 10⁻⁵ S cm⁻¹) is obtained for 8 wt.% LiClO₄ in the polymer complex at 304 K. The thermal stability of the electrolyte is examined by thermogravimetric/differential thermal analysis (TG/DTA).     

Study the effects of mechanical activation on Li–N–H systems with H and Li solid-state NMR

To gain insight into the effects of mechanical activation (MA) on the hydrogen desorption of the lithium amide (LiNH₂) and lithium hydride (LiH) mixture, LiNH₂ and LiH + LiNH₂ were mechanically activated by high-energy ball milling. The formed products were studied with in situ ¹H and ⁶Li nuclear magic angle spinning (MAS) magnetic resonance (NMR) spectroscopy from ambient temperature to 180 °C. Up-field chemical shift was observed in ⁶Li MAS NMR spectra with increased milling time, indicating that average local electronic structure around Li nuclei was modified during MA. ¹H MAS NMR was used to dynamically probe ammonia release from the activated LiNH₂ at temperature as low as 50 °C. In the case of activated LiH + LiNH₂ mixtures, the ¹H MAS NMR results implied that MA enhanced the dehydrogenation reaction of LiNH₂ + LiH = Li₂NH + H₂.     

Electrochemical characteristics and cycle performance of LiMn2O4/a-Si microbattery

A LiMn₂O₄ thin film and an amorphous Si (a-Si) thin film were prepared by radio-frequency (rf) magnetron sputtering. Each thin film was electrochemically evaluated by cyclic voltammetry (CV) and galvanostatic cycling. The rate of capacity fade on cycling was monitored as a function of the voltage window and current density. This was compared with the cycle performance of cathode and anode using two kinds of electrolyte, 1 M LiPF₆ in EC/DMC and PC, for 100 cycles. It was found that the discharge capacity of optimized LiMn₂O₄/a-Si full-cell reached 24 μAh/(cm²-μm) in the first cycle, and a reversible capacity of about 16 μAh/(cm² μm) was still maintained after 100 cycles. In a voltage window of 3.0–4.2 V, LiMn₂O₄/a-Si full-cell exhibits relatively stable cycle performance compared to a voltage window of 2.75–4.2 V.     

Predictions of the optimum ternary alkali-carbonate electrolyte composition for MCFC by computational calculation

Various kinds of phase diagrams for Li–Na–K ternary carbonate systems were plotted and the vapor pressures of chemical species such as alkali cations and oxygen molecule at various compositions and various temperatures were calculated by computational manipulation of thermodynamic databases. The liquidus temperature of (Li_0.52Na_0.48)₂CO₃–(Li_0.62K_0.32)₂CO₃, (Li_0.62K_0.32)₂CO₃–(Li_0.44Na_0.30K_0.26)₂CO₃, and (Li_0.44Na_0.30K_0.26)₂CO₃–(Li_0.52Na_0.48)₂CO₃ binary systems decrease with the increase of Li₂CO₃ content without any ternary intermediate compound. Total vapor pressure of alkali metal species governed by the summation of the vapor pressure of free Na and K and the vapor pressure of alkali metal species starts to decrease abruptly when the content of (Li_0.52Na_0.48)₂CO₃ is over 70 mol% in (Li_0.52Na_0.48)₂CO₃–(Li_0.62K_0.32)₂CO₃ system while over 50 mol% in (Li_0.44Na_0.30K_0.26)₂CO₃–(Li_0.52Na_0.48)₂CO₃ system. On the contrary, the equilibrium vapor pressure of oxygen molecule abruptly increases at the same composition range.     

Optimization of structural combinations on the performance of a PEMFC's MEA

In this study, the Taguchi method was applied to determine optimum structural combination of a membrane electrode assembly (MEA) in obtaining maximum power density of a PEMFC. Performance measure analysis was also followed by performing a variance analysis, in order to determine the optimum levels and relative magnitude of the effect of combinations. The optimum structural combinations of MEA were found to be membrane, Nafion 112 with a thickness of 51 μm, amount of platinum loaded by sputtering, 0.05 mg Pt cm⁻², Nafion ionomer content, 0.05 mg cm⁻² and support material of gas diffusion layer (GDL), carbon paper. Under these conditions, the amount of maximum power density was predicted as 563.75 mW cm⁻² by using experimental results obtained according to Taguchi's orthogonal array (OA) L₁₆(2⁴ × 2²). Verification experiment was done for the same optimum structural combination and maximum power density was observed as 566 mW cm⁻². According to the results of this optimization, it was seen that amount of platinum loaded by sputtering and thickness of membrane were the effective parameters.     

NaBH4-assisted ethylene glycol reduction for preparation of carbon-supported Pt catalyst for methanol electro-oxidation

A carbon-supported Pt catalyst (40 wt.% loading) is prepared by a modified ethylene glycol reduction method (Pt–EG-complex). In this procedure, a complex produced by reacting ethylene glycol with sodium borohydride (NaBH₄), serves as a reducing agent for the Pt precursor and as a stabilizer for preventing the growth of Pt particles. For purposes of comparison, two types of carbon-supported Pt catalyst (40 wt.% loading) are also prepared by a NaBH₄ reduction method, in which the Pt precursor is reduced in a ethylene glycol solution (Pt–EG–NaBH₄) and in de-ionized water (Pt–H₂O–NaBH₄). Analysis by X-ray diffraction and transmission electron microscopy reveal that the Pt–EG-complex catalyst is comprised of highly-dispersed Pt nanoparticles with a uniform size (2.9–3.1 nm) on the carbon support, while large Pt particles are observed in the Pt–EG–NaBH₄ (3.3–3.6 nm) and Pt–H₂O–NaBH₄ (5.7–6.2 nm) catalysts. The Pt–EG-complex catalyst has the highest electrochemical surface area and shows the highest catalytic performance for methanol electro-oxidation.     

A screen-printed Ce0.8Sm0.2O1.9 film solid oxide fuel cell with a Ba0.5Sr0.5Co0.8Fe0.2O3−δ cathode

Screen-printing technology was developed to fabricate Ce_0.8Sm_0.2O_1.9 (SDC) electrolyte films onto porous NiO–SDC green anode substrates. After sintering at 1400 °C for 4 h, a gas-tight SDC film with a thickness of 12 μm was obtained. A novel cathode material of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ was subsequently applied onto the sintered SDC electrolyte film also by screen-printing and sintered at 970 °C for 3 h to get a single cell. A fuel cell of Ni–SDC/SDC (12 μm)/Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ provides the maximum power densities of 1280, 1080, 670, 370, 180 and 73 mW cm⁻² at 650, 600, 555, 505, 455 and 405 °C, respectively, using hydrogen as fuel and stationary air as oxidant. When dry methane was used as fuel, the maximum power densities are 876, 568, 346 and 114 mW cm⁻² at 650, 600, 555 and 505 °C, respectively. The present fuel cell shows excellent performance at lowered temperatures.     

The development of MHD cold wall channels in the oil-fired condition

The durability of a cold wall MHD generator consisting of metal electrodes and alumina-coated peg insulators was experimentally examined in the oil-fired MHD condition with the additive of SO₂ corresponding to S = 0.54 wt%. The structure of the electrode wall and various anode and cathode materials were tested, with particular reference to developing long-life electrodes. It was clarified that Pt, SHOMAC (28.8 Cr−1.9 Mo) and SUS-304 as anodes and W---Cu (70 W−30 Cu) and WC---Ag (60 WC−40 Ag) alloys as cathodes were promising for durability and that the structure of an anode divided into two elements connected to each other with an SnO₂ resistor was very useful for uniformity of the anode corrosion pattern and the inter-anode voltages. It is reasonable to expect, from the test results, that the lifetime of a cold wall MHD generator in an oil-fired commercial plant will be over 4000 h, and therefore, a foundation for its commercial use has been established.     

Electrochemical performance of Nd0.6Sr0.4Co0.5Fe0.5O3−δ–Ag composite cathodes in intermediate temperature solid oxide fuel cells

The electrochemical performances of Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ–Ag composite cathodes have been investigated in intermediate temperature solid oxide fuel cells. The Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ–Ag cathodes prepared by ball milling followed by firing at 920 °C show the maximum performance (power density: 0.15 W cm⁻² at 800 °C) at 3 wt.% Ag. On the other hand, the Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ–Ag composite cathodes with 0.1 mg cm⁻² (0.5 wt.%) Ag that were prepared by an impregnation of Ag into Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ followed by firing at 700 °C (but the electrolyte–Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ assembly was prepared first by firing at 1100 °C) exhibit much better performance (power density: 0.27 W cm⁻² at 800 °C) than the composite cathodes prepared by ball milling, despite a much smaller amount of Ag due to a better dispersion and an enhanced adhesion. AC impedance analysis indicates that the Ag catalysts dispersed in the porous Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ cathode reduce the ohmic and the polarization resistances due to an increased electronic conductivity and enhanced electrocatalytic activity.     

Structural, magnetic and electrochemical properties of lithium iron orthosilicate

We report the structural and electronic characterization of Li₂FeSiO₄ synthesized by solid-state reaction. X-ray diffraction, Raman scattering, Fourier transform infrared (FTIR) spectroscopy, electron paramagnetic resonance (EPR) spectroscopy and magnetization measurements are analyzed. Magnetic susceptibility experiments give evidence that Li₂FeSiO₄ powders possess an antiferromagnetic ordering below T_N = 25 K due to long range Fe–O–Li–O–Fe interactions. Analysis of the paramagnetic region giving the Curie–Weiss parameters θ_p = −93.5 K and C_p = 4.13 emu K mol⁻¹ shows the divalent state of Fe cations. Electron paramagnetic resonance experiments confirm this electronic configuration. Electrochemical measurements were carried out in lithium cells with LiTFSI in a poly(ethylene oxide) (PEO) polymer electrolyte at 80 °C. The resulting cyclic voltammogram indicates a stable structure for the first cycle with redox peaks at 2.80 and 2.74 V versus Li⁰/Li⁺.     

Physicochemical properties and photocatalytic hydrogen evolution of TiO2 films prepared by sol–gel processes

Anatase TiO₂ films were obtained on glass substrates using a sol–gel method using titanium isopropoxide as a precursor. The thickness of the film was about 140 nm for one coating, and the thickness is controlled by the number of coating cycles. The spectra of UV-VIS absorption indicated that the absorption edge of the TiO₂ films is ca. 385 nm, corresponding to the band gap energy of 3.20 eV. We obtained TiO₂ films having a high activity for the hydrogen evolution from photocatalytic water cleavage. By loading with 0.3 wt% Pt rate of hydrogen production increases. No influence of film thickness and calcination temperature on the photocatalytic property is observed.     

NiO–ScSZ and Ni0.9Mg0.1O–ScSZ-based anodes under internal dry reforming of simulated biogas mixtures

Solid oxide fuel cells (SOFCs) with NiO–ScSZ and Ni_0.9Mg_0.1O–ScSZ-based anodes were operated by directly feeding a fuel mixture of CH₄, CO₂ and N₂ (CH₄ to CO₂ ratio of 3:2). Stable operation under constant current load (200 mA cm⁻²) was achieved with a NiO–ScSZ type anode during 200 h operating hours at 900 °C. Less stable operation occurred with a Ni_0.9Mg_0.1O–ScSZ type anode. In the case of SOFC with Ni_0.9Mg_0.1O–ScSZ as the anode, the methane reforming activity was higher than that with NiO–ScSZ. This was explained by change in the microstructure promoting reforming reactions. However, the addition of MgO resulted in degradation of electrochemical performance due to increase in ohmic resistance of the anode material during operation.     

Natural convection heat transfer enhancement in horizontal concentric annuli using nanofluids

Heat transfer enhancement in horizontal annuli using nanofluids is investigated. Water-based nanofluid containing various volume fractions of Cu, Ag, Al₂O₃ and TiO₂ nanoparticles is used. The addition of the different types and different volume fractions of nanoparticles were found to have adverse effects on heat transfer characteristics. For high values of Rayleigh number and high L/D ratio, nanoparticles with high thermal conductivity cause significant enhancement of heat transfer characteristics. On the other hand, for intermediate values of Rayleigh number, nanoparticles with low thermal conductivity cause a reduction in heat transfer. For Ra = 10³ and Ra = 10⁵ the addition of Al₂O₃ nanoparticles improves heat transfer. However, for Ra = 10⁴, the addition of nanoparticles has a very minor effect on heat transfer characteristics.     

Preparation and properties of transparent conducting zinc oxide and aluminium-doped zinc oxide films prepared by evaporating method

Undoped and aluminium-doped zinc oxide films have been prepared by thermal evaporation of zinc acetate [Zn(CH₃COO)₂ 2H₂O] and aluminium chloride [AlCl₃] onto a heated glass substrate. The structural and optoelectrical properties of the films have been studied. The effects of heat treatment for the as-deposited films in air and vaccum are investigated. Highly transparent films with conductivity as low as 2×10⁻³ Ω cm can be produced by controlling the deposition parameters. The electron carrier densities are in the range 0.2–7×10¹⁹ cm⁻³ with mobilities of 22–58 cm² V⁻¹ s⁻¹.