Synthesis,structure, CO oxidation,and H2 production activities of CaCu3−xMnxTi4−xMnxO12 (x = 0, 0.5, and 1.0)

Synthesis of nanocrystalline pristine and Mn-doped calcium copper titanate quadruple perovskites, CaCu_3?xMn_xTi_4?xMn_xO₁₂ (x = 0, 0.5, and 1.0) by modified citrate solution combustion method has been reported. Powder X-ray diffraction patterns attest the phase purity of the perovskite materials. Average particle sizes of all the materials obtained from the Scherrer's formula are in the range of 55–70 nm. The specific surface areas for all the perovskites obtained from BET isotherms are found to be low as expected for the condensed oxide systems and fall in the range of 13–17 m² g^?1. Transmission electron microscopy studies show a reduction in particle size of CaCu₃Ti₄O₁₂ with increase in Mn doping. Ca and Ti are present in +2 and +4 oxidation states in all the materials as demonstrated by X-ray photoelectron spectroscopy analyses. Cu²⁺ gets reduced in CaCu₃Ti₄O₁₂ with higher Mn content. Mn is observed to be present only in +3 oxidation state. All the materials have been examined to be active in CO oxidation as well as H₂ production from methanol steam reforming. CaCu₃Ti₄O₁₂ with ~14 at.% Mn is found to show best catalytic activities among these materials. A comprehensive analysis of the catalytic activities of these perovskites toward CO oxidation and H₂ production from MSR reveal the cooperative activity of copper-manganese in the doped perovskites and it is more effective at lower manganese content.     

SiC/SiC mini-composites with multilayer ZrSiO4 interphase: Room-temperature properties and toughening mechanism

SiC/SiC mini-composites reinforced with SiC fibers coated with different numbers of ZrSiO₄ sublayers prepared via a non-hydrolytic sol-gel process were fabricated. The tensile strength and work of fracture of the prepared SiC/SiC mini-composites were determined, and the relationship between their mechanical properties and fracture morphologies was discussed. The toughening mechanism and the variation tendency of their mechanical properties were further elaborated by analyzing the interfacial debonding morphologies of the SiC/SiC mini-composites with 1 and 4 layers of ZrSiO₄ interphase as well as the results of prior studies. A relatively rare phenomenon—the delamination of the multilayer ZrSiO₄ interphase in the SiC/SiC mini-composites but not on the SiC fibers—was observed, which clearly demonstrated the weak bonding between the ZrSiO₄ sublayers in the SiC/SiC mini-composites. The ZrSiO₄ sublayer delamination mechanism was then explained based on the high-magnification morphologies found in and beside the ZrSiO₄ interphase.     

Improving the multi-objective evolutionary optimization algorithm for hydropower reservoir operations in the California Oroville–Thermalito complex

This study demonstrates the application of an improved Evolutionary optimization Algorithm (EA), titled Multi-Objective Complex Evolution Global Optimization Method with Principal Component Analysis and Crowding Distance Operator (MOSPD), for the hydropower reservoir operation of the Oroville–Thermalito Complex (OTC) – a crucial head-water resource for the California State Water Project (SWP). In the OTC's water-hydropower joint management study, the nonlinearity of hydropower generation and the reservoir's water elevation–storage relationship are explicitly formulated by polynomial function in order to closely match realistic situations and reduce linearization approximation errors. Comparison among different curve-fitting methods is conducted to understand the impact of the simplification of reservoir topography. In the optimization algorithm development, techniques of crowding distance and principal component analysis are implemented to improve the diversity and convergence of the optimal solutions towards and along the Pareto optimal set in the objective space. A comparative evaluation among the new algorithm MOSPD, the original Multi-Objective Complex Evolution Global Optimization Method (MOCOM), the Multi-Objective Differential Evolution method (MODE), the Multi-Objective Genetic Algorithm (MOGA), the Multi-Objective Simulated Annealing approach (MOSA), and the Multi-Objective Particle Swarm Optimization scheme (MOPSO) is conducted using the benchmark functions. The results show that best the MOSPD algorithm demonstrated the best and most consistent performance when compared with other algorithms on the test problems. The newly developed algorithm (MOSPD) is further applied to the OTC reservoir releasing problem during the snow melting season in 1998 (wet year), 2000 (normal year) and 2001 (dry year), in which the more spreading and converged non-dominated solutions of MOSPD provide decision makers with better operational alternatives for effectively and efficiently managing the OTC reservoirs in response to the different climates, especially drought, which has become more and more severe and frequent in California.     

Efficient dye-sensitized solar cells based on CNTs and Zr-doped TiO2 nanoparticles

The light scattering, harvesting and adsorption effects in dye-sensitized solar cells (DSSCs) are studied by preparation of coated carbon nanotubes (CNTs) with TiO₂ and Zr-doped TiO₂ nanoparticles in the forms of mono- and double-layer cells. X-ray diffraction (XRD) analysis reveals that the phase composition of Zr-doped TiO₂ electrode is a mixture of anatase and rutile phases with major rutile content, whereas it is the same mixture with major anatase content for coated CNTs with TiO₂. Furthermore, the average crystallite size of Zr-doped TiO₂ electrode is slightly decreased with Zr introduction. Field emission scanning electron microscope (FE-SEM) images show that the porosity of Zr-doped TiO₂ electrodes is higher than that of undoped electrode, enhancing dye adsorption. UV–visible spectroscopy analysis reveals that the absorption onset of Zr-doped TiO₂ electrodes is slightly shifted to longer wavelength (the red-shift) in comparison with that of undoped TiO₂ electrode. Moreover, the band gap energy of TiO₂ nanoparticles is decreased by Zr introduction, enhancing light absorption. It is found that electron injection of monolayer TiO₂ electrode is improved by introduction of 0.025 mol% Zr, resulted in enhancement of its power conversion efficiency (PCE) up to 6.81% compared with 6.17% for pure TiO₂ electrode. Moreover, electron transport and light scattering are enhanced by incorporation of 0.025 wt% coated CNTs with TiO₂ in the over-layer of double layer electrode. Therefore, double layer solar cell composed of 0.025 mol% Zr-doped TiO₂ nanoparticles as the under-layer and mixtures of these nanoparticles and 0.025 wt% coated CNTs with TiO₂ as the over-layer shows the highest PCE of 8.19%.     

Polyimide/nano-TiO2 hybrid films having benzoxazole pendent groups: In situ sol–gel preparation and evaluation of properties

Polyimide/titania (PI/TiO₂) nanocomposite films have been successfully fabricated through the in situ formation of TiO₂ within a PI matrix via sol–gel method. Poly(amic acid) (PAA), which is the precursor of PI, was successfully synthesized by mixing pyromellitic dianhydride (PMDA), with equimolar amount of a diamine monomer having a pendent benzoxazole unit and two flexible ether linkages in N,N-dimethylformamide (DMF) solvent. Tetraethyl orthotitanate [Ti(OEt)₄] and acetylacetone were then added to the resulted PAA. After imidization at high temperature, PI/TiO₂ hybrid films were formed. The structure and morphology of the hybrid nanocomposites with different titania contents (0 wt%, 5 wt%, 10 wt%, and 15 wt%) were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, and transmission electron microscopy. The results indicate that the TiO₂ nanoparticles were homogeneously dispersed in the hybrid films. The thermogravimetric analysis of nanocomposites confirms the improvement in the thermal stability with the increase in the percentage of titania nanoparticle. Transmission electron microscopy showed that the nanoparticles with an average diameter of 25–40 nm were dispersed in the polymer matrix.     

High-voltage and low specific on-resistance power UMOSFET using P and N type columns

For the first time, we present the unique features exhibited by power 4H–SiC UMOSFET in which N and P type columns (NPC) in the drift region are incorporated to improve the breakdown voltage, the specific on-resistance, and the total lateral cell pitch. The P-type column creates a potential barrier in the drift region of the proposed structure for increasing the breakdown voltage and the N-type column reduces the specific on-resistance. Also, the JFET effects reduce and so the total lateral cell pitch will decrease. In the NPC-UMOSFET, the electric field crowding reduces due to the created potential barrier by the NPC regions and causes more uniform electric field distribution in the structure. Using two dimensional simulations, the breakdown voltage and the specific on-resistance of the proposed structure are investigated for the columns parameters in comparison with a conventional UMOSFET (C-UMOSFET) and an accumulation layer UMOSFET (AL-UMOSFET) structures. For the NPC-UMOSFET with 10 µm drift region length the maximum breakdown voltage of 1274 V is obtained, while at the same drift region length, the maximum breakdown voltages of the C-UMOSFET and the AL-UMOSFET structures are 534 and 703 V, respectively. Moreover, the proposed structure exhibits a superior specific on-resistance (R_on,sp) of 2 mΩ cm², which shows that the on-resistance of the optimized NPC-UMOSFET are decreased by 56% and 58% in comparison with the C-UMOSFET and the AL-UMOSFET, respectively.     

User activities and the heterogeneity of urban space:The case of Dahiyat Al Hussein park

Urban researchers have maintained a constant interest in the complexity and continuity of urban space usage. Some have applied actor–network theory (ANT) to investigate the heterogeneity of spaces and present them through the networks of their users’ activities. However, these accounts are predominantly limited in examining the extent to which these spaces may be heterogeneous when exploring such networks. This paper draws on recent ANT scholarship, which employs an ethnographic research conducted in a main park in a housing project at Dahiyat Al Hussein in Amman, Jordan. The findings describe the complex and unpredictable negotiations that occur within spaces by documenting the varieties and interrelations among user activity networks within this common and shared urban space. This research reveals the extent to which spaces, parks in this case, may be heterogeneous by unpacking their usage. The conclusions and insights assert the necessity of paying attention to design detail and creating designs that are responsive to evolving user activities.     

Crystal-field engineering of ultrabroadband mid-infrared emission in Co2+-doped nano-chalcogenide glass composites

Tunable and ultrabroadband mid-infrared (MIR) emissions in the range of 2.5–4.5 μm are firstly reported from Co²⁺-doped nano-chalcogenide (ChG) glass composites. The composites embedded with a variety of binary (ZnS, CdS, ZnSe) and ternary (ZnCdS, ZnSSe) ChG nanocrystals (NCs) can be readily obtained by a simple one-step thermal annealing method. They are highly transparent in the near- and mid-infrared wavelength region. Low-cost and commercially available Er³⁺-doped fiber lasers can be used as the excitation source. By crystal-field engineering of the embedded NCs through cation- or anion-substitution, the emission properties of Co²⁺ including its emission peak wavelength and bandwidth can be tailored in a broad spectral range. The phenomena can be accounted for by crystal-field theory. Such nano-ChG composites, perfectly filling the 3–4 μm spectral gap between the oscillations of Cr²⁺ and Fe²⁺ doped IIVI ChG crystals, may find important MIR photonic applications (e.g., gas sensing), or can be used directly as an efficient pump source for Fe²⁺: IIVI crystals which are suffering from lack of pump sources.     

Pt–Ru nanoparticles anchored on poly(brilliant cresyl blue) as a new polymeric support: Application as an efficient electrocatalyst in methanol oxidation reaction

The glassy carbon electrode is modified by poly(brilliant cresyl blue) (PBCB) to be applied as a new green and efficient platform for Pt and Pt–Ru alloy nanoparticles deposition. Surface composition, morphology and catalytic activity of these modified electrodes towards methanol oxidation are assessed by applying X-ray diffraction, field emission scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy techniques. The X-ray diffraction patterns reveal that the highly crystalline Pt and Pt–Ru alloy and RuO₂ nanoparticles with low crystallinity are deposited on the PBCB modified glassy carbon electrodes. The microscopic images indicate smaller size and better distribution of deposited nanoparticles on the surface of PBCB modified electrodes. Cyclic voltammetry and electrochemical impedance spectroscopy results reveal that PBCB supported Pt and Pt–Ru nanoparticles have better electrocatalytic performance and durability towards methanol oxidation rather than the unsupported nanoparticles. From the obtained results it can be concluded that the presence of PBCB not only improves the stability of nanoparticles on the surface, but also leads to the formation of smaller size and more uniform distribution of nanoparticles on the surface, which, in turn, cause the nanoparticles to provide a higher accessible surface area and more active centers for the oxidation of methanol. The results will be valuable in extending the applications of this polymer in surface modification steps and in developing promising catalyst supports to be applied in direct methanol fuel cells.