Electrochromic performance of a poly(3,4-ethylenedioxythiophene)-Prussian blue device encompassing a free standing proton electrolyte film

Electrochromic devices incorporating an electropolymerized poly(3,4-ethylenedioxythiophene) (PEDOT) film and a free standing, transparent film of a proton conducting polymer electrolyte with high ambient temperature ionic conductivity of 10⁻² S cm⁻¹ have been fabricated with and without the ion storage electrodeposited Prussian blue (PB) counter electrode layer. While coloration efficiency increases as a function of applied potential in the sole PEDOT device with largest values of CE_(max,VIS) ∼ 120 cm² C⁻¹ and CE_(max,NIR) ∼ 133 cm² C⁻¹ attained at V_c = −1.9 V, the PEDOT:PB device shows a digression from this trend. Much higher coloration efficiencies in the visible (247 cm² C⁻¹ at 570 nm) and NIR (116 cm² C⁻¹ at 1100 nm) regions are achieved for the PEDOT:PB device at a relatively lower reducing voltage of −0.8 V. The PEDOT:PB device shows fast switching redox process (t_c = 2.6 s and t_b = 1.3 s for a 50% optical contrast at 632.8 nm) and a highly reversible charge density as the ratio of Q_inserted to Q_extracted was found to vary between 0.8 and 1.0. When switched between the clear and blue states for 2000 cycles, the insignificant drop in peak current density maxima observed for the PEDOT:PB device, i.e. the good cycling stability, the facile fabrication of device assembly, the ease of scaling up the electrolyte and electrochromic coatings, indicate that this method can be adapted as a simple and inexpensive alternative to conventional electrochromic windows with high cost components.     

Carbon dioxide emission and its regulation at land–water interface downstream of a point source at Ganga River (India)

The streams and rivers are considered hotspots of CO₂ exchange; and representative direct CO₂ emission measurements are essential for a correct regional estimate. We measured CO₂ emission flux at 15 sites at land–water interface downstream of a point source during low flow for three consecutive months for the year 2017. The general range of CO₂ efflux observed here was close to the results of regional studies, although values near the point source were disproportionately high (>350 mg/m²/h). CO₂ emission flux showed strong dependence on total organic carbon (TOC; R² = 0.96; P < 0.001), (R² = 0.88; P < 0.001), soluble reactive‐P (SRP; R² = 0.91; P < 0.001) and microbial activity measured in terms of fluorescein diacetate activity (FDAase; R² = 0.92; P < 0.001) and substrate induced respiration (SIR; R² = 0.96; P < 0.001). Because point source‐associated interfaces provide heterogeneous habitats, our study suggests the need for large scale monitoring of CO₂ emission at land–water interface of major rivers for more correctly presenting the regional scale CO₂ budget.     

Efficiency enhancement in DSSC using metal nanoparticles: A size dependent study

The photoelectrode of Eosin-Y sensitised DSSC was modified by incorporating Au-nanoparticles to enhance the power conversion efficiency via scattering from surface plasmon polaritons. Size dependence of Au nanoparticle on conversion efficiency was performed in DSSC for the first time by varying the particle size from 20 to 94 nm. It was found that, the conversion efficiency is highly dependent on the size of the Au nanoparticles. For larger particles (>50 nm), the efficiency was found to be increased due to constructive interference between the transmitted and scattered waves from the Au nanoparticle while for smaller particles, the efficiency decreases due to destructive interference. Also a reduction in the V_oc was observed in general, due to the negative shifting of the TiO₂ Fermi level on the adsorption of Au nanoparticle. This shift was negligible for larger particles. When 94 nm size particles were employed the conversion efficiency was doubled from 0.74% to 1.52%. This study points towards the application of the scattering effect of metal nanoparticle to enhance the conversion efficiency in DSSCs.     

Pyrochlore type semiconducting ceramic oxides in Ca-Ce-Ti-M-O system (M = Nb or Ta)—Structure, microstructure and electrical properties

A new series of pyrochlore type ceramic semiconducting oxides in Ca-Ce-Ti-M-O (M = Nb or Ta) system has been synthesized by the conventional ceramic route. The electrical conductivity measurements show that these oxides exhibit semiconducting behavior and the conductivity increases with the Ce content in the compound. Activation energy of the current carriers is in the range of 0.5-1.6 eV. The electrical conductivity in these oxides is due to the presence of Ce³⁺, which remains in the reduced state without being oxidized to Ce⁴⁺ by structural stabilization. The photoluminescence and X-ray photoelectron spectroscopy analysis corroborate the presence of Ce in the 3+ state. Impedance spectral analysis is carried out to evaluate the transport properties and indicates that the conduction in these compounds is mainly due to electronic contribution. The X-ray powder diffraction and Raman spectroscopy analysis establishes that these oxides belong to a cubic pyrochlore type structure.     

Application of Sequential Learning Neural Networks to Civil Engineering Modeling Problems

A sequential orthogonal approach to the building and training of a single hidden layer neural network is presented in this paper. The Sequential Learning Neural Network (SLNN) model proposed by Zhang and Morris [1]is used in this paper to tackle the common problem encountered by the conventional Feed Forward Neural Network (FFNN) in determining the network structure in the number of hidden layers and the number of hidden neurons in each layer. The procedure starts with a single hidden neuron and sequentially increases in the number of hidden neurons until the model error is sufficiently small. The classical Gram–Schmidt orthogonalization method is used at each step to form a set of orthogonal bases for the space spanned by output vectors of the hidden neurons. In this approach it is possible to determine the necessary number of hidden neurons required. However, for the problems investigated in this paper, one hidden neuron itself is sufficient to achieve the desired accuracy. The neural network architecture has been trained and tested on two practical civil engineering problems – soil classification, and the prediction o strength and workability of high performance concrete.     

Electrochemically deposited sol-gel-derived silicate films as a viable alternative in thin-film design

Sol-gel-derived silicate films were electrochemically deposited on conducting surfaces from a sol consisting of tetramethoxysilane (TMOS). In this method, a sufficiently negative potential is applied to the electrode surface to reduce oxygen to hydroxyl ions, which serves as the catalyst for the hydrolysis and condensation of TMOS. The electrodeposition process was followed by the electrochemical quartz crystal microbalance and cyclic voltammetry. The electrodeposited films were characterized for their surface morphology, porosity, and film thickness using atomic force microscopy, electrochemical probe techniques, surface area and pore size analysis, and profilometry. The electrodeposited films were found to have a completely different surface structure and to be significantly rougher relative to spin-coated films. This is likely due in part to the separation of the gelation and evaporation stages of film formation. The electrodeposited films were found to be permeable to simple redox molecules, such as ruthenium(III) hexaammine and ferrocene methanol. Film thickness can be easily varied from < 75 nm to > 15 microm by varying the electrode potential from -600 mV to more than -1000 mV, respectively. The electrodeposition process was further applied for the electroencapsulation of redox molecules and organic dyes within the silicate network. Cyclic voltammograms for the gel-entrapped ferrocene methanol (FcCH2OH) and ruthenium(II) tris(bipyridine) (Ru(bpy)3(2+)) exhibited the characteristic redox behavior of the molecules. The electroencapsulation of organic dyes in their "native" form proved to be more difficult because these species typically contain reducible functionalities that change the structure of the dye.     

Advances In Peer-To-Peer Content Search

Peer-to-peer (P2P) computer networks have recently received tremendous attention due to their inherent scalability and flexibility, which facilitates a broad spectrum of innovative multimedia applications. Such networks rely on the power of participant nodes of the network (called peers) for communications and computation. Traditional applications of P2P multimedia include decentralized file sharing and content distribution. Yet, the value of the virtually unlimited amount of data distributed in the P2P network will be sacrificed if effective and efficient ways to locate the content are missing. This challenge has stimulated extensive research in recent years, and many new P2P content search methods have been proposed. This paper provides a timely review of influential work in the area of peer-to-peer (P2P) content search. We begin with a survey of text-based P2P search mechanisms and continue with an exposition of content-based and semantic-based approaches followed by a discussion of future directions.     

FTIR investigations of solid precursor materials for sol-gel deposition of WO3 based electrochromic films

Peroxypolytungstic acid derivative (APTA) and peroxypolytungstic acid derivative coupled with a dicarboxylic acid additive i.e., oxalic acid dihydrate (APTA + OAD) in xerogel form, synthesized by a wet chemistry route were the solid sol-gel precursors for casting WO₃ films. These bulk materials have a complex structure owing to the presence of several groups such as acetate, peroxy anions and water molecules in their basic matrix. Additionally, oxalate ions constitute an integral part of the structure in the APTA + OAD xerogel. Detailed FTIR analysis of these coordination compounds has thrown light on the modes of association of the various anions or groups with tungsten metal ion. The mode of coordination of the acetate ion as a bidentate as well as a monodentate ligand enabling chelate formation and the several other chemical linkages prevalent in APTA have been established. Upon the incorporation of OAD in APTA, the net ramifications are drastic changes in the structure inclusive of changes in the nature and strength of metal - ligand bonding, which is exemplified by FTIR studies of (APTA + OAD) xerogel.     

Influence of polyethylene glycol template on microstructure and electrochromic properties of tungsten oxide

Electrochemical synthesis of tungsten oxide (WO₃) thin film nanostructures by potentiostatically controlling the surface aggregates formed at the electrode–electrolyte interface, in the presence of a polymeric template (polyethylene glycol 400, PEG) from a plating sol of peroxotungstic acid (PTA) is presented. The nanoparticulate morphology of the WO₃ film changes drastically upon varying PEG content in the precursor sol; from an amorphous structure with randomly distributed pores for a film derived from a PTA sol with PEG:ethanol in a 3:7 volume ratio, to a mesoporous, nanocrystalline material with hybrid structures encompassing spherical grains and nanorod-like shapes with a triclinic modification for a film formed in a sol with PEG:ethanol in a 1:1 volume ratio. This approach highlights the role of the PEG proportion in controlling crystal growth, assembly patterns and pore structure. The film derived from the sol with PEG:ethanol in a 1:1 volume ratio exhibits superior transmission modulation and coloration efficiency as compared to the film obtained from a sol with PEG:ethanol in a 3:7 volume ratio. While the latter film deteriorates rapidly within 35 color-bleach cycles, the former film sustains more than 3500 cycles, without significant degradation. This film also exhibits fast switching between the clear and blue states; these are repercussions of the mesopore structure and the interconnected nanocrystallite phase.     

In situ growth of SiC wires on CVI densification of SiC foam

Silicon carbide (SiC) foam prepared by polymer infiltration and pyrolysis (PIP) process was further densified with β-SiC by chemical vapor infiltration (CVI) technique. Scanning electron microscopy and high-resolution transmission electron microscopy images confirmed the presence of highly entangled and branched in situ grown SiC wires of uniform diameter (∼500 nm) over the struts of open-cell SiC foam. A uniform rate increase in diameter from nanometer to micron range (∼11 μm) was observed with an increase in the CVI reaction period. X-ray diffraction results showed the formation of highly crystalline β-SiC structure along the <111> direction with stacking faults. The formation of SiC wires was explained by the vapor–liquid–solid mechanism and evenness of the surface and uniform growth rate of SiC confirmed the homogeneous concentration of gaseous species during CVI reaction. The compressive strength increased with relative density, with maximum values of 5.5 ± 1.26 MPa for ultimate SiC foam (ρ = 400 kg/m³) prepared by hybrid PIP/CVI technique. The thermo-oxidative stability of the resultant foam was evaluated up to 1650°C under air and shows excellent thermal stability compared to SiC foam prepared by PIP route. The densified SiC foam can find potential applications in the field of hot gas filters, catalyst supports, microwave absorption properties, and heat insulation for high-temperature applications.