The thermochromic properties of La1−xSrxMnO3 compounds

La_1−xSr_xMnO₃ (LSMO) compounds (0.175x0.30) were prepared by conventional solid-state reaction method. Temperature dependence of the total hemispherical emittance (ε_H) of the compounds from 173 to 373 K was measured on a calorimetric emissometer (CE) which was constructed based on the steady-state calorimetric method. The compounds show thermochromic properties and ε_H's have low value at low temperature and have high value at high temperature, because the compounds are dominated by metallic phase and insulator phase, respectively. We use the phase separation model to interpret the temperature dependence of ε_H.     

PEC behaviour of mixed single crystals of tungsten sulphoselenide grown by a CVT technique

Photoelectrochemical (PEC) solar cells have been fabricated with single crystals of WS_xSe_2−x (0x2) grown by chemical vapour transport (CVT) technique. Energy band location and redox analysis of the material have been done using Mott–Schottky plots. These studies justify the selection of appropriate electrolyte for the PEC work. Various solar cells with single crystals of WSe₂, WS_0.5Se_1.5, WSSe, WS_1.5Se_0.5 and WS₂ as photoelectrodes have been prepared. The solar cell parameters e.g. the fill factor (FF), open circuit voltage (V_oc), short circuit current (I_sc) and efficiency (η) for all the different cells have been determined. In order to see the effect of increasing the concentration of selenium on the photoresponse, the electrolyte and the intensity of illumination was kept constant and all the samples of WS_xSe_2−x were prepared from crystals showing absolutely plane faces. The results have been thoroughly described and the implications have been discussed.     

Thermochemical two-step water splitting by ZrO2-supported NixFe3−xO4 for solar hydrogen production

A thermochemical two-step water-splitting cycle using a redox metal oxide was examined for Ni(II) ferrites or Ni_xFe_3−xO₄ (0  x  1) for the purpose of converting solar high-temperature heat to hydrogen. The Ni(II) ferrite was decomposed to Ni-doped wustite (Ni_yFe_1−yO) at 1400 °C under an inert atmosphere in the first thermal-reduction step of the cycle; it was then reoxidized with steam to generate hydrogen at 1000 °C in the second water-decomposition step. Although nondoped Fe₃O₄ powders formed a nonporous, dense mass of iron oxide by the fusion of FeO and its subsequent solidification after the thermal-reduction step, Ni(II)–ferrite powders were converted into a porous, soft mass after the step. This was probably because Ni doping in the FeO phase raised the melting point of wustite above 1400 °C. Supporting the Ni(II) ferrites on m-ZrO₂ (monoclinic zirconia) alleviated the high-temperature sintering of iron oxide; as a result, the supported ferrites exhibited greater reactivity and assisted the repeatability of the cyclic water splitting process as compared to the unsupported ferrites. The reactivity increased with the doping value x, and was maximum at x = 1.0 in the Ni_xFe_3−xO₄/m-ZrO₂ system.     

Properties of brush plated CdxZn1−xTe thin films

Cd_xZn_1−xTe (0  x  0.5) thin films were deposited for the first time by the brush plating technique using cadmium sulphate, zinc sulphate and tellurium dioxide precursors. The deposition current density was maintained at 100 mA cm⁻². X-ray diffraction studies indicated the formation of cubic phase with (1 1 1), (2 2 0), (3 1 1) orientations. From optical absorption measurements the band gaps of the films are found to be direct. AFM studies indicate a surface roughness around 54 Å. Density of the films of different composition has been estimated. Laser Raman studies indicated CdTe like LO and TO phonons.     

Electrical conduction studies of hot wall deposited CdSexTe1−x thin films

CdSe_xTe_1−x thin films of different compositions have been deposited on cleaned glass substrates using the hot wall deposition technique under conditions very close to thermodynamical equilibrium with minimum loss of material. The electrical conductivity of the deposited films has been studied as a function of temperature. All the films showed a transition from phonon-assisted hopping conduction through the impurity band to grain-boundary-limited conduction in the conduction/valence band at temperature around 325 K. The conductivity has been found to vary with composition; it varied from 0.0027 to 0.0198 Ω⁻¹ cm⁻¹ when x changed from 0 to 1. The activation energies of the films of different compositions determined at 225 and 400 K have been observed to lie in the range 0.0031–0.0098 and 0.0285–0.0750 eV, respectively. The Hall-effect studies carried out on the deposited films revealed that the nature of conductivity (p or n-type) was dependent on film composition; films with composition x=0 and 0.15 have been found to be p-type and the ones with composition x=0.4, 0.6, 0.7, 0.85 and 1 have been observed to exhibit n-type conductivity. The carrier concentration has been determined and is of the order of 10¹⁷ cm⁻³. The majority of carrier mobilities of the films have been observed to vary from 0.032 to 0.183 cm² V⁻¹ s⁻¹ depending on film composition. The study of the mobility of the charge carriers with temperature in the range of 300–450 K showed that the mobility increased with power of temperature indicating that the type of scattering mechanism in the studied temperature range is the ionized impurity scattering mechanism.     

New trends to grow the n-CdZn (S1−xSex)2/p-CuIn(S1−xSex)2 heterojunction thin films for solar cell applications

The n-CdZn(S_1−xSe_x) and p-CuIn(S_1−xSe_x)₂ thin films have been grown by the solution growth technique (SGT) on glass substrates. Also the heterojunction (p–n) based on n-CdZn (S_1−xSe_x)₂ and p-CuIn (S_1−xSe_x)₂ thin films fabricated by same technique. The n-CdZn(S_1−xSe_x)₂ thin film has been used as a window material which reduced the lattice mismatch problem at the junction with CuIn (S_1−xSe_x)₂ thin film as an absorber layer for stable solar cell preparation. Elemental analysis of the n-CdZn (S_1−xSe_x)₂ and p-CuIn(S_1−xSe_x)₂ thin films was confirmed by energy-dispersive analysis of X-ray (EDAX). The structural and optical properties were changed with respect to composition ‘x’ values. The best results of these parameters were obtained at x=0.5 composition. The uniform morphology of each film as well as the continuous smooth thickness deposition onto the glass substrates was confirmed by SEM study. The optical band gaps were determined from transmittance spectra in the range of 350–1000 nm. These values are 1.22 and 2.39 eV for CuIn(S_0.5Se_0.5)₂ and CdZn(S_0.5Se_0.5)₂ thin films, respectively. J–V characteristic was measured for the n-CdZn(S_1−xSe_x)₂/p-CuIn(S_1−xSe_x)₂ heterojunction thin films under light illumination. The device parameters V_oc=474.4 mV, J_sc=13.21 mA/cm², FF=47.8% and η=3.5% under an illumination of 85 mW/cm² on a cell active area of 1 cm² have been calculated for solar cell fabrication. The J–V characteristic of the device under dark condition was also studied and the ideality factor was calculated which is equal to 1.9 for n-CdZn(S_0.5Se_0.5)₂/p-CuIn(S_0.5Se_0.5)₂ heterojunction thin films.     

Predictions of turbulent flow and heat transfer in gas–droplets flow downstream of a sudden pipe expansion

Droplets-laden turbulent flow downstream of a sudden pipe expansion has been investigated by using Euler/Euler two-fluid model for the gaseous and dispersed phases. Significant increase of heat transfer in separated flow at the adding of evaporating droplets has been demonstrated (more than 2 times compare with one-phase flow at the value of mass concentration of droplets M_L1  0.05). Addition of dispersed phase to the turbulent gas flow results in insignificant increase of the reattachment length. Low-inertia droplets (d₁  50 μm) are well entrained into the circulation flow and present over the whole pipe section. Large particles (d₁ ≈ 100 μm) go through the shear layer not getting into the detached area. Comparison with experimental data on separated gas–droplets flows behind the plane backward-facing step has been carried out.     

Entropy production due to free convection in partially heated isosceles triangular enclosures

A numerical analysis of the entropy production has been performed due to natural convection heat transfer and fluid flow in isosceles triangular enclosures with partially heated from below and symmetrically cooled from sloping walls. Governing equations are solved by finite difference method. Governing parameters on flow and temperature fields are Rayleigh number (10³  Ra  8.8 × 10⁵), dimensionless length of heater (0.25  (ℓ′ = ℓ/L)  1.0), dimensionless location of heater (0.25  (c′ = c/L)  0.75) and inclination angle of slopping walls (30°  β  60°). Heat transfer results are presented in terms of local and mean Nusselt numbers (Nu) while entropy production results are shown with entropy production number (N_s) and Bejan number (Be). Isotherms, streamlines, contours of entropy production due to heat transfer and fluid friction irreversibility are plotted. It is observed that entropy production number increases but Bejan number decreases with increasing of Rayleigh number. However, both entropy production due to heat transfer and fluid friction irreversibility are affected by higher inclination angle of triangle and length of heater.     

Highly conducting transparent nanocrystalline Cd1−xSnxS thin film synthesized by RF magnetron sputtering and studies on its optical, electrical and field emission properties

Transparent conducting Cd_1−xSn_xS thin films have been synthesized by radio frequency magnetron sputtering technique on glass and Si substrates for various tin concentrations in the films. X-ray diffraction studies showed broadening of peaks due to smaller crystal size of the Cd_1−xSn_xS films, and SEM micrographs showed fine particles with average size of 100 nm. Sn concentration in the films was varied from 0% to 12.6% as determined from energy-dispersive X-ray analysis. The room-temperature electrical conductivity was found to vary from 8.086 to 939.7 S cm⁻¹ and corresponding activation energy varied from 0.226 to 0.076 eV. The optimum Sn concentration for obtaining maximum conductivity was found to be 9.3%. The corresponding electrical conductivity was found to be 939.7 S cm⁻¹, and the mobility 49.7 cm² V⁻¹ s⁻¹. Hall measurement showed very high carrier concentrations in the films lying in the range of 8.0218×10¹⁸–1.7225×10²⁰ cm⁻³. The conducting Cd_1−xSn_xS thin films also showed good field emission properties with a turn on field 4.74–7.86 V μm⁻¹ with variation of electrode distance 60–100 μm. UV–Vis–NIR spectrophotometric studies of the films showed not needed the optical band gap energy increased from 2.62 to 2.80 eV with increase of Sn concentration in the range 0–12.6%. The optical band gap was Burstein–Moss shifted, and the corresponding carrier concentration obtained from the shift also well matched with that obtained from Hall measurement.     

Bulk p-CuInSe2 photo-electrochemical solar cells

Dense CuInSe₂ of high quality, prepared by the fusion technique in evacuated quartz ampoule from stoichiometric melt, crystallizes in the chalcopyrite structure. Compositional analysis carried out by secondary ion mass spectrometry (SIMS) and energy dispersive spectroscopy (EDS) indicates a uniform distribution of elements through the depth and a composition close to the stoichiometry. The diffuse reflectance spectrum gives a band gap at 0.94 eV. The electrical conductivity follows an Arrhenius-type law with activation energy of 23 meV in conformity with polarons hopping. Above 320 °C, CuInSe₂ undergoes an irreversible oxidation. The thermal variation of the thermopower indicates p-type behavior attributed to copper deficiency and a hole mobility μ_300 K of 0.133 cm² V⁻¹ s⁻¹, thermally activated. In KCl media, the compound exhibits an excellent chemical stability with a corrosion rate of 8 μmol cm⁻² month⁻¹. The photo-electrochemical properties, investigated for the first time on the ingots, confirm the p-type conductivity. From the capacitance measurements, the flat band potential (V_fb=−0.62V_SCE) and the holes density (N_A=4×10¹⁷ cm⁻³) were determined. The valence band, located at 4.43 eV below vacuum, is made up of mainly Se orbital with little admixture of Cu character. The change of the electrolyte causes a variation in the potential V_fb (dV_fb/dpH=−0.058 V pH⁻¹) indicating strong OH⁻ adsorption. The fill factor in S²⁻ media was found to be 0.54; such result was corroborated by semi-logarithmic plots.     

Three-stage growth of Cu–In–Se polycrystalline thin films by chemical spray pyrolysis

Structural, optical and electrical properties of polycrystalline Cu–In–Se films, such as CuInSe₂ and ordered vacancy compounds (OVC), prepared by three-stage process of sequential chemical spray pyrolysis (CSP) of In–Se (first stage), Cu–Se (second stage) and In–Se (third stage) solutions have been studied in terms of substrate temperature at the second stage (T_S2). The films grown at T_S2420 °C exhibited larger grains in comparison with the Cu–In–Se films grown by the usual CSP method. Optical gap energy was approximately 1.06 eV for 360 °CT_S2420 °C, but increased dramatically from 1.06 to 1.35 eV when the T_S2 rose from 420 to 500 °C. Conductivity type was p-type for T_S2<420 °C, but n-type for T_S2>420 °C.     

Characterization of a porous medium employing numerical tools: Permeability and pressure-drop from Darcy to turbulence

A large set of microscopic flow simulations in the Representative Elementary Volume (REV) of a porous medium formed by staggered square cylinders is presented. For each Reynolds number selected, 10 different porosities are simulated in the 5–95% range. The Reynolds number is varied from Re = 10⁻³ to Re = 10⁵, covering the Stokes flow regime, the laminar flow regime and the turbulence flow regime. Low and moderate Reynolds number flow solutions (Re  200) are achieved by numerically solving the 2D Navier–Stokes equations. Reynolds Averaged Navier–Stokes equations are employed to simulate the turbulence regime. Numerical results allow the investigation of the microscopic features of the flow as a function of the porosity and Reynolds number. Based on these microscopic results, the permeability of the porous medium is computed and a porosity-dependent correlation is developed for this macroscopic parameter. The Darcy–Forchheimer term or, equivalently, the friction factor, is also computed to characterize the porous medium for the complete range of porosity and Reynolds number simulated. The Forchheimer coefficient is found to be weakly dependent on the Reynolds number and strongly dependent on the porosity if the flow is fully turbulent. A porosity-dependent correlation is proposed for this quantity for high Reynolds numbers.     

Pyrite (FeS2) thin films prepared by spray method using FeSO4 and (NH4)2Sx

A simple spray method for the preparation of pyrite (FeS₂) thin films has been studied using FeSO₄ and (NH₄)₂S_x as precursors for Fe and S, respectively. Aqueous solutions of these precursors are sprayed alternately onto a substrate heated up to 120°C. Although Fe–S compounds including pyrite are formed on the substrate by the spraying, sulfurization of deposited films is needed to convert other phases such as FeS or marcasite into pyrite. A single-phase pyrite film is obtained after the sulfurization in a H₂S atmosphere at around 500°C for 30 min. All pyrite films prepared show p-type conduction. They have a carrier concentration (p) in the range 10¹⁶–10²⁰ cm⁻³ and a Hall mobility (μ_H) in the range 200–1 cm²/V s. The best electrical properties (p=7×10¹⁶ cm⁻³, μ_H=210 cm²/V s) for a pyrite film prepared here show the excellence of this method. The use of a lower concentration FeSO₄ solution is found to enhance grain growth of pyrite crystals and also to improve electrical properties of pyrite films.     

Battery effects in organic photovoltaics based on polybithiophene

Homopolymer photovoltaic devices based on thin films of polybithiophene, prepared by direct electrodeposition onto transparent fluorine-doped tin oxide electrodes followed by evaporation of an aluminium electrode to complete the device, were reported by Leguenza et al. [J. Solid State Electrochem. 11 (2007) 577.] to exhibit very high open-circuit voltages (V_oc) of up to 2 V at a very low light intensity of 6.6 W m⁻². In this letter, we report our attempts to reproduce the results. We achieved V_oc's0.8 V under a light intensity of 23 W m⁻². We also observed an unexpected V_oc in the dark suggesting that the high voltages previously reported might be attributed to the polarization of the polybithiophene layer, which lead to a battery effect in the dark and therefore not entirely a photovoltaic effect. We conclude that more work is needed before this observation can conceivably be applied in organic photovoltaics. Most notably, the application of this polarization effect depends on the demonstration of the high V_oc under high luminous intensities (i.e. >200 W m⁻²) and at high current densities (>1 mA cm⁻²) which has not been achieved yet.     

WO3−x nanowires based electrochromic devices

A simple method was developed to fabricate tungsten oxide (WO_3−x) nanowires based electrochromic devices. The WO_3−x nanowires are grown directly from tungsten oxide powders in a tube furnace. The WO_3−x nanowires have diameters ranging from 30 to 70 nm and lengths up to several micrometers. The WO_3−x nanowires based device has short bleach-coloration transition time and can be grown on a large scale directly onto an ITO-coated glass that makes it potential in many electrochromic applications. The structure, morphology, and composition of the WO_3−x nanowires were characterized using the scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and energy-dispersive spectrometer. The optical and electrochromic performance of the nanowires layer under lithium intercalation was studied in detail by UV–VIS–NIR spectroscope and cyclic voltameter.     

Synthesis and characterization of oxygen-rich delafossite CuYO2+x—Application to H2-photo production

Here we report the synthesis and photo electrochemical properties of super oxides CuYO_2.50 and CuYO_2.25 prepared from the delafossite CuYO₂, respectively, by thermal oxidation at 380 °C under O₂-flow and soft chemistry in NaBrO solution (5 N). Their applications as catalysts for H₂ evolution upon visible light were investigated. The oxygen insertion was accompanied by partial oxidation of Cu⁺. For CuYO_2.25, the chemical analyses revealed the presence of mixed valent states containing at least formally an equal number of Cu⁺ and Cu²⁺. The thermal analysis (TGA) under reducing atmosphere indicates that oxygen is inserted in different crystallographic sites, for CuYO_2.25 it exhibits a two-step reduction mechanism with restoration of the parent oxide. In air, CuYO_2+x is thermally stable up to 500 °C above which it undergoes irreversible conversion into Cu₂Y₂O₅. They display p-type behavior ascribed to oxygen insertion and the conduction occurs by hopping mechanism between mixed copper valences. Under illumination, the oxides are stabilized by hole consumption reactions involving SO₃²⁻ and S²⁻ as holes scavengers. The flat-band potentials, lying between 0.17 and 0.26 V_SCE, allow a spontaneous H₂-photo formation. The rate of H₂-evolution is altered by the oxygen insertion and the best photo activity (1.33 μmol h⁻¹ mg⁻¹) was obtained over CuYO_2.25 immersed in S²⁻ solution (0.025 M); CuYO₂ is also reported for a comparison goal. Over time, the photoactivity is slowed down because of the competitive reduction of H₂O with the final products namely S₂O₆²⁻ and S_n²⁻.     

A note on fast protonic solid state electrochromic device: NiOx/Ta2O5/WO3−x

In the present investigation, the electrochromic properties of a fast protonic solid state device: NiO_x/Ta₂O₅/WO_3−x prepared at room temperature (300 K) is reported. The non-stoichiometric tungsten oxide thin film is prepared by reactive DC magnetron sputtering technique on ITO coated glass; the oxides of tantalum (300 nm) and nickel (100 nm) are prepared by electron beam evaporation. This proton device has a coloration efficiency of 82.4 cm²/C and coloration and bleaching time of 6 and 5 s, respectively, and a transmittance variation of 60%. The work function of WO_3−x thin films by Kelvin probe in uncolored and colored states are 4.73 and 4.30 eV, respectively.     

Mixed convective heat transfer in rectangular enclosures driven by a continuously moving horizontal plate

The fluid flow and heat transfer induced by the combined effects of the mechanically driven lid and the buoyancy force within rectangular enclosures were investigated in this work. The fluid filled enclosures are heated and lid-driven either on the upper or on the lower horizontal wall, thermally isolated on the right vertical wall, and cooled on the other walls. The basis of the investigation was the numerical solutions of the equations for the conservation of mass, momentum, and energy transport using the finite difference method. The effects of the flow governing parameters including the Richardson and the Prandtl numbers, and the length-to-height aspect ratio, respectively, in the range 10⁻²  Ri  10², 10⁻³  Pr  10, and 1  AR  4 for a fixed Reynolds number, Re = 100, were studied. The results are presented in the form of the hydrodynamic and thermal fields, and the profiles for vertical and horizontal components of velocity, temperature, and the local heat flux. The fluid flow and energy distributions within the enclosures and heat flux on the heated wall are enhanced by the increase in the Richardson number. While an increase in the Prandtl number improves the heat flux on the heated wall, an increase in aspect ratio suppresses it. The results can be used as base line data in the design of systems in which mixed convection heat transfer in rectangular enclosures occurs.     

Heat and fluid flow resulting from the chimney effect in a symmetrically heated vertical channel with adiabatic extensions

An experimental study on a channel-chimney system was carried out in order to elucidate the behavior of heat transfer and fluid flow. The results are presented in terms of local air temperature measurements inside the symmetrically heated channel and between the adiabatic extensions. Different fluid motion regions are observed inside the chimney. Inflows of air are detected in the lower extension ratio, particularly for large values of the ratio of the width of chimney to that of the heated channel. Some typical configurations show the presence of a vortex structure for an expansion ratio greater than one close to the corner regions in the chimney. Some monomial correlation equations between the local Nusselt number, the channel Rayleigh number and the geometric parameters are proposed. The dimensionless parameters are in the following ranges: 10²Ra^*(B/b)10⁶; 1.5L/L_h4.0; 1.0B/b4.0, in which L is the total height of the system, L_h is the height of the heated channel, B is the width of the chimney and b is the width of the heated channel. A good agreement between the correlation and the experimental data is observed.     

Enhanced heat transfer in inclined solar chimneys by electrohydrodynamic technique

Heat transfer enhancement of natural convection inside the inclined solar chimneys is investigated using electrohydrodynamic technique. The interactions between electric field, flow field, and temperature field are analyzed. The ranges of parameters considered are 10⁴Ra10⁷, 7.5 kVV₀17.5 kV, 30°θ120°, and 2aspect ratio14. Flow and heat transfer enhancements are significantly influenced at low Rayleigh number. The optimum inclined angle which obtains maximum volume flow rate and heat transfer is found to be at θ=60°. A maximum volume flow rate enhancement is expressed in relation with the number of electrodes. The relation between aspect ratio of chimney and number of electrodes that performs the optimum condition between efficiency and economy is analyzed incorporating with all concerning parameters.