Spectrally selective laminated glazing consisting of solar control and heat mirror coated glass: preparation, characterization and modelling of heat transfer

In this study, solar control coatings were prepared by sequential depositions of thin films of ZnS (40 nm)–CuS (150 nm) and ZnS (40 nm)–Bi₂S₃ (75 nm)–CuS (150 nm) from chemical baths on 3 mm thick commercial sheet glass. These were laminated to 3 mm thick clear glass or commercially available SnO₂ based heat mirror coating of sheet resistance 15 Ω on float glass of 3 mm thickness using a poly(ethylene vinyl acetate), EVA, sheet of 0.36 mm thickness in a vacuum process at 120 °C for 30 min. In total, the thickness of the glazing was 6.35 mm. The glazings possess visible transmittance, weighted for D65 solar spectra and sensitivity of the human eye for daylight vision, of 36% or 14% with solar absorptance of 71% or 78% depending on the coating type, i.e ZnS–CuS or ZnS–Bi₂S₃–CuS-heat mirror respectively. The solar heat gain coefficient (SHGC) was evaluated for these glazings at exterior temperatures of 15 and 32 °C for an exterior convective heat transfer coefficient (h_ex) of 6–100 Wm⁻² K⁻¹ using a mathematical model. The model predicts the extent of reduction in SHGC through the presence of the heat mirror coating as a function of h_ex and hence helps to decide on the relative benefit, which may be derived through their use in different locations. Though the deposition technique mentioned here involves longer duration compared with vacuum techniques, it may be developed into a low throughput, low-capital alternate technology for small-scale production.     

Characterisation of high-temperature-resistant spectrally selective paints for solar absorbers

The spectrally selective paint coatings were prepared from organically modified siloxane resin and inorganic pigment (FeMnCuO_x-P320). To optimise the low-emittance properties, different thicknesses of paints were applied on high-reflecting Al foil by a draw bar coater. For all paints, optical and thermal properties were determined as well as their adhesion resistance. Pigment to volume concentration ratio was 20% and for thicknesses of about 1.7–2.0 g/m², the solar absorptance for these samples were a_s=0.90–0.92 with corresponding thermal emittance of e_T=0.20–0.25. Temperature stability of these samples was followed by FT-IR spectroscopy at 300°C. The obtained results indicated good temperature stability of prepared paint coatings.     

Characterization of Pr1−xSrxCo0.8Fe0.2O3−δ (0.2 ≤ x ≤ 0.6) cathode materials for intermediate-temperature solid oxide fuel cells

Cathode materials consisting of Pr_1−xSr_xCo_0.8Fe_0.2O_3−δ (x = 0.2–0.6) were prepared by the sol–gel process for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The samples had an orthorhombic perovskite structure. The electrical conductivities were all higher than 279 S cm⁻¹. The highest conductivity, 1040 S cm⁻¹, was found at 300 °C for the composition x = 0.4. Symmetrical cathodes made of Pr_0.6Sr_0.4Co_0.8Fe_0.2O_3−δ (PSCF)–Ce_0.85Gd_0.15O_1.925 (50:50 by weight) composite powders were screen-printed on GDC electrolyte pellets. The area specific resistance value for the PSCF–GDC cathode was as low as 0.046 Ω cm² at 800 °C. The maximum power densities of a cell using the PSCF–GDC cathode were 520 mW cm⁻², 435 mW cm⁻² and 303 mW cm⁻² at 800 °C, 750 °C and 700 °C, respectively.     

High-temperature optical properties and stability of AlxOy–AlNx–Al solar selective absorbing surface prepared by DC magnetron reactive sputtering

Al_xO_y–AlN_x–Al selective absorbing surface was prepared by DC magnetron reactive sputtering with aluminum alloy (LY13)¹ in air and argon. The studies were carried out to access the high-temperature (400°C–600°C) optical properties and stability of the coatings. The coatings were found to withstand heating at 600°C for 30 min in 4.5×10⁻³ Pa vacuum with absorptance 0.94 and emittance 0.07 after annealing. After heating at 450°C for 10 h, the specimen still had good performance whose absorptance and emittance was 0.93 and 0.07, respectively. Auger electron spectroscopy was used to analyse the structure of the solar selective surface before and after annealing.     

Copper based thin films to improve glazing for energy-savings in buildings

This paper presents research results for better window materials for energy saving purposes. Three alternatives of glazing treatments were developed in this project: Cu₂O, CuS + Cu₂O, and Cu + Cu₂O. The second and third alternatives present an adequate control in the infrared irradiance, achieving a significant reduction of the heat transfer through them. These windows allow the transmission of about half of the heat under hot weather condition, thus reducing the thermal load inside the building. The same windows also reduce the outwards flow of heat at half of the rate of windows without coating, improving comfort and reducing heat loss under cold weather conditions. The thin layers were produced using a sputtering technique with planar magnetrons. A high purity copper target (99.99%) was evaporated through plasma of argon–oxygen (70–30% respectively) in order to obtain Cu₂O. Soda-lime glass substrates of 600 × 400 mm were used. About 50% of the infrared is blocked by the Cu₂O window, when it is applied for thermal comfort. Thus, it was necessary to add another layer (CuS), which allowed a reduction of up to 20% in the NIR. The spectral behavior of the Cu + Cu₂O window showed a transmittance of about 50% in VIS range, while in the NIR, the transmittance decreased from 40% to 20%. The composite windows, which contained CuS, Cu, and Cu₂O are suitable solutions for solar control. Simulations of annual energy savings were carried out with the Energy-10 software for the Cu₂O + CuS window for two cities, Mexico City and Mexicali, the latter representing extreme weather conditions (over 35 °C in summer and below 6 °C in winter). The total energy saving was approximately 20% of the total energy demand for Mexicali. Thermal transmission measurements were also carried out at the center of these windows, giving values of about 4 W/m² K.     

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.     

Technical note Copper oxide coatings for use in a linear solar Fresnel reflecting concentrating collector

Electroplating selective copper oxide coatings were prepared on the surface of a rectangular absorber (α = 0.92 and ₁₀₀°C = 0.18) for operation in conjunction with a prototype linear solar Fresnel reflecting concentrating collector. Overall heat loss coefficients (U_L) of the selectively coated absorber at temperatures up to 300°C, optical efficiency (η_o) and stagnation temperature of the concentrator–absorber system were determined experimentally. The results have been compared with those obtained from an identical black painted absorber. Thermal efficiency (η_c) computed from the results of U_L and η_o measurements at a temperature of 250°C provides a value of 49% with the selectively coated absorber and 48% with the black painted absorber.     

More stable low gap a-Si:H layers deposited by PE-CVD at moderately high temperature with hydrogen dilution

In the present work, several series with variation of deposition parameters such as hydrogen dilution ratio, VHF-power and plasma excitation frequency f_exc have been extensively analyzed. Compared with “conventional” more-stable layers obtained at 200–250°C and high H₂ dilution ratios of about 10, it was observed that electrical transport properties after light-induced degradation of layers deposited at “moderately high” temperatures (300–350°C) are equivalent but required lower H₂ dilution ratios (between 2 and 4). As a consequence, the deposition rate of more stable layers obtained at moderately high temperatures is increased by a factor of 2. Moreover, optical gaps of a-Si:H deposited at 300–350°C are significantly lower (by approx. 10 meV); furthermore, they decrease with f_exc.     

Electrochromism in NiOx and WOx obtained by spray pyrolysis

Electrochromic films of NiO_x and WO_x were produced by the spray pyrolysis technique. The nickel-oxide-based coatings were obtained from an aqueous solution of nickel nitrate. Those obtained below 300° C did not show any diffraction peak when subjected to X-ray diffraction analysis, and those obtained above 400° C showed a diffraction pattern corresponding to cubic NiO. Films obtained below 300° C showed an electrochromic effect with an electrochromic efficiency of 30 cm²/C.Tungsten-oxide-based coatings were obtained from a solution of H₂WO₄ in aqueous ammonia. The films were grown at 150° C, and they showed a diffraction pattern corresponding to monoclinic WO₃ when subjected to a post-heat treatment at 400° C during ten minutes. The WO_x films showed a noticeable electrochromism under cation insertion, and presented an electrochromic efficiency of 42 cm²/C. Both as-deposited and heat-treated samples showed good electrochromism.     

Optical and electrical properties of vanadium dioxide films prepared under optimized RF sputtering conditions

Vanadium dioxide films were prepared by DC and rf reactive magnetron sputtering of a 99.7% pure vanadium target in an Ar+O₂ plasma with a well-controlled oxygen partial pressure. The films were deposited onto normal glass substrates at 400°C. The films showed a metal–semiconductor transition at the temperature, τ_c=65–68°C. Optical and electrical properties of the films were investigated around the metal–semiconductor phase transition and found to be very sensitive to the oxygen flow rate. Sheet resistance of the films were recorded using a two-point probe over the temperature range 26τ100°C. It was observed that the sheet resistance can change by three orders of magnitude when heating the films from room temperature to temperatures above the transition. Transmittance of the films was obtained in the 300λ2500 nm wavelength range at two extreme temperatures (i.e. 26°C and 100°C). The luminous transmittance for the films was rather unaffected with heating, whereas near-infrared transmittance showed lower values. Optical constants, n and k were measured using ellipsometry. The semiconducting state optical constants were found to be 2.67 and 0.04 for n and k, respectively, while the metallic state values were 2.26 for refractive index and 0.3 for the extinction coefficient. The samples showed a slow deterioration when left in the laboratory for a period of one year.     

Assessment of reservoir temperatures of thermal springs of the northern areas of Pakistan by chemical and isotope geothermometry

Chemical and isotope geothermometers, i.e. the Na–K, K–Mg, quartz and δ¹⁸O(SO₄–H₂O), have been applied to estimate the reservoir temperature of the thermal springs in the northern areas of Pakistan. The chemical types of the thermal waters and the effects of mixing of shallow cold water with the thermal end-members are discussed. These waters are neutral to slightly alkaline and have low dissolved contents. Sodium is the dominant cation in almost all the cases. In terms of anions, the hot waters of Budelas are of the SO₄ type, those of Tatta Pani are of mixed character (SO₄ and HCO₃), and the waters from the remaining areas show HCO₃ domination. An absence of tritium in Tatta Pani and Tato thermal springs indicates that they do not have any contribution of shallow young water. In the case of the Murtazabad springs, the wide range of tritium concentrations, negative correlations with surface temperature and Cl, and positive correlation between Na and Cl show that the shallow cold groundwater is mixing with thermal water in different proportions. For the mixed water of Murtazabad thermal springs, ‘isochemical modelling’ using the Na–K, K–Mg and quartz geothermometers indicates an equilibrium temperature in the range 185–200 °C. The δ¹⁸O(SO₄–H₂O) geothermometer gives relatively low temperatures for three springs, whereas two samples are close to the 185–200 °C temperature interval. The reservoir temperatures of Tatta Pani springs (100–120 °C), determined by Na–K and quartz geothermometers, are in good agreement. The δ¹⁸O(SO₄–H₂O) geothermometer gives a relatively higher range (140–150 °C) for most of the Tatta Pani springs. For Tato spring, the isotope and chemical geothermometers (except for the K–Mg) agree on an equilibrium temperature of about 170 °C. Reservoir temperatures of the remaining minor fields are not conclusive due to the lack of sufficient data.     

Electrochromic properties of Nb2O5 sol–gel coatings

Sol–gel niobium oxide coatings are promising electrochromic materials. The sols have been prepared by a sonocatalytic mixing of NbCl₅ powder, butanol and acetic acid. Thermal analysis (DTA/TG) coupled to mass spectrometry has been performed on Nb₂O₅ precipitates to quantitatively analyse the effluents. Transparent and defect-free single and multilayers coatings have been deposited on ITO-coated glass by a dip-coating process and then calcined between 400°C and 600°C. The coatings structure change from amorphous to crystalline (TT form) and the later ones are highly textured. The films present a reversible and fast insertion/extraction kinetics for Li⁺ ions. After insertion the amorphous coatings present a grey-brown color, while the crystalline ones are dark blue. The maximum charge density exchanged with a three-layer 200 nm thick coating sintered at 600°C was 16 mC/cm² with a corresponding spectral transmission change practically wavelength-independent varying from 80% to 20%. The coloring efficiency determined at λ=600 nm was 22 cm²/C.     

Synthesis of LiFePO4/polyacenes using iron oxyhydroxide as an iron source

LiFePO₄/polyacenes (PAS) composite is synthesized by iron oxyhydroxide as a new raw material and phenol–formaldehyde resin as both reducing agent and carbon source. The mechanism of the reaction is outlined by the analysis of XRD, FTIR as well as TG/DSC. The results show that the formation of LiFePO₄ is started at 300 °C, and above 550 °C, the product can be mainly ascribed to olivine LiFePO₄. The electrochemical properties of the synthesized composites are investigated by charge–discharge tests. It is found that the prepared sample at 750 °C (S750) has a better electrochemical performance than samples prepared at other temperatures. A discharge capacity of 158 mAh g⁻¹ is delivered at 0.2 C. Under high discharge rate of 10 C, a discharge capacity of 145 mAh g⁻¹ and good capacity retention of 93% after 800 cycles are achieved. The morphology of S750 and PAS distribution in it are investigated by SEM and TEM.     

Deposition of transparent and conductive Al-doped ZnO thin films for photovoltaic solar cells

The effect of the substrate temperature on the optoelectronic properties of ZnO-based thin films prepared by rf magnetron sputtering has been studied. Three different targets (Zn/Al 98/2 at%, ZnO:Al 98/2 at% and ZnO:Al₂O₃ 98/2 wt%) have been investigated in order to compare resulting samples and try to reduce the substrate temperature down to room temperature. From the ZnO:Al₂O₃ target, transparent conductive zinc oxide has been obtained at 25°C with the average optical transmission in the 400–800 nm wavelength range, T = 80–90% and resistivity, = 3−5 × 10⁻³ Ωcm. In Al:Zn0 layers, the spatial distribution of the electrical properties across the substrate placed parallel to the target has been improved by depositing at high substrate temperatures, above 200°C. Besides, owing to diffusion processes of CuInSe₂ and CdS take place at 200°C, an AI:ZnO/CdS/CuInSe₂ polycrystalline solar cell made with the Al:ZnO deposited at 25°C as the transparent conductive oxide, has shown a more efficient photovoltaic response, η = 6.8%, than the one measured when the aluminium-doped zinc oxide has been prepared at 200°C, η = 1.8%.     

Fundamental understanding and implementation of Al-enhanced PECVD SiNx hydrogenation in silicon ribbons

A low-cost, manufacturable defect gettering and passivation treatment, involving simultaneous anneal of a PECVD SiN_x film and a screen-printed Al layer, is found to improve the lifetime in Si ribbon materials from 1–10 μs to over 20 μs. Our results indicate that the optimum anneal temperature for SiN_x-induced hydrogenation is 700°C for EFG and increases to 825°C when Al is present on the back of the sample. This not only improves the degree of hydrogenation, but also forms an effective back surface field. We propose a three-step physical model, based on our results, in which defect passivation is governed by the release of hydrogen from the SiN_x film due to annealing, the generation of vacancies during Al–Si alloying, and the retention of hydrogen at defect sites due to rapid cooling. Controlled rapid cooling was implemented after the hydrogenation anneal to improve the retention of hydrogen at defect sites by incorporating an RTP contact firing scheme. RTP contact firing improved the performance of ribbon solar cells by 1.3–1.5% absolute when compared to slow, belt furnace contact firing. This enhancement was due to improved back surface recombination velocity, fill factor, and bulk lifetime. Enhanced hydrogenation and rapid heating and cooling resulted in screen-printed Si ribbon cell efficiencies approaching 15%.     

Electrodeposited cuprous oxide on indium tin oxide for solar applications

Semiconducting cuprous oxide films were prepared by electrodeposition onto commercial conducting glass coated with indium tin oxide deposited by spraying technique. The cuprous oxide (Cu₂O) films were deposited using a galvanostatic method from an alkaline CuSO₄ bath containing lactic acid and sodium hydroxide at a temperature of 60°C. The film's thickness was about 4–6 μm. This paper includes discussion for Cu₂O films fabrication, scanning electron microscopy and X-ray diffractometry studies, optical properties and experimental results of solar cells. The values of the open circuit voltage V_oc of 340 mV and the short circuit current density I_sc of 245 μA/cm² for ITO/Cu₂O solar cell were obtained by depositing graphite paste on the rear of the Cu₂O layer. It should be stressed that these cells exhibited photovoltaic properties after heat treatment of the films for 3 h at 130°C. An electrodeposited layer of Cu₂O offers wider possibilites for application and production of low cost cells, both in metal–semiconductor and hetero-junction cell structures, hence the need to improve the photovoltaic properties of the cells.     

Steam reforming and oxidative steam reforming of methanol over CuO–CeO2 catalysts

Steam reforming (SRM) and oxidative steam reforming of methanol (OSRM) were carried out over a series of coprecipitated CuO–CeO₂ catalysts with varying copper content in the range of 30–80 at.% Cu (= 100 × Cu/(Cu + Ce)). The effects of copper content, reaction temperature and O₂ concentration on catalytic activity were investigated. The activity of CuO–CeO₂ catalysts for SRM and OSRM increased with the copper content and 70 at.% CuO–CeO₂ catalyst showed the highest activity in the temperature range of 160–300 °C for both SRM and OSRM. After SRM or OSRM, the copper species in the catalysts observed by XRD were mainly metallic copper with small amount of CuO and Cu₂O, an indication that metallic copper is an active species in the catalysis of both SRM and OSRM. It was observed that the methanol conversion increased considerably with the addition of O₂ into the feed stream, indicating that the partial oxidation of methanol (POM) is much faster than SRM. The optimum 70 at.% CuO–CeO₂ catalyst showed stable activities for both SRM and OSRM reactions at 300 °C.     

The structural, transport and optical properties of screen printed CuxS thick films

The structural, transport and optical properties of screen printed CuxS thick films with possible application in photovoltaic and photothermal devices are reported. The X-ray diffraction studies show that the screen printed films are stable up to about 220°C in air and belong to the CuxS structure. Above this temperature it decomposes mainly to CuSO₄. The electrical conductivity depends on the sintering temperature and the amount of flux, Cu(NO₃)₂, used in the paste for screen printing. The differential scanning calorimetry studies reveal the phase changes occurring during heating and pertaining to the dependence of electrical conductivity on the sintering temperature. A configuration consisting of screen printed CuxS on chemically deposited and annealed (at 200°C) CdS thin film exhibited rectification.     

New Li ion-conducting ormolytes

The preparation and characterization of two new families of lithium-conducting solid-state electrolytes is reported. Both systems are silica (SiO₂) – polyethyleneglycol (PEG_n) hybrid materials with (type I) or without (type II) covalent organic-inorganic chemical bonds. Their electrical conductivity has been studied by complex impedance spectroscopy between 20°C and 100°C in the frequency range 1 Hz to 10 MHz as a function of the polymer chain length (200<n<1900), polymer concentration and lithium concentration (4<[O]/[Li]<80). The highest room-temperature ionic conductivity (σ6×10⁻² S cm⁻¹) has been found for type II material for ratios [O]/[Li]=15 and PEG₃₀₀/TEOS=1.0. The effect of the chain length on the polymer mobility has been studied by nuclear magnetic resonance by measuring the Li⁺ line widths and the spin-lattice relaxation time T₁ between -100°C and +100°C. The bonded chain mobility increases with the chain length (type II) while the opposite occurs with unbonded chain material (type I). Both types of materials present high ionic conductivity at room temperature and are adequate as Li⁺-conducting electrolyte in all solid-state electrochemical devices.     

Thermodynamic analysis of monomethylamine–water solutions in a single-stage solar absorption refrigeration cycle at low generator temperatures

A theoretical analysis of the coefficient of performance COP was undertaken to examine the efficiency characteristics of the monomethylamine–water solutions for a single-stage absorption refrigeration machine, using low generator temperatures (60–80°C), which allows the use of flat plate solar collectors. The thermodynamic analysis considers both, basic and refined cycles. The refined absorption cycle included a sensible heat recover exchanger (that is a solution heat exchanger). The thermal coefficients of performance COP_h for the basis cycle and COP_SHE for the refined cycle were calculated using the enthalpies at various combinations, at the operating temperatures and concentrations. The flow ratio F_R has been calculated as additional optimization parameter. Due to the relative low pressure and the high coefficients of performance, the monomethylamine–water solutions present interesting properties for their application in solar absorption cycles at moderate condenser and absorber temperatures (25–35°C), with temperatures in the evaporator from −10°C to 10°C which are highly usable for food product preservation and for air conditioning in rural areas.