Thermodynamic evaluation of water splitting by a cation-excessive (Ni, Mn) ferrite

Water-splitting potential by cation-excessive (Ni, Mn) Ferrite, Ni_{0.5(1 + )}Fe_{1.99(1 + )}O₄ was evaluated using the standard Gibbs free energy change (ΔG°) for the cation-excessive ferrite formation in different O₂ partial pressures. The cation-excessive degree ranged from 0.026 to 0.16 in pO₂ values of 7.9 × 10⁻⁷ to 1.0 × 10⁻¹. From the relation between value of (Ni, Mn) ferrite and oxygen partial pressure, equilibrium constant K(th) was determined. Furthermore ΔH°s for O₂ releasing and water-splitting reactions with cation-excessive (Ni, Mn) ferrite were evaluated from the van't Hoff plot and compared with that for magnetite-wüstite system; where ΔH°s were assumed to be the same values for both (Ni, Mn) ferrite and magnetite-wüstite system: +300 kJ for O₂ releasing and −35 −63 kJ for water-splitting. ΔG°s evaluated for water-splitting with cation-excessive (Ni, Mn) ferrite and wüstite were −38 kJ and −35 kJ, respectively, at 298K. It suggests that water splitting with cation-excessive (Ni, Mn) ferrite proceed easily compared with that with wüstite. ΔS°s for water-splitting are −0.93 kJ K⁻¹ for the former and −0.83 kJ K⁻¹ for the latter. H₂ generation rates by reaction with H₂O for (Ni, Mn) ferrite were studied at temperatures of 573 K-1073 K. It reached the maximum at 1000 K while it proceeds preferentially below 830 K from thermodynamics.     

Combined heat and mass transfer by natural convection at horizontal cylinder electrodes

Simultaneous heat and mass transfer in free convection at horizontal cylinder electrodes has been investigated experimentally using the electrochemical limiting diffusion current technique. The convective flow patterns occuring have been observed using Schlieren photography. The results confirmed the use of a combined Grashof number (GR_m) to account for thermal and concentration buoyancy effects. Various combinations of electroactive species concentration, cylinder diameter and cylinder surface temperature have been used. Results have been successfully correlated by the equations , 7×10⁷ < GR_mSc< 4×10⁹ and , 4×10⁹ mSc<10¹¹ The experiments cover the range of mass transfer and heat transfer Grashof numbers 3.64×10⁴ m <3.02×10⁶, 5.67×10⁴ h <6.55×10⁶     

Large area CIGS2 thin film solar cells on foils: nucleus of a pilot plant

In earlier research, conversion efficiency of 10.4% (AM1.5) and 9.9% (AM0) has been achieved on small area CuIn_xGa_1−xS₂ (CIGS2) solar cell on 127 μm thick stainless steel substrate. The area of research is mainly focused on studying CIGS2 thin films as solar cell absorber material and growing high efficiency cells on ultralightweight and flexible metallic foils such as 127 μm thick stainless steel and SiO₂ coated 25 μm thick Ti foils. This paper presents the scaling up process of CIGS2 thin film substrate from 2.5 × 2.5 cm² to 10 × 10 cm². Initial scaling up efforts focused on achieving uniform thickness and stress-free films. Process of scaling up consisted of refurbishment of selenization/sulfurization furnace, design and fabrication of scrubber and enlargement of new CdS deposition setup. The scaling up from 2.5 × 2.5 cm² to 10 × 10 cm² substrate size has laid the foundation for PV Materials Lab of Florida Solar Energy Center becoming the nucleus of a pilot plant.     

Low temperature μc-Si film growth using a CaF2 seed layer

This paper describes low temperature thin film Si growth by remote plasma chemical vapor deposition system for photovoltaic device applications. Using CaF₂/glass substrate, we were able to achieve an improved μc-Si film at a low process temperature of 300°C. The μc-Si film on CaF₂/glass substrate shows that a crystalline volume fraction of 65% and dark conductivity of 1.65×10⁻⁸ S/cm with the growth conditions of 50 W, 300°C, 88 mTorr, and SiH₄/H₂=1.2%. XRD analysis on μc-Si/CaF₂/glass showed crystalline film growth in (1 1 1) and (2 2 0) planes. Grain size was enlarged as large as 700 Å for a μc-Si/CaF₂/glass structure. Activation energy of μc-Si film was given as 0.49 eV. The μc-Si films exhibited dark- and photo-conductivity ratio of 124.     

Electrical and optical properties of F-doped textured SnO2 films deposited by APCVD

This paper presents the structural, electrical and optical properties of transparent conducting F-doped textured SnO₂ films prepared by atmosphere pressure chemical vapour deposition (APCVD). Polycrystalline SnO₂:F films having a variable preferred orientation have been obtained with resistivity as low as 5 × 10⁻⁴ Ωcm, with carrier concentrations between 3.5 × 10²⁰ and 7 × 10²⁰ cm⁻³, and Hall mobilities from 15.7 to 20.1 cm²/V/s. The average transmittance (including diffusion transmittance) is as high as 94% in the wavelength range of the visible spectrum and the maximum infrared reflectance reaches 92% for a film 655 nm thick. The figure of merit ƒ_TC = T10/_sh, (7.12 × 10⁻² S) of these films is the highest amongst the results reported on doped SnO₂ films.     

Membranes based on phosphotungstic acid and polybenzimidazole for fuel cell application

Composite membranes based on phosphotungstic acid (PWA) adsorbed on silica (SiO₂) and polybenzimidazole (PBI) have been prepared and their physico-chemical properties have been studied. The membranes with high tensile strength and thickness of less than 30 μm can be cast. They are chemically stable in boiling water and thermally stable in air up to 400°C. Proton conductivity is influenced by the temperature (range: 30–100°C), relative humidity and PWA loading in the membrane. Maximum conductivity of 3.0×10⁻³ S/cm is obtained at 100% relative humidity and 100°C with membrane containing 60 wt.% PWA/SiO₂ in PBI. Conductivity measurements performed at higher temperatures, in the range from 90°C to 150°C, give almost stable values of 1.4–1.5×10⁻³ S/cm at 100% relative humidity.     

Out of the cell performance of reforming catalysts for direct molten carbonate fuel cells (DMCFC)

Nickel catalysts supported on commercial MgO and LiAlO₂ have been tested and compared in the methane steam reforming reaction at temperatures ranging from 798 to 923 K and GHSV from 5.4 × 10⁶s⁻¹ to 5.4 × 10⁸s⁻¹. Initial molar ratio of the reactants, R = P_H2O/P_CH4 was 2.54. Results of the influence of the catalyst reduction temperature have been reported. Preliminary results of the reaction kinetic analysis, adopting first order pseudohomogeneous model, are given. The suitability of using these catalysts into the molten carbonate fuel cells (MCFC), to generate hydrogen directly by the methane steam reforming, is discussed.     

Optical and electrochemical characteristics of niobium oxide films prepared by sol-gel process and magnetron sputtering A comparison

Electrochromic niobia (Nb₂0₅) coatings were prepared by the sot-gel spin-coating and d.c. magnetron sputtering techniques. Parameters were investigated for the process fabrication of sol-gel spin coated Nb₂0₅ films exhibiting high coloration efficiency comparable with that d.c. magnetron sputtered niobia films. X-ray diffraction studies (XRD) showed that the sot-gel deposited and magnetron sputtered films heat treated at temperatures below 450°C, were amorphous, whereas those heat treated at higher temperatures were slightly crystalline. X-ray photoelectron spectroscopy (XPS) studies showed that the stoichiometry of the films was Nb₂0₅. The refractive index and electrochromic coloration were found to depend on the preparation technique. Both films showed low absorption and high transparency in the visible range. We found that the n, k values of the sot-gel deposited films to be lower than for the sputtered films. The n and k values were n = 1.82 and k = 3 × 10⁻³, and n = 2.28 and K = 4 × 10⁻³ at 530 urn for sot-gel deposited and sputtered films, respectively. The electrochemical behavior and structural changes were investigated in 1 M LiC10₄/propylene carbonate solution. Using the electrochemical measurements and X-ray photoelectron spectroscopy, the probable electrode reaction with the lithiation and delithiation is Nb₂O₅ + x Li⁺ + x e⁻ ↔ Li_xNb₂0₅. Cyclic voltametric (CV) measurements showed that both Nb₂0₅ films exhibits electrochemical reversibility beyond 1200 cycles without change in performance. “In situ” optical measurement revealed that those films exhibit an electrochromic effect in the spectral range 300 < λ < 2100 nm but remain unchanged in the infrared spectral range. The change in visible transmittance was 40% for 250 nm thick electrodes. Spectroelectrochemical measurements showed that spin coated films were essentially electrochemically equivalent to those prepared by d.c. magnetron sputter deposition.     

Kinetics of the NCO radical reacting with atoms and selected molecules

Rate constants for the reaction of isocyanate radicals (NCO) in its electronic ground state ( ²Π) with oxygen atoms were determined at 2.5 Torr total pressure in the temperature range 302–757 K. Excimer laser photolysis (ELP) of chlorine isocyanate (ClNCO) produced NCO radicals detected by laser-induced fluorescence (LIF). The reaction NCO + O exhibits a negative temperature dependence, described by the two-parameter equation: k_NCO+O(T) = (4.3_−2.2^+3.2) × 10⁻⁸ × T^{−1.14_−0.12+0.08} cm³ molecule⁻¹ s⁻¹. Measurements at 298 K and total pressures of 2.5 and 9.9 Torr, respectively, indicated a slight pressure dependence. For the reaction of NCO radicals with hydrogen atoms, the rate constant k_NCO+H = (2.2 ± 1.5) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹was obtained at 298 K and a total pressure of 2.6 Torr for the first time by a direct measurement. From a single measurement k = (3.8 ± 1.6) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ was determined at 548 K and 2.4 Torr total pressure. In addition, rate constants for the reactions of NCO radicals with molecular oxygen (O₂), carbon dioxide (CO₂), molecular hydrogen (H₂), and carbon monoxide (CO), which is a dissociation product of CO₂ in a microwave discharge, were measured at two different temperatures. At room temperature these reactions were slow and at the detection limit of the ELP/LIF technique. However, at elevated temperatures at least the rate constants of the reactions NCO + O₂ and NCO + H₂ become significantly larger and, therefore, should be taken into account, when modeling combustion processes under certain conditions.     

Temperature effect on the electrical and optical properties of indium-selenide thin-films

Indium-Selenide thin-films have been prepared by the thermal-evaporation technique at a pressure of 4.5×10⁻⁶ torr and a temperature of 673–873 K. For both the as-deposited and annealed films, (i) the electrical conductivity increased with increasing temperature and (ii) the variation of activation energy follows the island structure theory. The temperature co-efficient of resistance (T.C.R.) and Hall-effect measurements indicate that the sample is a n-type carrier. The optical spectra for both types of films were obtained in the wavelength range 0.3<λ<2.5 μm, and by comparing the magnitude of transmittance spectra, it is found that the annealed films are more transparent than the as-deposited ones in the UV and visible range. The integrated transmittance and reflectance values were obtained: the high values of T_lum and T_sol for the annealed films suggest that indium selenide may be used in selective-surface devices.     

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.     

生物质成型机成型模孔内表面摩擦力分形预测

选择2种模孔材料,利用粗糙仪测出其表面形貌,提取轮廓数据,采用尺码法计算出表面分形参数D和G,再基于经典接触公式和M-B分形接触模型建立成型模孔内表面滑动摩擦力分形预测模型并进行模拟,最后利用摩擦磨损试验台进行验证。结果表明：当环模模孔内表面的粗糙度R_a值3.428 μm时（45钢）,D值为1.373,G值为1.55×10_-6 m;而当其R_a值为4.002 μm时（40Cr）,D值为1.359,G值为0.82×10_-6 m;摩擦力随真实接触面积的增加呈增大趋势,单位摩擦力随真实接触面积的增加呈减小趋势;在A_rrc时,摩擦力增大速度较快,单位摩擦力减小速度较快;在A_r>A_rc时,摩擦力增幅较平缓,单位摩擦力降幅较平缓。经实验验证,摩擦力模拟结果比试验结果略高,且随真实接触面积的增大,摩擦力的模拟值正逐渐接近实验值,模型预测较准确。     

Electrocatalysis for dioxygen reduction by a μ-oxo decavanadium complex in alkaline medium and its application to a cathode catalyst in air batteries

The redox behavior of a decavanadium complex [(V=O)₁₀(μ₂-O)₉(μ₃-O)₃(C₅H₇O₂)₆] (1) was studied using cyclic voltammetry under acidic and basic conditions. The reduction potential of V(V) was found at less positive potentials for higher pH electrolyte solutions. The oxygen reduction at complex 1 immobilized on a modified electrode was examined using cyclic voltammetry and rotating ring-disk electrode techniques in the 1 M KOH solutions. On the basis of measurements using a rotating disk electrode (RDE), the complex 1 was found to be highly active for the direct four-electron reduction of dioxygen at −0.2 V versus saturated calomel electrode (SCE). The complex 1 as a reduction catalyst of O₂ with a high selectivity was demonstrated using rotating ring-disk voltammograms in alkaline solutions. The application of complex 1 as an oxygen reduction catalyst at the cathode of zinc–air cell was also examined. The zinc–air cell with the modified electrode showed a stable discharge potential at approximately 1 V with discharge capacity of 80 mAh g⁻¹ which was about five times larger than that obtained with the commonly used manganese dioxide catalyst.     

Electrochemistry of poly(vinylferrocene) modified electrodes in aqueous acidic media

A cyclic voltammetric study of the electrochemistry and chemical stability of the poly(vinylferrocene) (PVFc) redox couple, coated on a gold substrate, in aqueous solutions of H₂SO₄, HClO₄ and HCl was carried out. It was found that the anodic peak potential (E_pa) did not depend on the acid concentration in the range (1.0 × 10⁻² to 1.0 × 10⁻⁷ mol L⁻¹). However, the E_pa values shifted linearly to less positive potentials when investigated in more concentrated acid solutions in the range 1–5 mol L⁻¹. The slope of the E_pa versus acid concentration graph was found to be in the order H₂SO₄ > HCl > HClO₄. In this regard PVFc behaved very similar to 1,1′-bis(11-mercaptoundecyl)ferrocene (Fc(C₁₁SH)₂) except for its chemical stability. In H₂SO₄ media the PVFc was found to be much less stable than 1,1′-Fc(C₁₁SH)₂. The dependence of E_pa on acid concentration could be used to monitor state of charge of lead-acid batteries. However, for this application Fc(C₁₁SH)₂ would be a better choice because of its superior chemical stability.     

Influence of carbon content and tempering temperature on fatigue threshold characteristics of a low alloy steel

This paper attempts to describe the effect of carbon content on the fatigue threshold characteristics ΔK_th in various heat treated conditions. Essentially it has been shown that a tempering treatment increased ΔK_th while increasing the carbon content of steels from 0·13% to 0·8% significantly decreased the ΔK_th value by over 100%. At intermediate fatigue crack growth rates all the data show a linear relationship with ΔK level.

In terms of yield strength σ_y, the threshold stress intensity level could be given by the expression: ΔK_th = 8·74 − 3·42 × 10⁻³(σ_y).

At near threshold fatigue crack growth levels significant amounts of isolated intergranular failure were observed in the 400°C tempered condition. In the other heat treated microstructures only a flat trans-granular ductile striated failure mode was evident. A maxima in the amount of intergranular facets occurred at ΔK values approaching 15 to 20 MPa√m. It has been shown the existence of intergranular failure resulted from environmentally induced fracture (through the diffusion of hydrogen) that occurred within the crack tip enclave.     

On the computer simulation of the P–C isotherms of ZrFe2 type hydrogen storage materials

This paper deals with computer simulation of the P–C isotherms of some ZrFe₂ type (Zr(Fe_1−xCr_x)₂, Zr_1−xTi_xFe_1.4Cr_0.6, Zr_1−2xMm_xTi_xFe_1.4Cr_0.6 : x00.4) of hydrogen storage materials. A feasible mathematical model has been developed to simulate the P–C isotherms. The randomized variables in the model applied for simulating the P–C isotherms of the above-mentioned ZrFe₂ type hydrogen storage materials correspond to change in enthalpy (ΔH) and entropy (ΔS) of hydride formation. Several ZrFe₂ type materials as in above have been synthesized and their P–C isotherms, enthalpy and entropy change has been evaluated experimentally in order to have input data for simulation. A special software was developed to simulate the P–C isotherms using the said model. A close match between the experimentally observed and simulated P–C isotherms for the above said ZrFe₂ type alloys has been obtained.     

The hydrogen evolution reaction in acid medium on nickel electrodeposited with PW12O40

The hydrogen evolution reaction (h.e.r.) was performed in acid medium at room temperature on nickel electrodeposited cathodes with and without PW₁₂O⁴⁻₄₀ (the later electrodes are named here by NiPW₁₂). An important increase of the exchange current density (i_o) and a significant decrease of the overvoltage (η) was obtained for NiPW₁₂. These results were attributed to an activation of the electrodes due to the active species of the reduction of PW₁₂O³⁻₁₀. A model involving these reduced species for the h.e.r. was proposed. These species sensitized the proton reduction for the h.e.r. It has been shown that the exchange current density can effectively be used as an electrochemical parameter for the h.e.r. rate due to the electrocatalytic properties of different interfaces involving these electrodes. The NiPW₁₂ cathodes showed stable overpotentials during electrolysis of water in acid medium more than 1500 h, and were not adversely affected by extended open circuit exposure. They showed high resistance to common electrocatalyst poisons. Scanning electron microscopy showed that this was due to a good resistance of the material to electrochemical decomposition.     

Waste incineration and energy recovery

We discuss the implications of waste incineration on energy production at currently achieved conversion efficiencies to electricity and for realistic estimates of incinerable fractions of municipal, hazardous, and biomedical wastes. We find approximate steady-state contributions in the U.S. of 6.1 × 10³, (3.0–3.9) × 10³ and 0.5 × 10³ MW_e for these three technologies, respectively. A combustion-research agenda for waste incinerators is summarized briefly. Its implementation may be expected to contribute to the efficacious development of waste-incineration technologies and associated energy recovery.     

Improvement of the catalytic properties of Ti-doted Raney-Nickel for H2-Anodes of alkalione fuel cells by Ni(OH)2-surface coating

This paper belongs to a series of three dealing with the latest improvements in the alkaline H₂---O₂ fuel cells operating under mild conditions thanks to their Raney-Ni-catalysts. The first of these papers describes the benefication of a Ni(OH)₂ surface coating on the catalytic activity of Ti-doted Raney-Ni in supported electrodes. This Ni(OH)₂ surface coating is produced by carefully optimized oxidation. A Ni(OH)₂-content of 5 up to 6wt% increases the attainable current density by the factor 3–4. In addition, the exchange current density is markedly enlarged up to a Ni(OH)₂-fraction by 5%, but remains unchanged when further increasing the Ni(OH)₂ percentage. Thus, one may conclude that the Ni(OH)₂ surface coating improves markedly the charge exchange reaction. On the other side, the surface diffusion of H-atoms on the pore walls to the location of charge exchange reaction is hindered by too much Ni(OH)₂.     

Thermodynamical properties of La–Ni–T (T = Mg, Bi and Sb) hydrogen storage systems

The hydrogen absorption properties of LaNi_4.8T_0.2 (T = Mg, Bi and Sb) alloys are reported. The effects of the substitution of Ni in the LaNi₅ compound with Mg, Bi and Sb are investigated. The ability of alloys to absorb hydrogen is characterized by the pressure–composition (p–c) isotherms. The p–c isotherms allow the determining thermodynamic parameters enthalpy (ΔH^des) and entropy (ΔS^des) of the dehydrogenation processes. The calculated ΔH^des and ΔS^des data helps to explain the decrease of hydrogen equilibrium pressure in alloys doped with Al, Mg and Bi and its increase in the Sb-doped LaNi₅ compound. Generally, partial substitution of Ni in LaNi₅ compound with Mg, Bi and Sb cause insignificant changes of hydrogen storage capacity compared to the hydrogen content in the initial LaNi₅H₆ hydride phase. However, it is worth to stress that, in the case of LaNi_4.8Bi_0.2, a small increase of H/f.u. up to 6.8 is observed. The obtained results in these investigations indicate that the LaNi_4.8T_0.2 (T = Al, Mg and Bi) alloys can be very attractive materials dedicated for negative electrodes in Ni/MH batteries.