Compared imbibitions of ordinary and high performance concrete with null or positive water pressure head

A method to simultaneously measure the moisture diffusion coefficient, D_θ, of unsaturated concrete, and the saturated concrete hydraulic conductivity, K_l, was developed for cylindrical specimens placed on a container filled with water that could be maintained at a given hydraulic pressure. Ordinary Portland cement Concrete (OPC) with a moderate and High Performance Concrete (HPC) with a low water to cement ratio were tested. The time dependent distribution of water content in the specimens was measured using a non-intrusive method based on gamma-ray attenuation. The measurements were conducted with varying hydraulic head (positive or null). Boltzmann's transformation was used to analyze the experimental results obtained at different hydraulic pressures and the difference between the null (or atmospheric) and positive pressure results is used to accurately determine K_l and also D_θ . This paper will present the results obtained using this original method, possible interpretations and future research.     

On mass transfer effect due to electrolytically evolved gas

Based on the Ibl penetration model mass transfer equations for gas-evolving electrodes were derived and compared to the effect of forced convection. Experimental studies were conducted in a rectangular flow channel with the working electrode facing downward. The variables were linear bubble velocity, linear electrolyte velocity, nature of the gas and electrode position. Up to bubble velocities (U_x) of 2 and 6 cm s⁻¹ for O₂ and H₂ gases respectively, the thickness of the Nernst diffusion layer (δ_av) was described well by the equation δ_av = [Dd_eL/(U_x)_av]^1/3. Intermediate slopes between − 1/3 and − 1 were observed for O₂ bubble velocities between 2 and 6 cm s⁻¹. A theoretical derivation suggests that in the absence of bubble coalescence, the mass transfer effect due to laminar flow induced by electrolytically evolved gas exceeds that due to forced external laminar flow for all practical channel designs.     

Effect of electro-chemical properties of sodium salts of various anions on their diffusional parameters in symmetrical cellulose acetate membranes

A relation was obtained between electro-chemical properties of sodium salts (NaCl, NaBr, and Na₂SO₄), and the thermodynamic property of permeability in symmetrical cellulose acetate membranes, the distribution coefficient K and the kinetic property, the overall diffusion coefficients D. K and D were obtained by the method we proposed using measured unsteady- and steady-state dialysis data. The K values increase with the increase of water content and are in the range of 10⁻² for sodium halides and 10⁻³ for Na₂SO₄. D is found to increase with the increase of the solute concentration, and the extrapolated values of D to zero concentration D⁽⁰⁾ are obtained as 0.015–0.03 μm²/s and increase with the increase of water content in the membrane. D can be divided into the concentration independent diffusion coefficients in the dense part of the membrane D_d and in the porous D_p, applying a two-part (perfect or dense and imperfect or porous) model of the membrane. Contrary to D_d, D_p increases with the increase of W_w and can be correlated as D_p,c = _d exp (γ × W_w). It is shown that the averaged D_d, _D increases with the increase of the quantity of the ionic mobility u of the solutes at infinite dilution divided by valence, and that the parameter γ increases with the increase of the ionic mobility u. The value of K increases slightly with the increase of water content and decreases with the increase of the Flory—Huggins parameter χ. The Flory—Huggins parameter χ is calculated from the measured values of distribution coefficients and data obtained from the literature. And it was found that the gradient of linear decrease of χ (λ_cation) depends on equivalent ionic conductivity of anion of salt, λ_an.     

Fabrication and thermoelectric properties of heavily rare-earth metal-doped SrO(SrTiO3)n (n = 1, 2) ceramics

To clarify the effect of substitutional electron doping on the thermoelectric figure of merit (ZT = S²σTκ⁻¹) of Ruddlesden–Popper phase SrO(SrTiO₃)_n (or Sr_n+1Ti_nO_3n+1), measurements were conducted for several thermoelectric parameters, e.g. electrical conductivity (σ), Seebeck coefficient (S) and thermal conductivity (κ), of (Sr_1−xRE_x)_n+1Ti_nO_3n+1 (n = 1 or 2, RE (rare earth): La or Nd, x = 0.05 and 0.1) dense ceramics prepared by a conventional solid-state reaction and hot-pressing technique. Crystal structures of the resultant ceramics were represented as (Sr_1−xRE_x)_n+1 Ti_nO_3n+1 evaluated by powder X-ray diffraction followed by the Rietveld analysis. All the ceramics exhibited electrical conductivity and the σ values simply depended on the dopant concentration, indicating that both La³⁺ and Nd³⁺ ions act as electron donors. The |S| values increased with temperature due to decrease in the chemical potential. Significant reduction of the κ values was observed as compared to cubic-perovskite SrTiO₃. The ZT value increased with temperature and reached 0.15 at 1000 K for (Sr_0.95La_0.05)₃Ti₂O₇.     

Experimental studies of air-blast atomization on the CO2 capture with aqueous alkali solutions

In this work, an air-blast atomizing column was used to study the CO₂ capture performance with aqueous MEA (mono-ethanol-amine) and NaOH solutions. The effects of gas flow rate, the liquid to gas ratio (L/G), the CO₂ concentration on the CO₂ removal efficiency (η) and the volumetric overall mass transfer coefficient (K_Ga_v) were investigated. The air-blast atomizing column was also compared with the pressure spray tower on the studies of the CO₂ capture performance. For the aqueous MEA and NaOH solutions, the experimental results show that the η decreases with increasing gas flow rate and CO₂ concentration while it increases with increasing L/G. The effects on K_Ga_v are more complicated than those for η. When the CO₂ concentration is low (3 vol%), K_Ga_v increases with increasing gas flow rate while decreases with increasing L/G. However, when the CO₂ concentration is high (9.5 vol%), as the gas flow rate and L/G increases, K_Ga_v increases first and then decreases. The aqueous MEA solution achieves higher η and K_Ga_v than the aqueous NaOH solution. The air-blast atomizing column shows a good performance on CO₂ capture.     

Water electrolysis under microgravity: Part 1. Experimental technique

Water electrolysis was conducted in both alkaline (25 wt.% KOH, 2 wt.% KOH) and acid (0.1N H₂SO₄) solutions for 8 s under microgravity environment realized in a drop shaft. The gas bubble formation of hydrogen and oxygen on platinum electrodes was observed by CCD camera. In alkaline solutions, a bubble froth layer grew on the electrode surface. Hydrogen bubble size was smaller than that of oxygen. The current density at constant potential decreased continually with time. In spite of the growth of a bubble froth layer on the electrode, the electrolysis never stopped, apparently because fresh electrolyte is supplied to the electrode surface by microconvection induced by the gas bubble evolution. In acid solution, hydrogen gas bubbles frequently coalesced on the cathode surface, yielding a larger average bubble than that of oxygen. The current density did not vary at constant potentials from –0.4 to −0.8 V versus reversible hydrogen electrode (RHE), because the effective electrode surface area was significantly reduced by the larger bubble size compared to alkaline electrolyte. The present experiments indicate that, especially in a microgravity environment, the bubble evolution behavior and the resultant current–potential curves are significantly influenced by the wettability of the electrode in contact with the electrolyte.     

垂直惰性阳极铝电解槽内的析气行为

垂直惰性阳极铝电解槽内,析气行为会影响氧化铝浓度分布和电流效率。利用新设计的透明电解槽进行了电解试验,观察了大尺寸惰性阳极气泡的析出及逸出过程。试验结果表明：在阳极底掌下,气泡进行周期性的生长、长大、并聚和脱离,但大尺寸阳极上气泡的滑动和并聚过程与小尺寸阳极上的不同。阳极工作面上则形成了气泡群,新形成的气泡迅速脱离。紧贴着阳极的气泡运行速度慢,外层的气泡运动速度快。所有气泡最终都经液面逸出,大部分气泡到达液面时立即逸出,少部分未及时逸出的气泡随着电解质做一段水平运动后才逐步逸出。测量到的惰性阳极的气泡运动速度为0.006~0.445 m·s^-1,底部的气泡运动速度分布范围宽,然而,受电解质的限制,中上部的范围窄。     

Electrochemical properties of non-stoichiometric V6O13

Non-stoichiometric V₆O_13±0.2 (VO_y) prepared by thermal decomposition of NH₄VO₃ in N₂ atmosphere is investigated cathode material for Li batteries. The maximum lithium composition is found to be Li_2y-3VO_y. The emf vs composition relationship of Li/Li_xVO_2.144 is determined in the interval 0 < x < 1.3, yielding a theoretical energy density of 890 Wh kg⁻¹. The kinetics and reversibility of the VO_y electrode is investigated by cyclic voltammetry and cycling of test cells. The lithium diffusion coefficient and the electronic conductivity of the oxide is found to decrease with increasing lithium content. The cyclability of very thin electrodes is found to be excellent, but inferior results are obtained with practical cells, presumably due to degradation of electrode structure.     

Enhanced electrochemical performance of garnet-based solid-state lithium metal battery with modified anodic and cathodic interfaces

Due to high ionic conductivity and wide electrochemical window, the garnet solid electrolyte is considered as the most promising candidate electrolyte for solid-state lithium metal batteries. However, the high contact impedance between metallic lithium and the garnet solid electrolyte surface seriously hampers its further application. In this work, a Li-(ZnO)_x anode is prepared by the reaction of zinc oxide with metallic lithium and in situ coated on the surface of Li_6.8La₃Zr_1.8Ta_0.2O₁₂(LLZTO). The anode can be perfectly bound to the surface of LLZTO solid electrolyte, and the anode/electrolyte interfacial resistance was reduced from 2319 to 33.75 Ω·cm². The Li-(ZnO)_0.15|LLZTO|Li-(ZnO)_0.15 symmetric battery exhibits a stable Li striping/plating process during charge-discharging at a constant current density of 0.1 mA·cm^-2 for 100 h at room temperature. Moreover, a Li-(ZnO)_0.15|LLZTO-SPE|LFP full battery, comprised of a polyethylene oxide-based solid polymer electrolyte (SPE) film as an interlayer between LiFePO₄ (LFP) cathode and LLZTO solid electrolyte, presents an excellent performance at 60 ℃. The discharge capacity of the full battery reaches 140 mA·h·g^-1 at 0.1 C and the capacity attenuation is less than 3% after 50 cycles.     

Mechanical behaviour of partially stabilized zirconia crystals with terbia and ceria additives

Mechanical behaviour of partially stabilized zirconia crystals (PSZC) with terbia and ceria additives was investigated under bending and indentation conditions. Test specimens were oriented along the [010] direction and along the axis of crystal growth. The PSZC bending strength (σ_b) was dependent on the crystallographic orientation of the specimens. The specimen volume subjected to stress influenced the PSZC strength. The highest mechanical characteristics were measured for ceria-doped crystals (σ_b = 1.9 GPa, K_lc = 11.4 MPa m^1/2, E_d = 366 GPa). The failure process was studied on the Vickers indentation, with special emphasis put on the development and propagation of lateral cracks. Anisotropy of lateral cracks in the (100) plane associated with that of the elastic moduli was revealed. At the same time anisotropy of radial cracks and hardness was not found. A new version of the equation to evaluate the fracture toughness (K_c^v) on the Vickers indentation was derived. The K_c^v values calculated by this equation correspond to those (K_lc) obtained by an SENB method.     

Thermodynamics of ionic-association in aqueous solutions of Ca and Mg organic salts using ion-selective electrode technique—I. Formates, acetates, propionates and butyrates

The divalent selective electrode together with high precision solid state, digital pH -mv -meter makes broader application of potentiometry in physical and inorganic chemistry a certainty. The above set-up is used to determine the stoichiometric constants, K, for Ca and Mg ions association with formates, acetates, propionates and butyrates at 25°, 35° and 45°C in aqueous media. The K-values were converted to infinite dilution K_A values were found to be 8.4 LM⁻¹, 10.4 LM⁻¹, 19.1 LM⁻¹ and 19.3 LM⁻¹ for calcium salts of formate, acetate, propionate and butyrate respectively. Also K_A values for Mg salts of formate, acetate, propionate and butyrate were found to be 7.8 LM⁻¹, 9.5 LM⁻¹, 13.1 LM⁻¹ and 13.1 LM⁻¹ respectively. Other thermodynamic parameters such as ΔG°, ΔH° and ΔS° are also obtained from the variation of K_A with temperature for each salt. The data are interpreted relative to each other on basis of pK_a of the corresponding organic acid. Their temperature behaviour is similar to those salts derived from strong acids such as sulphates, rather than weak acids.     

CO2, NOx and SO2 emissions from the combustion of coal with high oxygen concentration gases

The emissions of CO₂, NO_x and SO₂ from the combustion of a high-volatile coal with N₂- and CO₂-based, high O₂ concentration (20, 50, 80, 100%) inlet gases were investigated in an electrically heated up-flow-tube furnace at elevated gas temperatures (1123–1573 K). The fuel equivalence ratio, φ, was varied in the range of 0.4–1.6. Results showed that CO₂ concentrations in flue gas were higher than 95% for the processes with O₂ and CO₂-based inlet gases. NO_x emissions increased with φ under fuel-lean conditions, then declined dramatically after φ=0.8, and the peak values increased from about 1000 ppm for the air combustion process and 500 ppm for the O₂(20%)+CO₂(80%) inlet gas process to about 4500 ppm for the oxygen combustion process. When φ>1.4 the emissions decreased to the same level for different O₂ concentration inlet gas processes. On the other hand, NO_x emission indexes decreased monotonically with φ under both fuel-lean and fuel-rich combustion. SO₂ emissions increased with φ under fuel-lean conditions, then declined slightly after φ>1.2. Temperature has a large effect on the NO_x emission. Peak values of the NO_x emission increased by 50–70% for the N₂-based inlet gas processes and by 30–50% for the CO₂-based inlet gas process from 1123 to 1573 K. However, there was only a small effect of temperature on the SO₂ emission.     

Effect of quartz particle size on the strength of triaxial porcelain

The effect of the quartz component on strength, σ_f, and fracture toughness, K_Ic, of a triaxial porcelain was studied by varying the size distribution of the quartz particles. Both σ_f and K_Ic were found to increase and then to pass over a maximum as the quartz distribution became finer. Improvements in σ_f and K_Ic of more than a factor of 2 were achieved. The flaw size that controlled failure was shown to equal the maximum quartz particle size in the material containing the coarsest quartz component and to be a constant independent of the quartz size in the other materials. The toughness increase was attributed to microcrack toughening of the glass matrix, the microcracks being formed by thermal mismatch stresses between the quartz particles and the glass matrix on cooling from the sintering temperature.     

锂离子电池电极材料Li1+xV3O8研究进展

钒酸锂（Li_1+xV₃O₈）具有比容量大的优点,可用作传统锂离子电池正极材料及水溶液锂离子电池负极材料,是一种重要的锂离子电池活性材料。Li_1+xV₃O₈作为传统锂离子电池正极材料已被广泛研究,近年来Li_1+xV₃O₈作为水溶液锂离子电池负极材料的研究备受瞩目,成为了锂离子电池研究领域的热点与前沿。本文综述了Li_1+xV₃O₈作为传统锂离子电池正极材料的研究现状,从结构与充放电机理、合成方法及改性等方面进行了讨论,此外,综述了Li_1+xV₃O₈作为水溶液锂离子电池负极材料的研究现状并指出了其发展趋势。     

Solid state protonic conductor NH4PO3–(NH4)2Mn(PO3)4 for intermediate temperature fuel cells

A new proton-conductive composite of NH₄PO₃–(NH₄)₂Mn(PO₃)₄ was synthesized and characterized as a potential electrolyte for intermediate temperature fuel cells that operated around 250 °C. Thermal gravimetric analysis and X-ray diffraction investigation showed that (NH₄)₂Mn(PO₃)₄ was stable as a supporting matrix for NH₄PO₃. The composite conductivity, measured using impedance spectroscopy, improved with increasing the molar ratio of NH₄PO₃ in both dry and wet atmospheres. A conductivity of 7 mS cm⁻¹ was obtained at 250 °C in wet hydrogen. Electromotive forces measured by hydrogen concentration cells showed that the composite was nearly a pure protonic conductor with hydrogen partial pressure in the range of 10²–10⁵ Pa. The proton transference number was determined to be 0.95 at 250 °C for 2NH₄PO₃–(NH₄)₂Mn(PO₃)₄ electrolyte. Fuel cells using 2NH₄PO₃–(NH₄)₂Mn(PO₃)₄ as an electrolyte and the Pt–C catalyst as an electrode were fabricated. Maximum power density of 16.8 mW/cm² was achieved at 250 °C with dry hydrogen and dry oxygen as the fuel and oxidant, respectively. However, the NH₄PO₃–(NH₄)₂Mn(PO₃)₄ electrolyte is not compatible with the Pt–C catalyst, indicating that it is critical to develop new electrode materials for the intermediate temperature fuel cells.     

Water electrolysis under microgravity: Part II. Description of gas bubble evolution phenomena

Water electrolysis is carried out in both alkaline (25 and 2 wt.% KOH) and acidic (0.1N H₂SO₄) solutions for 8 s under a microgravity (μ-G) environment realized in a drop shaft. The effects of gravitational strength on gas bubble evolution behavior are analyzed in consideration of various factors (bubble movement, bubble assembly and single bubble). Under a μ-G environment, a collection of fine gas bubbles forms a froth layer in alkaline solutions, whereas bubbles frequently coalesce in acidic solution. Moreover, H₂ gas bubbles in alkaline jump from a cathode surface and O₂ bubbles often coalesce on an anode. In acidic solution both H₂ and O₂ bubbles frequently coalesce on electrode surfaces. Such gas bubble movements are reflected in the coalescence number and bubble residence time. A single bubble is characterized by the bubble size and the dynamic contact angle between a gas bubble and a Pt electrode, however, these factors are not essentially influenced by the gravitational strength.     

Experimental investigation on bubbling behavior in anode channel of passive DMFC

将被动式DMFC阳极通道内气泡形成过程简化为CO₂气体注入充满静态甲醇溶液中形成气泡的过程。利用可视化实验研究了气体垂直注入静态甲醇溶液中形成气泡以及气泡脱离的过程,考察了气体流量、液层高度、孔径大小、甲醇浓度对气泡形成及长大脱离过程的影响。结果表明：在气泡的生长过程中,接触角先是快速下降后又迅速上升,然后趋于稳定值直到脱离。随着气体流量的增加,脱离时气泡的直径变化甚微,脱离时间先下降较快后趋于稳定。随着液层高度的增加,气泡的脱离直径变小,产生的频率加快,脱离时间先是减小后趋于稳定;气体流量在此条件下对脱离时间的影响减弱。随着孔径的增加,气泡的脱离直径增加,产生气泡的频率减慢,气泡的脱离时间减小。随着甲醇浓度的增加,气泡的脱离直径变小且波动明显,气泡产生的频率变快,脱离时间先是减小后趋于稳定,对低浓度的溶液影响较为明显。     

Electrolyte—solvent interaction in the dipolar aprotic solvent dimethyl sulphoxide at 25°C

Conductance measurements are reported for s-alkylisothiouronium bromide, iodide and picrate salts in the dipolar aprotic solvent DMSO at 25°C. The data were analysed by Fuoss's equation (1975–1980) for 1:1 electrolytes, from which the values of Λ₀, the Gurney's cosphere diameter R and K_A are obtained. The results are discussed in the light of the recorded values of the constants K_R and K_S and the free energy term G_s.     

Microstructure, Conductivity, and NO2 Sensing Characteristics of α-Al2O3-Doped (8 mol% Sc2O3)ZrO2 Composite Solid Electrolyte

α-Al₂O₃-doped (8 mol % Sc₂O₃)ZrO₂ composite solid electrolyte has been investigated in the fabrication of solid-state ceramic gas sensors. The microstructure and electrical conductivity of the composite solid electrolyte have been measured over a range of temperature from 240°C to 596°C. The composite solid electrolyte has been found to exhibit a higher conductivity compared with the commonly used (8 mol% Y₂O₃)ZrO₂ at temperatures above ∼448°C. The sensing characteristics for NO₂ detection have been studied in the temperature range of 500–650°C at the low concentration from 10 to 30 ppm and at high concentration from 100 to 500 ppm of NO₂. The NO₂ sensor was found to respond reproducibly and rapidly to the variations of NO₂, concentration, indicating that the composite solid electrolyte has promising application as a solid electrolyte for on-board exhaust gas monitoring.     

Mass Transfer Studies in Stirred AirLift Reactor

In the present work, water and three phase compositions of Solka-Floc, a cellulose fiber for simulating the biomass in bacteria, yeast, and fungal fermentation were studied in a 1.4 m³ stirred airlift reactor. The fractional dispersed phase holdup and the overall volumetric mass transfer coefficients were measured. The dispersed phase riser gas holdup and overall volumetric mass transfer coefficients both increased with increasing riser superficial dispersed phase velocity (0.02-0.1 ms^-1) and agitator speed in the range of 0-5 rs^-1. An increase in the Solka-Floc concentration (1-3% w/v) was found to reduce ε_GR and K_La_L. Empirical correlations have been developed for fractional dispersed phase gas holdup and overall volumetric mass transfer coefficients.