Mathematical modeling of gas evolution from flowing electrolytes on stable porous anodes of finite matrix phase conductivity

A mathematical model was developed to simulate the effects of the matrix phase conductivity on the behavior of flow-through porous anode operating for gas evolution reaction. The anode material was assumed to be stable and has a finite conductivity. The model accounts for the conductivities of the solution and the matrix phases, the electrode kinetics, hydrodynamics and gas bubble formation. The different ratios and values of the matrix conductivity group, K_σ (a measure of the matrix conductivity) and the electrolyte conductivity group, K_κ (a measure of the electrolyte conductivity) were found to have significant effects on the distributions of current, potential and gas void fraction. When K_σ was a finite value the reaction was pushed towards the back of the electrode and when K_κ was finite the reaction was pushed towards the front face. The effects of the bubble group, χ on the potential and current distributions were investigated under different impacts of K_σ and K_κ. When K_σ was limited the gas bubbles formed at the back of the electrode were forced to travel within the whole bed with the electrolyte streams, causing larger accumulation of the bubbles and hence higher polarization within the bed. The gas bubble formation limited the conductivity of the pore electrolyte resulting in potential and current distributions similar to the case of finite electrolyte conductivity.     

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.     

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.     

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.     

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.     

Insight into solute-solute and solute-solvent interactions of semicarbazide hydrochloride in water and D-glucose/D-sucrose+water solutions at temperatures (293.15 to 318.15) K

The solute-solute and solute-solvent interactions of drug semicarbazide hydrochloride with carbohydrates (D-glucose/D-sucrose) are investigated by using volumetric, viscometric and acoustic properties. The measurements of the densities ρ, ultrasonic speeds u, and viscosities η. of semicarbazide hydrochloride in 5% and 10% D-glucose/D-sucrose+water (w/w) solutions were carried out at temperatures (293.15-318.15) K and at pressure, p=101 kPa. The apparent molar volumes, V_ϕ, limiting apparent molar volumes,V_ϕ°, apparent molar compressibilities, K_{s, ϕ}, limiting apparent molar compressibilities, K_s,ϕ°, partial molar expansibilities, E_ϕ°, transfer volumes, V_ϕ,tr° and transfer compressibilities, K_s,ϕ,tr° have been calculated from the experimental data. The viscosity data were examined by using the Jones-Dole equation and the viscosity A and B coefficients were evaluated. The results are discussed in terms of solute-solute and solute-solvent interactions in these solutions. The structure making/breaking ability of semicarbazide hydrochloride is examined using the sign of temperature derivative of B-coefficient, dB/dT.     

ANN-Based Models for Moisture Diffusivity Coefficient and Moisture Loss at Equilibrium in Osmotic Dehydration Process

Equations were developed using artificial neural networks to predict water diffusivity coefficient (D_e) and moisture loss at equilibrium point (ML_∞) in order to get the moisture loss (ML) at any time in osmotic dehydration of fruits. These models mathematically correlate nine processing variables (temperature and concentration of osmotic solution, water and solid composition of the fruit, porosity, surface area, characteristic length, solution-to-fruit mass ratio, and agitation level) with D_e and ML_∞. Models were developed using a wide variety of data from the literature and they were able to predict D_e (r = 0.98) and ML_∞(r = 0.94) in a wide range of variable conditions. With these two parameters known, ML can be calculated using Crank's solutions of Fick's second law. The wide range of processing variables considered for the formulation of these models, and their easy implementation in a spreadsheet, using a set of equations, makes them very useful and practical for process design and control.     

Microwave dielectric properties of rutile (Zn1/3Nb2/3)0.40(Ti1−xSnx)0.60O2 (0.15 ≤ x ≤ 0.30) ceramics

Microwave dielectric properties of (Zn_1/3Nb_2/3)_0.40(Ti_1−xSn_x)_0.60O₂ ceramics were investigated as a function of SnO₂ content (0.15 ≤ x ≤ 0.30). A single phase with tetragonal rutile structure was obtained through the entire composition. The unit-cell volume of the specimens was increased with SnO₂ content, due to the larger ionic radius of Sn⁴⁺ (0.69 Å) than that of Ti⁴⁺ (0.605 Å) for octahedral site. Dielectric constant (K) of the sintered specimens was affected by the dielectric polarizability. Quality factor (Qf) was dependent on the degree of reduction of Ti⁴⁺ ion. With an increase of SnO₂ content, the temperature coefficient of resonant frequency (TCF) of the specimens decreased due to the decrease of the octahedral distortion of rutile structure.     

Significance of specimen size for the KR-curve behavior of quasi-brittle materials

The influence of specimen size on the crack resistance (K_R-curve) behavior of a coarse-grained carbon is investigated using compact tension samples of varying size. The results are compared to previous measurements on asbestos cement. In order to analyse and estimate the toughening contribution appearing due to crack-wake related processes, the unloading compliance is measured during the K_R curve test. Subsequent renotching of the extended crack and comparison with the behavior of an ideal linear-elastic body enables the crack-closure forces to be estimated.     

Relationships between crystal structure and microwave dielectric properties of (Zn1/3B2/3)xTi1 − xO2 (B = Nb, Ta) ceramics

Dependence of microwave dielectric properties on the crystal structure of (Zn_1/3B_2/3⁵⁺)_xTi_1 − xO₂ (B⁵⁺ = Nb, Ta) ceramics was investigated as a function of Zn_1/3B_2/3⁵⁺O₂ (B⁵⁺ = Nb, Ta) content (0.4 ≤ x ≤ 0.7). Dielectric constant (K) and the temperature coefficient of resonant frequency (TCF) of sintered specimens were strongly dependent on the structural characteristics of oxygen octahedra in rutile structure. Cation rattling and the distortion of oxygen octahedra were dependent on the bond length ratio of apical (d_apical)/equatorial (d_equatorial) of oxygen octahedra. The quality factor (Qf) was dependent on the reduction of Ti ion as well as the microstructure of the sintered specimens.     

Polymerization of methyl methacrylate in the presence of molecular oxygen — a kinetic study

Methyl methacrylate was polymerized in aqueous medium initiated by a copper(II)-ascorbic acidoxygen system at 40°C and a kinetic study of the reaction is presented. The rate of polymerization, R_p showed an increase, constancy and then a decrease with increase in the [Cu²⁺]. The order with respect to [Cu²⁺] was 0.5 in the rate increase region. The order in monomer concentration changed gradually from 1.0 to 2.0 with increase in [Cu²⁺]. R_p became independent of ascorbic acid (AA) concentration and oxygen concentration at high concentrations. These results indicate that termination by mutual interaction of chain radicals predominates at low [Cu²⁺] while termination was exclusively by metal ions at high [Cu²⁺]. R_p was also observed to increase with temperature and ionic strength and to K_p/K_t^1/2 value was calculated and compared with literature values. Chain lengths were determined by viscometry for the polymers obtained under various experimental conditions.     

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.     

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.     

Fabrication and Properties of 2-2 Cement Based Piezoelectric Composites

Composites with 2-2 connectivity were fabricated from lead magnesium niobate-lead zirconate-lead titanate(PMN) and sulphoaluminate cement by cut-filling process. The influences of PMN volume fraction and water/cement ratio on the properties of the composite were investigated. The results show that the piezoelectric strain constant d₃₃ increase rapidly with increasing volume fraction of PMN. When the PMN volume fraction is about 0.60, the d₃₃ value is up to 357 pCN^-1. The planar electromechanical coupling coefficient K_p of the composites is lower than that of PMN ceramic, while the thickness electromechanical coupling coefficient K_t is higher than that of PMN ceramic. The water/cement ratio has little influence on piezoelectric properties of 2-2 cement based piezoelectric composite.     

Correlation between equation of state and temperature and pressure dependence of self-diffusion coefficient of polymers and simple liquids

Correlation between the equation of state and the temperature dependence of the self-diffusion coefficient D for polymers such as polystyrene (PS) and polydimethyl siloxane (PDMS) and simple liquids such as argon, methane and benzene and the pressure dependence of D for oligomers such as dimethyl siloxane (DMS) and simple liquids such as cyclohexane and methanol has been examined based on the equation of state derived previously. The experimental data used were published by Antonietti et al. and McCall et al. for polymers, by McCall for linear dimethylsiloxanes and by Jonas et al. and Woolf et al. for simple liquids. The expression for D in this work is given by

where A₁(M) is a function of molecular weight M_w, C₁(T) and P₁(T) are functions of temperature and B₁, n₁ and m₁ are constants determined experimentally. For simple liquids, the values of n₁ obtained range from 0.3 to 1.2, with an average , and m₁ is in the range 0.5–1.2, with . For polymers, values of n₁ are in the range 2.5–7.0 for PS and 0.5–1.3 for PDMS and m₁ for DMS is in the range 0.8–1.0. The relation Dη/T = f(M) is found to be useful for simple liquids over a wide range of temperature including the critical region and for pressures up to ≈5 kbar

1 kbar = 100 MPa There is a close correlation between ln(D/T) and _p and β_T through ln(D/T)ln D_c−⁻¹_p−β⁻¹_T, where D_c is D at the critical temperature and _p and β_T are the thermal expansion coefficient and compressibility, respectively. The molecular weight dependence of D for polymers and simple liquids is discussed based on the experimental data and recent theory of Doi and Edwards. A new model for the mechanism of self-diffusion in the liquid state is proposed.     

Synthesis and study of RO performance of aromatic polyamide hydrazide membranes

Aromatic polyamide hydrazide polymeric membranes were synthesized by dissolving freshly prepared polymer in dimethyl acetamide using lithium salt as additive. The effect of various casting parameters like polymer to solvent ratio, additive to polymer ratio, time and temperature of solvent evaporation, etc., on the RO membrane performance was studied. The membrane performance under various operational parameters like applied pressure, feed molarity and temperature are presented. The membranes prepared from the polymer samples were characterised in terms of pure water permeability constant (A) and solute transport parameter (D_AM/Kδ).     

The glass temperature of polymer blends

The entropy theory of glasses is used to derive the glass temperature, T_g, of a binary polymer blend in terms of the glass temperatures of the two substituents. The formula is T_g = B₁T_g1 + B₂T_g2, where B_i is the fraction of flexible bonds of substituent i. A bond is flexible if rotation about it changes the shape of the molecule. Bonds in side groups as well as in the backbone are to be counted. This formula assumes that the free volume, taken here to be the volume fraction of empty lattice sites, is the same for each of the three materials. It has no parameters. The above equation expressed in weight fractions, W_i, is (T_g − T_g1)W₁(γ₁/ω₁) + (T_g − T_g2)W₂(γ₂/ω₂) = 0, where ω_i is the weight of a monomer unit and gg_i is the number of flexible bonds per monomer unit. A more general treatment is given. One variation of the more general treatment which expresses the properties of the blend in purely additive terms gives T_g = B₁T_g1 + B₂T_g2 + KB₁B₂(T_g1 − T_g2)(V₀₁ − V₀₂), where V_0i are the free volume fractions of the homopolymers at their glass temperatures and K is a constant. The added term is usually small. The most general form of the equation requires the energy of interaction between the two unlike molecules, which can be estimated by volume measurements on the blend.     

Defect formation and mechanical stability of perovskites based on LaCrO3 for solid oxide fuel cells (SOFC)

Perovskites on the basis of LaCrO₃ are of interest as ceramic interconnect materials for the development of solid oxide fuel cells (SOFCs). The interconnects are exposed to oxidising and reducing atmospheres under operating conditions. Oxygen vacancy formation was determined as a function of oxygen partial pressure between 1 and 10⁻²² bar at temperatures between 900 and 1100 °C. Different perovskite compositions made of (La,Ca/Sr)CrO_3−δ, La(Cr,Mg)O_3−δ, La(Cr,Mg/Cu/Co,Al)O_3−δ, and (La,Ca)(Cr,Al)O_3−δ were investigated. Defect models were evaluated to describe the oxygen vacancy formation and the respective thermodynamic data were determined. The results are used to explain existing literature data on the isothermal expansion of LaCrO₃ based perovskites under reducing conditions. Complementary mechanical measurements with selected perovskite compositions revealed that lower oxygen partial pressure causes higher stiffness, strength and fracture toughness. The change in properties is discussed in terms of the observed ferroelastic domains and the interaction of the domain wall motion with the oxygen vacancies.     

The use of tension testing to investigate the effect of W/C ratio and cement type on the resistance of concrete to sulfate attack

Concrete specimens were cast and partially immersed in a sulfate solution for varying periods of time up to 1 year. The effects of water/cement ratio (0.45 and 0.65) and cement type (ordinary and sulfate resistant) were investigated. Concrete performance was evaluated based on compressive strength and tensile strength, which was measured with the pressure tension test. Results indicated that water/cement ratio had a greater influence on the resistance of the concretes to sulfate attack than did cement type. The pressure tension test appeared to be more sensitive than the compressive strength test in detecting internal damage, particularly at early ages.