Effective diffusion constant and adsorption constant of synthesized alumina,zirconia, and alumina–zirconia composite material

In this study, Al₂O₃, ZrO₂, and Al₂O₃–ZrO₂ composite materials were prepared with the sol–gel technique. X-ray diffraction analysis, differential scanning calorimetry–thermogravimetry, scanning electron microscopy–energy-dispersive X-ray spectrometry, nitrogen adsorption isotherm measurements, and helium pycnometry were used to characterize the resultant materials. Effective diffusion coefficients of helium and hydrogen and the adsorption equilibrium constant of hydrogen in the resultant materials were determined using single-pellet moment technique. The effective diffusivities of helium and hydrogen in both ZrO₂ and Al₂O₃–ZrO₂ composite pellets were found to be smaller than the value found for Al₂O_3, due to the lower tortuosity factor values of the Al₂O₃ pellet. It was found that hydrogen was weakly adsorbed on all resultant materials.     

Influence of constant magnetic field on the electrodeposition of Co–Mo–W alloys

The aim of this study was to investigate the effect of a constant magnetic field (CMF) on the electrodeposition of Co–Mo–W alloys, and to observe changes in the topography of the alloy surface and its chemical composition. The investigation included the use of Cyclic Voltammetry (CV), Coulometry (C), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Analysis (EDX). At higher electrolyte concentrations (so-called II), the CV method revealed an increase in cathode current density in a CMF environment. During crystallisation of the Co–Mo–W alloy, fractures appeared on the surface due to internal stresses. The application of CMF reduced the fracture widths resulting from the increased concentration of electroactive particles at the working electrode and the greater deposited alloy mass. Electrolyte motion under the influence of CMF caused an increase in the percentage of the main ferromagnetic component (Co) in the alloy.     

The positive correlation of the strain hysteresis of textured PMN–24%PT ceramics with domain wall damping

High strain hysteresis is a stumbling block for the application of piezoelectric ceramics. This research affords a new insight into the origin of the ultra-low strain hysteresis of textured 76%Pb(Mg_1/3Nb_2/3)O₃–24%PbTiO₃ ceramics (PMN–24%PT). Highly textured PMN–24%PT ceramic system with some doping was successfully fabricated. This system shows unipolar strain curve approximately matching a straight line. The maximum hysteresis falls in 7%–11%. Compared to other representative piezoceramic system, current PMN–24%PT textured ceramics possess the least strain hysteresis. In addition, Mn²⁺ substitution for Nb⁵⁺ can inhibit domain wall mobility. The positive correlation between the ultra-low strain hysteresis and the domain wall damping is demonstrated by experiment and finite element simulation. In a conclusion, this work can enhance the understanding of strain hysteresis and contribute to high-precision piezoelectric actuators.     

Verification of the Maxwell–Stefan theory for tracer diffusion in zeolites

Using the Maxwell–Stefan theory for diffusion we derive a simple formula to relate the tracer (i.e. self) diffusivity D¹ and Maxwell–Stefan (MS), or jump, diffusivity $\text{D}\text{–}$. The presence of the interchange coefficient $\text{D}\text{–}{}_{\mathrm{ij}}$ in the MS formulation causes the self diffusivity to be lower than the jump diffusivity. Assuming the interchange coefficient to be given by $\text{D}\text{–}$/F we derive:$\text{D}{}^1\text{=}\text{D}\text{–}\text{1+Fθ}$where F is a factor to take account of topology effects within the zeolite matrix.The validity of the MS formulation is established by performing kinetic Monte Carlo simulations for diffusion of methane, perfluoromethane, 2-methylhexane and iso-butane in silicalite. Furthermore, it is shown that the exchange coefficient $\text{D}\text{–}{}_{\mathrm{ij}}$ is a quantification of correlation effects during the hopping of molecules. For iso-butane, the isotherm inflection leads to a sharp inflection in the diffusion behaviour. The influence of molecular repulsive forces on the loading dependence of the jump and self-diffusivities is also discussed with the aid of published Molecular Dynamics simulations for methane.     

An experimental model for predicting the piezo and dielectric constant of PVDF-PZT nanocomposite fibers with 0–3 and 1–3 connectivity

Energy harvesting from mechanical energy around ambient by flexible nanogenerators is one of the most efficient ways to generate green and renewable energy. Lead zirconate titanate (PZT) particles were embedded into a polyvinylidene fluoride (PVDF) polymer matrix to prepare mixed 0–3 and 1–3 connectivity nanocomposite fibers by electrospinning method. Various theoretical models of Maxwell-Garnett, Rayleigh, and Tinga etc were presented at two different Classes to predict the dielectric constant of PVDF-PZT nanocomposite fibers and compared the predicted results with the experimental results. Also, the piezoelectric properties like the piezoelectric coefficient (d₃₃) and piezoelectric voltage coefficient (g₃₃) were predicted by the Furukawa model and the predicted values were compared with the experimental values. Finally, the experimental model was derived to predict the dielectric constant of binary composites with mixed 0–3 and 1–3 connectivity. Compared to well-known models, the proposed experimental model accurately predicted the dielectric constant of PVDF-PZT nanocomposite fibers. The highest and lowest difference between the theoretical and the experimental results were obtained 12.24% and 0.12% for PZT volume fractions 1.1 and 17, respectively. Also, due to the linear relationship between the dielectric constant and piezoelectric coefficients, this model was generalized to predict the piezoelectric coefficients.     

Design and magneto-optical characteristics of Ge–Sb–S–PbI2 chalcogenide glasses with a high Verdet constant

To develop high-performance magneto-optical chalcogenide glasses and clarify the mechanisms of the Verdet constant, a series of GeS₂–Sb₂S₃–PbI₂ chalcogenide glasses were designed and fabricated, and their Faraday effects were investigated at a wavelength of 980 nm. A new parameter, that is, average polarizability, was proposed, and the results show that the Verdet constant has a good linear relationship with average polarizability, meaning that the Verdet constant of a chalcogenide glass can be directly estimated by its chemical constituents. The Verdet constant is as large as 0.200 min G⁻¹ cm⁻¹ at 980 nm for 22.5GeS₂–67.5Sb₂S₃–10PbI₂ composition glass, which is the largest value reported thus far for sulfide glasses; this glass also possesses good thermal and optical properties and therefore might be an attractive candidate for mid-infrared magneto-optical device applications.     

Analytical solutions of reaction–diffusion phenomena by porous cylindrical pellets with finite length

Analytical solutions were derived to predict transient change of intra-particle concentration inside cylindrical pellets with finite length immersed in an infinitely large medium. After the derivation of steady-state concentration by eigenfunction expansion, a transient solution was obtained by the separation of variables. Effects of the Thiele modulus (Φ) and aspect ratio of the pellet (H/R) were studied by calculating the average intra-particle concentration at a stationary state. The effectiveness factor (η) was also affected by H/R and Φ, since irreversible first order kinetics was assumed. As Biot number (Bi) increased, both intra-particle concentration and η increased due to the decrease of the mass transfer resistance of the surrounding film. Good agreement between analytical and numerical solutions was confirmed for both steady-state and transient solution by comparing the analytical results with the numerical solutions by finite element method. To extend the results to a batch reactor with finite volume, Duhamel's theorem was applied by assuming time-dependent boundary conditions to reflect the change in bulk concentration as a function of time. A method was proposed to measure intra-particle diffusivity for batch adsorber by setting Φ = 0. To investigate the effect of H/R, η could be included in material balance of batch, continuously stirred tank reactor (CSTR), and fixed bed reactors to predict reactor performance assuming a pseudo-steady state. First-order reaction by egg-shell catalysts as well as nonlinear reaction with two reactants could be solved numerically assuming finite cylindrical pellets. By solving coupled differential equations of material and energy balances, dynamic catalysis was confirmed from the enhancement of conversion, assuming forced oscillation of inlet temperature in CSTR.     

Experimental investigation of laminar LPG–H2 jet diffusion flame with preheated reactants

This paper presents an experimental investigation of the effect of H₂ addition on flame length, soot free length fraction (SFLF), flame radiant fraction, gas temperature and emission level in LPG–H₂ composite fuel jet diffusion flame for two preheated cases namely, (i) preheated air and (ii) preheated air and fuel. Results show that the H₂ addition leads to a reduction in flame length which may be caused due to an increased gas temperature. Besides this, the flame length is also observed to be reduced with increasing reactants temperature. The soot free length fraction (SFLF) increases as H₂ is added to fuel stream. This might have been caused by decrease in the C/H ratio in the flame and is favorable to attenuate PAH formation rate. Interestingly, the SFLF is observed to be reduced with increasing reactants temperature that may be due to reduction in induction period of soot formation caused by enhanced flame temperature. Moreover, the decreased radiant heat fraction with hydrogen addition is pertinent with the reduction in soot concentration level. The reduction in NO_x emission level with H₂ addition to the fuel stream is also observed. On the contrary, NO_x emission level is found to be enhanced significantly with reactant temperature that can be attributed to the increase in thermal NO_x through Zeldovich mechanism.     

Ionic conductivity of CaO–Y2O3–ZrO2 materials with constant oxygen vacancy concentration

Structural modification of the fully stabilised zirconia is a possible way to improve its electrical properties. Electrical properties, especially ionic conductivity, of cubic zirconia solid solutions are strictly related to the ionic radius and valency of cations incorporated into the zirconia structure. Nanopowders with a constant oxygen vacancy concentration of 8 and 10 mol% were prepared by a hydrothermal treatment of co-precipitated zirconia hydrogels in a NaOH environment. The desired oxygen vacancy concentrations were obtained by introducing calcia and yttria, at different ratios, to the zirconia solid solutions. Phase compositions and lattice parameters of the respective phases were determined using X-ray diffraction analysis. Electrical properties of the samples were described on the basis of complex impedance spectroscopy analysis. It has been stated that substitution of calcia for yttria or yttria for calcia in zirconia solid solutions leads to ionic conductivity enhancement. Samples with a cubic structure, close to the stabilisation threshold, had the highest conductivity.     

Mathematical modeling of the simultaneous convection–anomalous diffusion processes in porous media

ABSTRACT

After a brief overview of most important general features of the nonclassical diffusion on the base of the extended irreversible thermodynamics, the relevant mathematical formulae are incorporated into general formalism of the simultaneous convection–diffusion processes taking place in porous media. Then, using the simplest variant of the convection–diffusion equation, novel-type analytic solutions are derived for transport processes with both subdiffusion and superdiffusion characters in Lagrangian representation.     

Mass transfer in continuous mixtures with Maxwell–Stefan diffusion using the adaptive characterization method

The adaptive pseudocomponent characterization method for continuous mixtures was extended to mass transfer problems using the Maxwell–Stefan diffusion model. It is based on the direct quadrature method of moments (DQMoM), using a quadrature rule to discretize the molar fraction distribution of the continuous mixture. The solution method was applied to two one-dimensional mass transfer problems: the transient diffusion in a Loschmidt tube and the steady-state diffusion in a thin film. In the latter, it was showed that the DQMoM equations reduce to an equivalent problem with a fixed characterization and solution methods for linearized theory problems can be employed. For these two problems, the proposed method was verified against the discrete component model (DCM), whose implementation was also verified against existing solutions. Results showed that the adaptive method with five pseudocomponents predicts the mixture properties with maximum relative deviation smaller than 1% when compared to the DCM with 57 components.     

Unified model for the prediction of consecutive solid–liquid filtration and expression at the constant pressure

Unified nonlinear model is proposed for the prediction of consecutive solid–liquid filtration and expression at the constant pressure. This model is based on the Darcy–Terzaghi filtration-consolidation equations modified to consider power-law pressure dependence of the specific cake resistance, and transforming Darcy law to the linear form. The model considers nonuniform structure of compressible filter cakes obtained by filtration and following expression. The profiles of local compressive pressure and local cake characteristics are simulated and compared for different moderately and highly compressible filter cakes (H.K. kaolin, CaCO₃, silica, activated sludge) based on the analytical and numerical solutions of the model. It is shown that the behavior of solid–liquid expression depends from the initial structure of compressed materials. Consolidation ratio U of the filter cakes with initially nonuniform structure formed by filtration differs from that of semi-solid materials with initially uniform structure. Different methods of determination of consolidation coefficient are analyzed and compared for nonuniformly structured filter cakes.     

Prediction of solid–gas equilibria with the Peng–Robinson equation of state

In many applications related to Supercritical-Fluid (SCF) technology, solids are dissolved in SC fluids. Experimental data are now available for many systems but cannot cover all cases of potential practical interest. The prediction of solid solubilities in SC fluids, often in the presence of co-solvents, is useful for rational design of SCF extraction and related processes. Recently, thermodynamics has made considerable steps towards describing complex systems (gases with polar compounds) at high pressures using the so-called Equation of State/Excess Gibbs Free Energy (EoS/G^E) models. The success of these models is so far restricted to Vapor–Liquid Equilibria (VLE) for which they have been primarily developed and tested. In this work we evaluate such a predictive model, the LCVM EoS, for solid–gas equilibria (SGE) including systems with co-solvents. LCVM is chosen due to its success for VLE of asymmetric systems such as CO₂ with heavy alkanes and alcohols. Successful predictions are obtained for several solids as well as for some systems with co-solvents, but the results are less satisfactory for complex, multifunctional solids. A discussion of several factors, which affect modeling of SGE with cubic EoS, is included.     

Application of the Vrentas–Duda free-volume theory of diffusion below the glass-transition temperature: Application to hypromellose acetate succinate–solvent systems

The Vrentas–Duda free-volume theory for diffusion characterizes the diffusivity of a solvent in a polymer in terms of the concentration and size of the solvent, the temperature, and the glass transition temperature (T_g) of the individual components. The effective T_g of the polymer, however, is a function of the concentration of the solvent. This article introduces a modification that corrects for this change in the glass-transition temperature, thus providing more accurate diffusivities. The model has been verified by comparison with experimental diffusivities of water, acetone, methanol, and tetrahydrofuran in hypromellose acetate succinate (HPMCAS). HPMCAS is widely used in the production of pharmaceutical formulations. One common application is the formation of amorphous solid dispersions with poorly soluble active pharmaceutical ingredients (APIs) for dissolution and solubility enhancement. Frequently, the APIs and HPMCAS are put into solution and spray dried at an outlet temperature below the normal glass-transition temperature. The modified free-volume theory is able to directly predict or correlate with only one adjustable parameter the diffusivities as a function of the concentration and temperature. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47351.     

Evaluation of the performance of a constructal mixer with the iodide–iodate reaction system

A novel fluidic mixer, which takes advantage of impingement mixing and is designed according to the constructal approach, is evaluated by the Villermaux/Dushman method. The effects of different configurations (including the structure of the fluid collector and the diameter of the nozzles on the fluid injector) on the mixing performance (i.e. the segregation index and the energy dissipation rate) are determined. The segregation index is smaller, or in other words the degree of mixing is better, when a branch type fluid collector or smaller nozzles are used, however, at the cost of higher energy dissipation rate. When the flow rate is sufficiently high, mixing caused by the impingement of streams is almost complete, rendering the mixing in the branched channels unnecessary. As a result, if very high degree of mixing is pursued, the collector with a simple empty space should be used in the mixer to reduce energy consumption.     

Enhanced dielectric constant of acrylonitrile–butadiene rubber/barium titanate composites with mechanical reinforcement by nanosilica

Acrylonitrile–butadiene rubber (NBR), a synthetic rubber having C≡N dipoles, was chosen as a polymer matrix with a higher dielectric constant than other non-polar rubber like silicone rubber or ethylene–propylene–diene monomer. Barium titanate (BaTiO₃), as a ferroelectric material, with a high dielectric constant and low dielectric loss was selected as a main filler to further enhance the dielectric constant of NBR. An effective silane coupling agent (KH845-4), selected from five types of silane coupling agents with different characteristic functional groups, was used to modify the surface of BaTiO₃ particles to enhance its interfacial adhesion to the matrix. Fourier transform infrared spectroscopy (FTIR) was used to verify the successful modification. The addition of BaTiO₃ obviously enhanced the dielectric constants. In particular, an uncommon pattern of dielectric loss has been displayed and analyzed in this paper. Nevertheless, the reinforcing effect of mechanical strength of the NBR/treated BaTiO₃ composites is limited. On this basis, the addition of nanosilica (SiO₂), replacing part of NBR, improved the mechanical strength. Confirmed by scanning electron microscopy (SEM), the SiO₂ and treated BaTiO₃ particles were dispersed well in the NBR matrix. The tensile strength was increased from 4.33 to 6.12 MPa when SiO₂ accounted for 4%. Moreover, the curing characterizations, crosslinking density, resistivity, and oil resistance were evaluated. This composite material can be used in manufacturing electronic devices, which are subjected to oily environments for a long time.