Separation of Co(II) and Mn(II) from sulphate media via a HFSLM: Reaction flux model and experimental verification

Separation of Co(II) and Mn(II) from sulphate media through triple HFSLM in series using D2EHPA was explored. Mn(II) was extracted preferentially over Co(II) at the pH value of 5, 100 ppm of Co(II) and Mn(II), 5% (v/v) of D2EHPA, 0.2 M HCl. The highest extraction percentage of Mn(II) was 98.14%, and Co(II) remained at 94.05% in the raffinate stream. The reaction order (n) and the reaction rate constant (k_f) were found to be 1.00 and 0.0180 min⁻¹, respectively. Furthermore, the reaction flux model proved to be in good agreement with the experimental data at an average deviation of 2.24%.     

Mass transfer from a single fluid sphere to power-law liquids at moderate Reynolds numbers

The steady-state convective inter-phase mass transfer from a single Newtonian fluid sphere (free from surfactants) to a continuous phase with power-law viscosity has been studied at moderate Reynolds and Schmidt numbers under the conditions when the resistance to mass transfer in the dispersed phase is negligible. The species continuity equation, segregated from the momentum equations of both phases, has been numerically solved using a finite difference method. The effects of the Reynolds number (Re_o), power-law index (n_o), internal to external fluid characteristic viscosity ratio (k) and Schmidt number (Sc) on the local and average Sherwood number (Sh) have been analysed over the following ranges of conditions: 5?Re_o?200, 0.6?n_o?1.6, 0.1?k?50 and 1?Sc?1000. It has been observed that irrespective of the values of the Reynolds number and of the power-law index, as the value of k increases the average Sherwood number decreases for intermediate to large values of the Peclet number. As the value of the power-law index increases, the rate of mass transfer decreases for all values of the Reynolds number and the characteristic viscosity ratio thereby suggesting that shear-thinning behaviour facilitates mass transfer, whereas shear-thickening behaviour impedes it. Based on the present numerical results, a simple predictive correlation is proposed which can be used to estimate the rate of inter-phase mass transfer of a fluid sphere sedimenting in power-law liquids.     

Microwave dielectric properties of Re3Ga5O12 (Re: Nd,Sm, Eu,Dy and Yb) ceramics and effect of TiO2 on the microwave dielectric properties of Sm3Ga5O12 ceramics

Re₃Ga₅O₁₂ (Re: Nd, Sm, Eu, Dy and Yb) garnet ceramics sintered at 1350–1500 °C had a high quality factor (Q × f) ranging from 40,000 to 192,173 GHz and a low dielectric constant (ɛ_r) of between 11.5 and 12.5. They also exhibited a relatively stable temperature coefficient of resonant frequency (τ_f) in the range of −33.7 to −12.4 ppm/°C. In order to tailor the τ_f value, TiO₂ was added to the Sm₃Ga₅O₁₂ ceramics, which exhibited good microwave dielectric properties. The relative density and grain size increased with addition of TiO₂, resulting in the enhancement of Q × f value. The τ_f increased with the addition of TiO₂. Excellent microwave dielectric properties of ɛ_r = 12.4, Q × f = 240,000 GHz and τ_f = −16.1 ppm/°C were obtained from the Sm₃Ga₅O₁₂ ceramics sintered at 1450 °C for 6 h with 1.0 mol% TiO₂. Therefore, Re₃Ga₅O₁₂ ceramics, especially TiO₂-added Sm₃Ga₅O₁₂ ceramics are good candidates for advanced substrate materials in microwave integrated circuits (MICs) applications.     

Coupled CFD–DEM of particle-laden flows in a turning flow with a moving wall

The nature of the particle–solid interactions and particle–fluid interactions in rectangular duct bend geometry with/without a moving wall is studied, taking into account particle collision, colloidal, and hydrodynamic forces, and four way coupling between the fluid flow and particles. The focus is on systems where particles and fluid phase have similar length scales, fluid Reynolds number (Re_f) ∼ 1, and particle's Stokes number (St) ∼ 1. Particles move toward the walls of the channel near the bend, and have long residence times in these regions. Buoyancy force has negligible effect on particle motion, where adhesion and drag forces lead to particle motion and agglomeration patterns. The effect of a free surface on agglomeration sites in the turning flow is elucidated.     

Concentration polarisation in tubular membranes —a numerical approach

A theoretical investigation ofparticle deposition onto a permeable surface of a tubular membrane is presented. Themass transport mechanisms are mathematically expressed using the two-dimensional convective diffusion equation. A numerical scheme is presented to solve the two-dimensional convective diffusion equation at the steady state for the case of nonuniform permeation velocity. This equation is solved numerically using a finite difference method. The numerical prediction of mass transfer in the mass boundary requires the use of a very dense grid. The concentration profiles along the membrane surface and the mass boundary layer are predicted. The effect of the Reynolds number, the wall Reynolds number and the Schmidt number were investigated. Correlations for the concentration boundary layer thickness δ_c/D=2(z/D)^0.33(ReSc)^{− 0.33} Re_w^−0.3 (1-0.4377 Sc^−0.0018 Re_w^−0.1551), and for the Sherwood number Sh =1.230 [(D/z) ReSc] ^0.33 (1 + 0.010 Re^−0.125Sc^1.055 Re_w.^1.132) based on the predicted values of the solute concentration profiles, are proposed, in the operating condition ranges 300 < Re < 1000, 0.02 < Re_w < 0.3 and 600 < Sc < 3200.     

Study of kinetics in the biosorption of lead onto native and chemically treated olive stone

In this research, olive stone was used as precursor for the development of new biosorbents for lead ions. Chemical treatments were analyzed in terms of their effects on physical–chemical properties and kinetics of lead removal. A kinetic study of the biosorption of lead ions by olive stone was analyzed according to six different kinetic models (pseudo first, pseudo second, pseudo n-order, Elovich, solid diffusion and double exponential models). The biosorption kinetic data were successfully described with pseudo-nth order and double exponential models for all biosorbents. The double exponential model allowed estimating the values of external and internal mass transfer coefficients. The values of external mass transfer coefficient (k_e) ranged from 42.62 × 10⁻⁶ to 508.3 × 10⁻⁶ m min⁻¹ and the internal mass transfer coefficient (k_i) from 3.76 × 10⁻⁶ to 73.4 × 10⁻⁶ m min⁻¹. On the other hand, the analysis of experimental data showed that chemical treatments of the biomass led to increase biosorption capacity of the native biomass.     

Investigation of the relations between structure and microwave dielectric properties of divalent metal tungstate compounds

The microwave dielectric characteristics of AWO₄ (A = Mg, Zn, Mn, Ca, Sr, Ba) compounds and their relations with structure have been investigated as a function of A cations. Crystal structure was investigated by XRD; the structure changed from wolframite to scheelite with increasing size of A cation. Dielectric properties such as permittivity, temperature coefficient of resonant frequency (τ_f), and quality factors (Q × f) were found to be correlated with the size of A cations and the structure of compounds. Permittivity decreased with the size of A cations, and temperature coefficient of resonant frequency was correlated with unit cell volume. AWO₄ compounds are suitable for the applications of low-k dielectric materials; permittivity = 8–15, τ_f = −50 to −70, and Q × f = 60,000–70,000.     

The effect of sintering temperature and time on microwave properties of Sm(Zn1/2Ti1/2)O3 ceramics for resonators

The microwave dielectric properties of Sm(Zn_1/2Ti_1/2)O₃ ceramics have been investigated. Sm(Zn_1/2Ti_1/2)O₃ ceramics were prepared by conventional solid-state route with various sintering temperatures and times. The prepared Sm(Zn_1/2Ti_1/2)O₃ exhibited a mixture of Zn and Ti showing 1:1 order in the B-site. Higher sintered density of 7.01 g/cm³ can be produced at 1310 °C for 2 h. The dielectric constant values (ɛ_r) of 22–31 and the Q × f values of 4700–37,000 (at 8 GHz) can be obtained when the sintering temperatures are in the range of 1250–1370 °C for 2 h. The temperature coefficient of resonant frequency τ_f was a function of sintering temperature. The ɛ_r value of 31, Q  ×  f value of 37,000 (at 8 GHz) and τ_f value of −19 ppm/°C were obtained for Sm(Zn_1/2Ti_1/2)O₃ ceramics sintered at 1310 °C for 2 h. For applications of high selective microwave ceramic resonator, filter and antenna, Sm(Zn_1/2Ti_1/2)O₃ is proposed as a suitable material candidate.     

Microwave dielectric properties of Mg3(VO4)2–xBa3(VO4)2 ceramics for LTCC with near zero temperature coefficient of resonant frequency

The Mg₃(VO₄)₂–xBa₃(VO₄)₂ ceramics have been investigated to obtain a low-temperature co-fired ceramic (LTCC). The highest quality factor (Q_f) of approximately 114,000 GHz was obtained when the ceramic with x = 0.2 was sintered at 950 °C for 5 h in air. The temperature coefficient of resonant frequency (τ_f) of the ceramics sintered at 1025 °C varied from −90 to 60 ppm/°C as the amount of xBa₃(VO₄)₂ increased, and was a near zero value in the sample obtained at x = 0.5 where the dielectric constant (ɛ_r) and the Q_f values were approximately 12 and 55,000 GHz, respectively. In order to reduce the sintering temperatures of Mg₃(VO₄)₂–xBa₃(VO₄)₂ ceramics, the effects of Li₂CO₃ addition as a sintering aid on the microwave dielectric properties of Mg₃(VO₄)₂–0.5Ba₃(VO₄)₂ ceramics were also characterized in this study. The Li₂CO₃ addition was effective in reducing the sintering temperature without detrimental effects on the Q_f values of the ceramics. One result: the microwave dielectric properties of Mg₃(VO₄)₂–0.5Ba₃(VO₄)₂ with 0.0625 wt%-doped Li₂CO₃ ceramic, which was sintered at 950 °C for 5 h in air, has a ɛ_r value of 13, a Q_f value of 74,000 GHz, and a τ_f value of −6 ppm/°C.     

Effect of sintering temperature and dopant concentration on microstructure and electrical conductivity of ultra-fine-grained ZrO2–Sc2O3 ceramics

Phase transformations in ZrO₂ + xSc₂O₃ solid solutions (6.5 < x < 11 mol%) at sintering of ceramics obtained from nanopowders produced by laser evaporation of the ceramic targets have been studied. The Sc₂O₃ concentration increasing from 6.5 to 11 mol% is accompanied by the sintering temperature decreasing and the average grain size growth from 130 nm to 760 nm. At concentration of about 7 mol% Sc₂O₃ an abrupt increase of the average grain size and electric conductivity is observed. The sinterability of the ZrO₂ − хSc₂O₃ ceramics is affected by the prehistory of nanopowders preparation. The characteristics of ceramics obtained from nanopowders evaporated from the targets based on (ZrO₂ + xmol% Sc₂O₃) mixture and on the (ZrO₂ − 11mol% Sc₂O₃) solid solution significantly differ, namely, in the latter the sintering temperature is markedly lower and the shrinkage rate is higher. Besides, its average grain size is substantially lower and the conductivity is higher.     

Statistical evaluation of a liquid desiccant dehumidification system using RSM and theoretical study based on the effectiveness NTU model

In the present study the performance of an air dehumidifier using lithium bromide (LiBr) as a desiccant was investigated. Response surface methodology (RSM) was used to assess individual and interactive effects of the six main factors (velocity, temperature and humidity of air, flow rate, temperature and concentration of desiccant) on dehumidification mass rate. A reduced quadratic statistical model was derived to predict dehumidification mass rate. The maximum dehumidification mass rate was obtained 0.154 g/s under the optimal conditions of an air velocity of 4.1 m/s, desiccant flow rate of 0.035 kg/s, air humidity ratio of 0.0185 kg/kg, desiccant concentration of 0.48 kg/kg, air temperature of 29.5 °C, and desiccant temperature of 21.8 °C. The effectiveness number of transfer unit (NTU) model was employed to describe the coupled heat and mass transfer. The results of the model and the experimental data show good agreement. Dimensionless mass and heat transfer coefficients correlations are proposed; the average absolute differences between the predicted values and the experimental findings for Sh and Nu numbers were calculated as 2.14% and 5.27%, with the discrepancies mainly within ±9% and ±13%, respectively.     

Grain size effect on piezoelectric and ferroelectric properties of BaTiO3 ceramics

A series of dense barium titanate (BaTiO₃, BTO) ceramics with different grain sizes (GS) were prepared by two-step sintering method. The effect of GS on piezoelectric coefficient (d₃₃) and planar electromechanical coupling factor (k_p) displayed a trend similar to that on relative permittivity (ɛ′). The values of d₃₃, k_p, and ɛ′ increased significantly with decreasing GS, reaching maximum values (ɛ′ = 6079, d₃₃ = 519 pC/N and k_p = 39.5%) at approximately 1 μm, and then decreased rapidly with further decreasing GS. The results revealed that high-performance BTO ceramics could be effectively prepared by controlling GS. Polarization–electric field hysteresis loops and temperature dependence of ɛ′ were also investigated.     

Kinetic model of CaO/fly ash sorbent for flue gas desulphurization at moderate temperatures

Characteristics of the sulphation reaction between SO₂ and CaO/fly ash sorbent were analyzed based on TGA results to develop a kinetic model for a dry moderate temperature (400–800 °C) FGD process. It was found that SO₂ diffusion within sorbent particles involved three sub-processes: inter-particle diffusion, inter-grain diffusion and diffusion through product layers and the diffusion dominated the whole sulphation reaction process. The activation energy for product layer diffusion E_diff of 49.3 kJ mol⁻¹ being greater than the chemical reaction activation energy E_a of 13.9 kJ mol⁻¹ verified the importance of the diffusion. Predictions using the kinetic model in which k₀ varies with temperature agree well with the experimental data.     

Preparation and ionic conduction of CaZr1−xScxO3−α ceramics

A series of CaZr_1−xSc_xO_3−α (x=0, 0.05, 0.10, 0.15) perovskite oxide ceramics were successfully fabricated at 1400 °C for 10 h and then further sintered at 1650 °C for 10 h via a solid-state reaction sintering process. Conductivities of the ceramics were measured under the atmosphere that contains 1% H₂/Ar and 5.63 kPa H₂O/Ar by the electrochemical impedance spectra technique. It was found that the conductivities of CaZr_1−xSc_xO_3−α (x=0, 0.05, 0.10, 0.15) ceramics increased with the increase of the measuring temperature, and the conductivity achieved its maximum value of 2.03×10⁻⁵–6.5×10⁻³ S cm⁻¹ when the doping amount of Sc (x) was 0.10. Additionally, element doping can increase the conductivities and decrease the conductivity activation energies of CaZr_1−xSc_xO_3−α ceramics. The results of transport number measurement indicated that the CaZr_0.9Sc_0.1O_3−α is almost a pure protonic conductor at 500–750 °C, while it is a mixed protonic-oxygen ionic-electronic conductor at 750–1300 °C.     

CFD evaluation of internal manifold effects on mass transport distribution in a laboratory filter-press flow cell

The internal manifold geometry strongly influences the flow distribution inside an electrochemical reactor. The mass transport coefficient is a function of the flow pattern and is a key parameter in successful electrochemical reactor design and scale-up. In this work, a commercial computational flow dynamics (CFD) package was used to describe the flow pattern in the FM01-LC reactor at controlled volumetric flow rates (corresponding to mean linear flow velocities past the electrode surface between 0.024 and 0.11 m s^?1). Numerical Re numbers were obtained for each local flow velocity at different positions in the reactor channel. From a known mass transport correlation (based on dimensionless groups, i.e. Sh, Re, Sc), numerical k _m values were obtained (in the range 200 < Re < 1,000) at different positions in the reactor channel. Computed k _m numbers are compared against experimental values. This computational approach could be useful in reactor design or selection since it facilitates a fast, preliminary reactor flow and mass transport characterisation without experimental electrochemical measurements.     

Broadband dielectric spectroscopy of PbMg1/3Nb2/3O3–PbSc1/2Nb1/2O3 ceramics

Broadband dielectric spectroscopy results of various ordered and disordered (1 ? x)Pb(Mg_1/3Nb_2/3)O₃–(x)Pb(Sc_1/2Nb_1/2)O₃ (PMN–PSN) ceramics are investigated in the temperature range from 80 K to 300 K and frequency range from 20 Hz to 2 THz. Dielectric dispersion is very broad and in the ferroelectrics case (x = 1, 0.95) consists of two parts: low-frequency part caused by ferroelectric domains and higher frequency part caused by soft mode. The relaxational soft mode exhibits pronounced softening close to phase transition temperature, as it is typical for order–disorder phase transitions. By substituting Sc³⁺ by Mg²⁺ in PMN–PSN ceramics relaxation slows down, and for relaxors (x = 0.2) the most probable relaxation frequency decreases on cooling according to Vogel–Fulcher law.     

Microwave dielectric properties and crystal structure of the tungstenbronze-type like (Ba1 − αSrα)6(Nd1 − βYβ)8Ti18O54 solid solutions

A study of the dielectric properties, especially the Q × f value, of the tungstenbronze-type like (Ba_1 − αSr_α)_6 − 3xNd_8 + 2xTi₁₈O₅₄ solid solutions in x = 0 system was carried out. These compositions near x = 0 have very low Q × f values. To improve the Q × f value of these materials, we tried two substitutional systems, which are (Ba_1 − αSr_α)₆Nd₈Ti₁₈O₅₄ and Ba₄Sr₂(Nd_1 − βY_β)₈Ti₁₈O₅₄. In the former composition, the Q × f value was increased from 206 to 5880 GHz in the range of 0 ≤ α ≤ 0.5. And we found that Sr ions substituted for Ba ions in A1 sites have good effect on increasing the Q × f value, but Sr ions substituted for Ba ions in A2 sites have poor effect on increasing it. The latter composition also has a small effect on increasing the Q × f value.     

Effects of sintering parameters and Nd doping on the microwave dielectric properties of Y2O3 ceramics

Y₂O₃ ceramics with good dielectric properties were prepared via co-precipitation reaction and subsequent sintering in a muffle furnace. The effects of Nd doping and sintering temperature on microwave dielectric properties were studied. With the increase in sintering temperature, the density, quality factor (Q×f), and dielectric constant (ε_r) values of pure Y₂O₃ ceramics increased to the maximum and then gradually decreased. The Y₂O₃ ceramics sintered at 1500 °C for 4 h showed optimal dielectric properties: ε_r=10.76, Q×f=82, 188 GHz, and τ_f=−54.4 ppm/°C. With the addition of Nd dopant, the Q×f values, ε_r, and τ_f of the Nd: Y₂O₃ ceramics apparently increased, but excessive amount degraded the quality factor. The Y₂O₃ ceramics with 2 at% Nd₂O₃ sintered at 1460 °C displayed good microwave dielectric properties: ε_r=10.4, Q×f=94, 149 GHz and τ_f=−46.2 ppm/°C.     

Morphotropic phase boundary in the BNT–BT–BKT system

Lead-free x Bi_0.5Na_0.5TiO₃–y BaTiO₃–z Bi_0.5K_0.5TiO₃ piezoelectric ceramics were synthesized by a conventional solid state reaction method. The microstructure, ferroelectric and piezoelectric properties of the ceramics were investigated. Structure measurements by X-ray diffraction with Rietveld refinement have allowed us to specify more precisely the morphotropic phase boundary (MPB) in this system. For (1 ? x) BNT–x BT solid solution ceramics, the 0.94 BNT–0.06 BT morphotropic composition shows the higher values with d₃₃ = 170 pC/N, k_p = 0.35 and k_t = 0.53. In the case of (1 ? x) BNT–x BKT compositions, the d₃₃, k_p and k_t are, respectively, 137 pC/N, 0.39 and 0.54 for the 0.80 BNT–0.20 BKT ceramic. On the other hand, the ternary 0.865 BNT–0.035 BT–0.100 BKT morphotropic composition shows high piezoelectric constant and electromechanical coupling factors (d₃₃ = 133 pC/N, k_p = 0.26 and k_t = 0.57).     

The effect of cation ordering and domain boundaries on low loss Ba(BI1/3BII2/3)O3 perovskite dielectrics revealed by high-angle annular dark-field scanning transmission electron microscopy (HAADF STEM)

High quality ceramics of Ba((Co_0.7Zn_0.3)_1/3Nb_2/3)O₃ (BCZN), Ba(Mg_1/3Nb_2/3)O₃ (BMN) and Ba(Mg_1/3Ta_2/3)O₃ (BMT) were prepared by the mixed oxide route using sintering temperatures up to 1620 °C. Products with a high degree of cation ordering exhibited dielectric Q × f values from 83,000 GHz (BCZN) to 360,000 GHz (BMT). High Resolution TEM and aberration-corrected scanning transmission electron microscopy (STEM) revealed ordering domains and type I, II and III boundary structures. High-Angle Angular Dark Field (HAADF) STEM images provided direct evidence of 1:2 ordering and stacking sequences, and the presence of disordered regions within domain boundaries. The exceptionally high Q × f values for BMT are associated with a high degree of B-site ordering and the removal of domain boundaries in large, single domain grains. The catastrophic degradation of Q × f values in BMN after prolonged sintering is associated with formation of a lossy ferroelectric secondary phase (Ba₃Nb₂O₈), and changes to composition and stoichiometry of BMN grains.