General formula for bending beam determination of case II diffusion in polymer-containing bilayer structures

An exact formula has been presented to correlate the bending curvature cariation ratio, Ω, of any given bilayer structure comprising a solvent-swellable polymer layer with diffusion time, t, under case II diffusion. The formula can be used to determine the diffusion front velocity, v, for layered structures comprising a thick polymer film on a thin substrate or vice versa when subjected to solvent diffusion. According to this formula, there is little effect from plasticization or swelling in the transverse direction on the diffusion curve of Ω vs. t if the polymer layer to be investigated is relatively thin and its intrinsic hygroscopic strain ratio is less than unity. By using this model, the diffusion of N-methyl pyrollidinone (NMP) in a 18-μm rodlike pyromellitic dianhydride p-phenylene-diamine (PMDA-PDA) polymide film, coated on a 75-μm silicon substrate, is found to be case II with a diffusion front velocity of 1.84 × 10^-7 cm/s. © 1995 John Wiley & Sons, Inc.     

Ion‐exchange adsorption of calcium ions from water and geothermal water with modified zeolite A

The modified zeolite A was prepared by a two‐step crystallization method to remove scale‐forming cations from water and geothermal water. The adsorption kinetics, mechanism and thermodynamics were studied. The calcium ion adsorption capacity of the modified zeolite A was 129.3 mg/g (1 mg/g = 10^?3 kg/kg) at 298 K. The adsorption rate was fitted well with pseudo‐second‐order rate model. The adsorption process was controlled by film diffusion at the calcium ion concentration less than 250 mg/L (1 mg/L = 10^?3 kg/m³), and it was controlled by intraparticle diffusion at the concentration larger than 250 mg/L. The calculated mass‐transfer coefficient ranged from 2.23 × 10^?5 to 2.80 × 10^?4cm/s (1 cm/s = 10^?2m/s). Dubinin–Astakhov isotherm model could appropriately describe the adsorption thermodynamic properties when combined with Langmuir model. The adsorption process included not only ion exchange but also complexation between calcium and hydroxyl ions. The adsorption was spontaneous and endothermal. The high adsorption capacity indicates that the modified zeolite A is a suitable adsorption material for scale removal from aqueous solution. © 2014 American Institute of Chemical Engineers AIChE J, 61: 640–654, 2015     

A measure of effective crosslinks in formaldehyde-modified cotton celluloses

Sol-gel fractions have been measured for cotton celluloses crosslinked with formaldehyde under widely different conditions of reaction and have been employed for estimation of the efficiency of crosslinking in the various processes. Most efficient utilization of formaldehyde for insolubilization of molecular chains is indicated for an aqueous process (form W′) and least efficient utilization is indicated for a nonaqueous process (form D′), the difference in efficiency being approximately a factor of 40. Interpretation of sol-gel data has been made relative to a model assuming random reaction of crosslinking agent throughout the cotton cellulose and by relationships developed by Charlesby and Pinner and by Shultz. This leads to estimates of relative numbers (moles) of effective chain elements per gram, v_e (i.e., twice the number of effective crosslinks), which decrease in the following sequence for cottons at the 0.20% level of formaldehyde (i.e., 6.7 × 10^?5 mole/g.): aqueous process, higher formaldehyde concentration (W′, v_e = 4.8 × 10^?5), vapor process (V, v_e = 1.75 × 10^?5), bake-cure process (C, v_e = 1.37 × 10^?5), aqueous process, lower formaldehyde concentration (W, v_e = 0.95 × 10^?5), nonaqueous process (D, v_e = 0.03 × 10^?5).     

Determination of diffusion coefficient of oxygen into polymers by using electron spin resonance spectroscopy. I. Poly(methyl methacrylate)

A simple technique has been proposed for the measurement of the diffusion coefficient of oxygen into polymeric spheres. The technique is based on the scavenging of radicals produced by high energy radiation by oxygen. The diffusion coefficient of oxygen determined for poly(methyl methacrylate) has shown an inverse dependency on the dose received. Diffusion coefficient determined for low doses (D = 3.4 × 10^?8 cm²/s) as well as that determined after extrapolation to zero dose (D₀ = 3.7 × 10^?8 cm²/s) are in excellent agreement with the values reported in the literature.     

Discharge behaviour of plane nickel hydroxide electrodes

Plane nickel oxide electrodes were prepared by electrochemical deposition of nickel hydroxide on flexible nickel strips. Compact and adherent deposits were obtained, with thickness up to 4 × 10^?3 cm. They were cycled in 6 M KOH solution, and owing to the flexibility of the supporting nickel strips, did not show detaching. The results obtained from galvanostatic discharge curves fit the Peukert equation iⁿt = constant, giving an n value of 1.23 for the 1 × 10^?3 cm thick film and a value of 1.10 for the 4 × 10^?3 cm think film. The diffusion coefficients of moving species are in the order of magnitude of 10^?5 ?10^?6 cm²s^?1; the rate of discharge does not seem to be limited by proton diffusion. The proton diffusion in solid phase is not the only factor to be taken into account in the discharge process; diffusion and migration OH^? and H₂O species play an important role in plane thick nickel oxide film discharge.     

Kinetics of leaching of tunisian phosphate ore particles in dilute phosphoric acid solutions

Van der Sluis et al.'s model was used to determine the rate of the partial dissolution of a Tunisian phosphate rock with dilute phosphoric acid (1.5 mass% P₂O₅). When the temperature rises from 25 to 90°C, for a given particle size, the mass-transfer coefficients, k_L°, vary from 3 × 10^?3 to 8 × 10^?3 m ·s^?1. The corresponding diffusion coefficients, D, lies between 6 × 10^?7 and 27 × 10^?7 m²·s^?1. Activation energy is equal to 14 kJ·mol^?1 and values of k_L°, at 25°C, are in the range of 0.28 × 10^?3 and 4 × 10^?3 m·s^?1 when the agitation speed goes from 220 to 1030 rpm, showing that the leaching process is controlled by diffusion rather than by chemical reaction.     

Adsorption equilibrium,thermodynamics, kinetics,mechanism and process design of zinc(II) ions onto cashew nut shell

Cashew nut shell (CNS) is an agricultural waste was investigated as a new adsorbent for the removal of zinc(II) from aqueous environment. Effects of solution pH, CNS dose, contact time, initial zinc(II) concentration and temperature on removal efficiency were tested and optimum conditions were evaluated. The equilibrium data were fitted well with Langmuir isotherm model and pseudo‐second‐order kinetic model. Langmuir monolayer adsorption capacity of CNS was examined as 24.98 mg/g. Changes in standard Gibbs free energy (?G°), standard enthalpy (?H°) and standard entropy (?S°) showed that the sorption of zinc(II) ions onto CNS are spontaneous and exothermic at 303–333 K. Sorption process was found to be controlled by both surface and pore diffusion. A batch adsorber was designed for different CNS dose to effluent volume ratios using Langmuir equation. Effective diffusivity values were found to be 1.927 × 10^?11 (10 mg/L), 2.135 × 10^?11 (20 mg/L), 2.267 × 10^?11 (30 mg/L), 2.305 × 10^?11 (40 mg/L) and 2.362 × 10^?11 (50 mg/L) m²/s. © 2011 Canadian Society for Chemical Engineering     

Osmotic Dehydration Kinetics of Pumpkin Fruits Using Ternary Solutions of Sodium Chloride and Sucrose

The objective of this work was to obtain experimental data and modeling of osmotic dehydration kinetics of pumpkin fruits (Cucurbita pepo L.) with aqueous NaCl/sucrose solutions. For this purpose, effective diffusion coefficients for water, sucrose, and NaCl were calculated by means of a simple model based on Fick's second law. Water loss achieved 80%, sucrose 13%, and NaCl 6% of the initial sample weight. Effective diffusion coefficients ranged from 0.58–1.40 × 10^?9 m²/s, 0.75–1.23 × 10^?9 m²/s, and 2.60–4.11 × 10^?9 m²/s for water, sucrose, and NaCl, respectively. The proposed model gave a good correlation of the experimental data. The quality of the operation was evaluated by analysis of the values of WL/SG ratio.     

Determination of diffusion coefficient of oxygen into polymers by using electron spin resonance spectroscopy. II. Poly(vinyl acetate)

Electron spin resonance spectroscopy has been used to follow the kinetics of radical decay during postirradiation oxidation of poly(vinyl acetate). The oxygen uptake of γ-irradiated spherical poly(vinyl acetate) has been determined from changes in the intensity of the ESR signal. The diffusion coefficient (D) of oxygen determined by this technique showed an inverse relation with dose. The value of the diffusion coefficient of oxygen obtained in this study, after correcting for dose and size effects is 4.5 × 10^?8 cm²/s, and is in very good agreement with the literature value of D = 5.1 × 10^?8 cm²/s.     

Dynamic adsorption behaviors between Cu2+ ion and water‐insoluble amphoteric starch in aqueous solutions

Dynamic adsorption behavior between Cu²⁺ ion and water‐insoluble amphoteric starch was investigated. The sorption process occurs in two stages: external mass transport occurs in the early stage and intraparticle diffusion occurs in the long‐term stage. The diffusion rate of Cu²⁺ ion in both stages is concentration dependent. In the external mass‐transport process, the diffusion coefficient (D₁) increases with increasing initial concentration in the low‐ (1 × 10^?3‐4 × 10^?3M) and high‐concentration regions (6 × 10^?3‐10 × 10^?3M). The values of adsorption activation energy (k_d1) in the low‐ and high‐concentration regions are 15.46–24.67 and ?1.80 to ?11.57 kJ/mol, respectively. In the intraparticle diffusion process, the diffusion coefficient (D₂) increases with increasing initial concentration in the low‐concentration region (1 × 10^?3‐2 × 10^?3M) and decreases with increasing initial concentration in the high‐concentration region (4 × 10^?3‐10 × 10^?3M). The k_d2 values in the low‐ and high‐concentration regions are 9.96–15.30 and ?15.53 to ?10.71 kJ/mol, respectively. These results indicate that the diffusion process is endothermic in the low‐concentration region and is exothermic in the high‐concentration region for both stages. The external mass‐transport process is more concentration dependent than the intraparticle diffusion process in the high‐concentration region, and the dependence of concentration for both processes is about equal in the low‐concentration region. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2849–2855, 2001     

Effect of Scanning Speed on Copper Line Deposition Using Nanoparticle Deposition System (NPDS) for Direct Printing Technology

Cu nanoparticles (100 nm) were deposited on a silicon substrate using Nanoparticle Deposition System (NPDS) at 300 μm of stand-off distance (SoD). It was found that the lines deposited at a scanning speed below 5 μm/s showed ohmic contact; their resistivities were 1.68 × 10^?4 Ω·cm at 5 μm/s, 3.91 × 10^?5 Ω·cm at 2 μm/s, 1.70 × 10^?5 Ω·cm at 1 μm/s, and 1.28 × 10^?5 Ω·cm at 0.5 μm/s, respectively. However, samples fabricated at scanning speed of 8 and 10 μm/s showed schottky contact behavior. To study relationship between resistances of the deposited copper lines at various scanning speeds and density of the line, porosity of the deposited copper lines and SEM images of Cu lines were studied. As a result, average porosity of the copper lines was found to be 16% at 5 μm/s, 8% at 2 μm/s, 2% at 1 μm/s, and 6% at 0.5 μm/s. The porosity values are closely related to the resistance of the deposited copper lines. Therefore, the deposited copper line at 1 μm/s of scanning speed was shown to be the best one with the lowest porosity and resistance with its maximum thickness. This indicates that both the resistance and density of the deposited line improved at low scanning speed.

Copyright 2013 American Association for Aerosol Research     

Graft copolymerization of 4‐vinyl pyridine onto konjac glucomannan initiated by ammonium persulfate

The grafting of 4‐vinyl pyridine (4‐VP) onto konjac glucomannan (KGM) by ammonium persulfate (APS) as the initiator was studied in an acid aqueous solution under an inert atmosphere. The grafting ratio (G%) and grafting efficiency (E%) were evaluated comparatively. The dependence of these parameters on the initiator concentration, sulfuric acid concentration, ratio of monomer to KGM, temperature, and reaction time was also investigated. Under conditions of [KGM] = 1.00 g/L, [APS] = 1.00 × 10^?2 mol/L, [4‐VP] = 9.32 × 10^?2 mol/L, [H⁺] = 5.00 × 10^?2 mol/L, temperature = 35°C, and time = 120 min, the optimum G% and E% were 307.27 and 52.75%, respectively. The proof of grafting was obtained from thermogravimetric analysis and infrared spectra. Preliminary research of the graft's adsorption capacity for heavy‐metal ions [Cr(VI), Cu(II), Pb(II), and Cd(II)] was done. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Transport of Co(II) Ions through Di(2-ethylhexyl) Phosphoric Acid-CCl4 Supported Liquid Membranes

Abstract

A liquid membrane transport study of Co(II) using di(2-ethylhexyl) phosphoric acid (D2EPHA) as carrier and CCl₄, as diluent supported on polypropylene microporous film has been carried out. The carrier concentration in the membrane and HCl concentration in the stripping phase have been varied to see the effect on transport of Co(II) ions across the membrane. Maximum flux and permeability values of 1.23 × 10^?5 mol · m^?2 · s^?1 and 7.66 × 10^?11 m²/s, respectively, at a 0.87 mol/dm³ carrier concentration in the membrane have been found. At 1 mol/dm³ HCl concentration in the stripping phase the flux and permeability have maximum values of 1.4 mol · m^?2 · s^?1 and 5.27 × 10^?11 m²/s, respectively. The distribution coefficient of Co(II) ions into organic phase has been found to increase with increasing carrier concentration. The diffusion coefficient determined varies from 13.73 × 10^?11 to 0.83 × 10^?11 m²/s, which is the reverse order of the values of the distribution coefficient and explains the permeability of the Co(II) D2EPHA complex through the membrane.     

The interaction of hydrogen sulfide with lead- and barium–cadmium–zinc-stabilized poly(vinyl chloride)

Poly(vinyl chloride) polymers stabilized with tribasic lead sulfate discolor upon exposure to hydrogen sulfide gas as a result of lead sulfide formation. The discoloration occurs for samples in both cord and sheet forms and is shown to be a function of total H₂S exposure, reaching a limiting value that is determined by the amount of lead stabilizer used in the polymer formulation. The permeation and diffusion constants for H₂S through PVC stabilized with tribasic lead sulfate and with a liquid Ba–Cd–Zn formulation are found to be P_Pb = (6.0 ± 0.2) × 10^?9, P_BaCdZn = (5.2 ± 0.2) × 10^?9 (both in cm³ gas?cm film/cm² area?sec?cm Hg), D_Pb = (1.3 ± 0.2) × 10^?7 cm²/sec, and D_BaCdZn = (6.4 ± 0.6) × 10^?8 cm²/sec, all measured at 21°C. The stabilizing efficiencies of the formulations were assessed by HCl evolution measurements, which show that exposure to H₂S decreases the initial polymer stability for both Pb-stabilized and Ba–Ca–Zn-stabilized formulations. Protection of stabilized PVC formulations from diffusing hydrogen sulfide is thus advisable for long-term stability as well as for color integrity.     

Preparation and properties of bisphenol A‐based sulfonated poly(arylene ether sulfone) proton exchange membranes for direct methanol fuel cell

Novel bisphenol A‐based sulfonated poly(arylene ether sulfone) (bi A‐SPAES) copolymers were successfully synthesized via direct copolymerization of disodium 3,3′‐disulfonate‐4,4′‐dichlorodiphenylsulfone, 4,4′‐dichlorodiphenylsulfone, and bisphenol A. The copolymer structure was confirmed by Fourier transform infrared spectra and ¹H NMR analysis. The series of sulfonated copolymers based membranes were prepared and evaluated for proton exchange membranes (PEM). The membranes showed good thermal stability and mechanical property. Transmission electron microscopy was used to obtain the microstructures of the synthesized polymers. The membranes exhibit increased water uptake from 8% to 66%, ion exchange capacities from 0.41 to 2.18 meq/g and proton conductivities (25°C) from 0.012 to 0.102 S/cm with the degree of sulfonation increasing. The proton conductivities of bi A‐SPAES‐6 membrane (0.10–0.15 S/cm) with high‐sulfonated degree are higher than that of Nafion 117 membrane (0.095–0.117 S/cm) at all temperatures (20–100°C). Especially, the methanol diffusion coefficients of membranes (1.7 × 10^?8 cm²/s–8.5 × 10^?7 cm²/s) are much lower than that of Nafion 117 membrane (2.1 × 10^?6 cm²/s). The new synthesized copolymer was therefore proposed as a candidate of material for PEM in direct methanol fuel cell. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The Effect of External Mass Transfer Resistance during Drying of Fermented Sausage

The drying mechanism of fermented sausages (sucuks) that were cylindrical rod shaped, 40 cm long and 4 cm diameter, during ripening under natural convection conditions at different temperatures (15 to 30°C) was examined. To simulate the experimental drying curves, three empirical models and a diffusional model assuming negligible external mass transfer resistance were evaluated. The drying rate curves of sucuk samples were also simulated taking into account the influence of the external mass transfer resistance. The equation was solved using the trial-and-error solution algorithm developed in this study and the mass transfer coefficient, k _c , and effective moisture diffusivity, D _eff , were simultaneously determined (1.44 × 10^?8 to 1.93 × 10^?8 m/s and 4.30 × 10^?10 to 6.85 × 10^?10 m²/s, respectively). The proposed model considering the effect of external resistance allowed the accurate simulation of the experimental drying data of sucuks at different temperatures.     

Separation of mercury and arsenic from produced water via hollow fiber contactor: Kinetic and mass transfer analysis

The separation of Hg(II) and As(V) from produced water by hollow fiber contactors was investigated. Two identical hollow fiber modules were employed. The first module was used for extraction, while the second module was used for stripping. The optimum conditions achieved were 14% (v/v) of Aliquat336, 0.07 M thiourea, volumetric flow rate of 100 mL/min for aqueous solution and 0.02 M HCl of stripping solution. At such conditions, the maximum extraction of Hg(II) and As(V) attained 100% and 78.78%, respectively. Concurrently, the maximum stripping of Hg(II) and As(V) reached 47.88% and 6.66%, respectively. The overall mass transfer coefficients of Hg(II) and As(V) extraction were 2.31×10^?6 and 1.15×10^?6m/s, while the Hg(II) and As(V) stripping exhibited the overall mass transfer coefficients of 8.37×10^?7 m/s and 9.05×10^?7 m/s, respectively. Mass transfer coefficients of the organic layer diffusion (k₀) had the most effect on the overall mass transfer coefficients.     

A kinetic model for pyrolysis of cellulose

It has been shown that the pyrolysis of cellulose at low pressure (1.5 Torr) can be described by a three reaction model. In this model, it is assumed that an “initiation reaction” leads to formation of an “active cellulose” which subsequently decomposes by two competitive first-order reactions, one yielding volatiles and the other char and a gaseous fraction. Over the temperature range of 259–341°C, the rate constants of these reactions, k_i (for cellulose → “active cellulose”), k_v (for “active cellulose” → “volatiles”), and k_c (for “active cellulose” → char + the gaseous fraction) are given by k_i = 1.7 × 10²¹e^{? (58,000/RT)} min ^?1, k_v = 1.9 × 10¹⁶e^{? (47,300/RT)} min^?1, and k_c = 7.9 × 10¹¹e^{? (36,600/RT)} min^?1, respectively.     

Drying Kinetics of Apple Tissue Treated by Pulsed Electric Field

The aim of this work was to study the influence of pulsed electric field (PEF) on the drying kinetics of apple tissue. Therefore, mathematical models that are commonly used in the literature were applied to describe the process. PEF treatment of the samples was carried out at an intensity of E = 5–10 kV/cm and 10–50 pulse numbers. Subsequently, the apples were convectively dried at 70°C and air velocity of 2 m/s. Based on electrical conductivity measurement, the cell disintegration index Z _p was computed. Midilli et al.'s(Drying Technology, Vol. 20, pp. 1503–1513, 2001) model was evaluated as the most adequate to describe the moisture transfer in PEF-treated and intact samples. PEF pretreatment induced a reduction in drying time of up to 12% when 10 kV/cm and 50 pulses were applied. For instance, after 60 min of drying, the dimensionless moisture ratio for PEF-treated (10 kV/cm, 50 pulses) samples was 0.18 compared to 0.26 for the untreated apples. The effective moisture diffusivity, calculated on the basis of the Fick's second law, was 1.04 × 10^?9 m/s for intact samples and from 1.09 × 10^?9 to 1.25 × 10^?9 m²/s for PEF-treated samples at 10 pulses at 5 kV/cm and 50 pulses at 10 kV/cm, respectively.     

Continuous crystallization of potassium carbonate

Continuous crystallization of potassium carbonate was investigated in a mixed suspension mixed product removal (MSMPR) crystallizer with 7.0 1 working volume. Highly polydispersed product was obtained, with x ₅₀ varying between 320 and 670 μm. Crystal growth rates can be described by the model of Abegg, Stevens and Larson (ASL) (size dependent crystal growth rate). Values of G₀ = 8.6 × 10^?9 to 3.6 × 10^?8 m/s and B₀/φ = 2.7 × 10⁸ to 4.2 × 10⁹ 1/m³s were obtained for m_T = 45 to 92 kg/m³ and ε = 0.45 ± 0.05 W/kg. Nucleation kinetics at 27 °C can be described by the equation: B₀/φ = k_Bφ_sε^0.73G₀^2.5. Since G₀ ∝ σ, convection and/or diffusion rather than surface integration are the crystal growth controlling mechanisms.