A comparative study on the free volume theories for diffusivity through polymeric membrane in pervaporation process

In this work, free volume theories are coupled with a thermodynamic model and generalized Fick's law to develop a mass transfer model based on solution‐diffusion mechanism for pervaporation process with a hydrophobic polymeric membrane. The Wesselingh, Fujita and Vrentas‐Duda's theories are used to calculate concentration‐dependent diffusion coefficient of permeants inside polydimethylsiloxane membrane. The sorption and pervaporation experiments on aqueous ethanol solutions are performed to validate the sorption and pervaporation models. The results reveal that the proposed models are able to predict influences of feed concentration and temperature as well as permeate‐side pressure on partial fluxes through the membrane. The comparative investigation indicated that Wesselingh's free volume theory underestimated the diffusion coefficients inside the membrane and the accuracy of the model used this theory is very low for prediction of the permeation flux. Generally, Fujita and Vrentas‐Duda's theories are found to be much more accurate especially for dilute aqueous feed solutions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40581.     

A practical model of the diffusion of oil-based fluid into polyethylene

It is possible to modify the properties of semicrystalline polymers using diffusion to introduce additional functionality. For example, Vitamin E infused polyethylene has antioxidant properties, which enhances the longevity of the polyethylene. Lipiodol ultra fluid, an iodinated oil-based contrast agent, can be used to enhance the X-ray attenuation of medical grade polyethylene. To manufacture a part geometry with a sufficiently even distribution of oil for radiopacity, while maintaining the thermally dependent properties of the polymer (e.g., crystallinity) is a challenge. Rather than relying on trial and error, this study aimed to identify the simplest, most practical model, which could assist with planning for manufacturing of such parts. Models in 1D, 2D, and 3D were examined but only the 3D Fickian model was able to predict the profile of oil diffusion within polyethylene with suitable performance (as low as 7% inaccuracy for some diffusion conditions). The model was more accurate at the surface of the samples and at lower diffusion temperatures. The 3D Fickian model used in this study was capable of estimating the oil concentration in the surface of a polyethylene part after diffusion to a sufficient accuracy for planning manufacturing processes of oil-infused polyethylene parts.     

A kinetic model for the adsorption of gold from I2/I− solutions onto a porous polymer membrane

A model for the adsorption of gold from I₂/I^? aqueous solutions onto a cellulose acetate (CA)‐polyaniline (PANI) porous membrane is presented. The adsorption of gold is represented by an ion‐exchange overall reaction in which AuI₂^? ions replace the Cl^? ions at the active sites of the polyaniline matrix. The model incorporates the external mass transfer of AuI₂^? from the bulk solution to the membrane surface, followed by the pore diffusion of AuI₂^? to reach the active sites in the membrane. The overall ion‐exchange reaction was assumed to achieve local instantaneous equilibrium. Verification of the kinetic model with the experimental data showed that the effective diffusivity of AuI₂^? within the membrane is about 8.3 × 10^?6 cm²/s. The potential applications of the present formulation are discussed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Creep mechanical properties and creep model of high water material under step loading

High water material, a kind of filling and supporting material, is widely used in underground engineering, whose creep mechanical properties are directly related to the underground engineering stability. In this paper, creep tests of different types of high water material are carried out. The results show that: for the complete specimen and the single and double crack specimens with crack inclination angles of 0°, 30°, and 60°, the curves present initial elastic, creep attenuation and creep stabilization in the first four stages, and the creep acceleration appears in the fifth stage, leading to the final failure of the specimen; for the single and double crack specimens with a crack inclination angle of 90°, no creep acceleration appears. According to the test results, a new nonlinear viscoplastic body is proposed, and connected with the traditional Nishihara model, forming the nonlinear Nishihara model. The new model can clearly describe the creep characteristics of complete and cracked specimens at different stages. Finally, according to the new creep model, crack parameters are discussed with the creep rate index and the starting time of accelerated failure.     

Predictive calculations of gas solubility and permeability in glassy polymeric membranes: An overview

The possibility to evaluate in a predictive way the relevant transport properties of low molecular weight species, both gases and vapors, in glassy polymeric membranes is inspected in detail, with particular attention to the methods recently developed based on solid thermodynamic basis. The solubility of pure and mixed gases, diffusivity and permeability of single gases in polymer glasses are examined, considering in particular poly(2,6-dimethyl-1,4-phenylene oxide) as a relevant test case. The procedure clearly indicates what are the relevant physical properties of the polymer matrix and of the penetrants required by the calculations, which can be obtained experimentally through independent measurements. For gas and vapor solubility, the comparison with direct experimental data for mixed gases points out also the ability to account for the significant variations that solubility-selectivity experiences upon variations of pressure and/or feed composition. For gas and vapor permeability, the comparison with direct experimental data shows the possibility to account for the various different trends observed experimentally as penetrant pressure is increased, including the so-called plasticization behavior. The procedure followed for permeability calculations leads also to clear correlations between permeability and physical properties of both polymer and penetrant, based on which pure predictive calculations are reliably made.

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Determination of the Hansen solubility parameters with a novel optimization method

The Hansen solubility parameters (HSPs) are useful for predicting solvent–solute affinity. In this study, the HSPs and the sphere radii (Ro's) of poly(ether sulfone), bitumen, and lignin were determined by a novel optimization method. A hybrid algorithm, which could locate multiple optima, was developed and used to solve optimization problems for maximizing the fitness (F) and minimizing both Ro and the numbers of good solvent and total outliers. For most selected samples, improved results with higher F and reduced Ro and number of outliers were obtained. The results clarify the correlations among three criteria for an optimal solubility sphere, namely, the smallest Ro, highest F, and lowest number of outliers. They can be satisfied simultaneously only when outliers are avoided; otherwise, a reduction in Ro decreases F but can retain the same outliers. Thereby, defining the solubility sphere as the one having the smallest Ro and the lowest number of outliers is more reasonable according to the physical significance in both cases. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43328.     

Effect of optimization methods on Hansen solubility ellipsoids

In Hansen solubility parameters (HSPs) space, the solubility region of a solute is modeled as an axis‐aligned ellipsoid, of which Hansen sphere is a special case. The solubility ellipsoids of six materials are determined by the data fit function proposed by Hansen and a new objective function, both solved by a hybrid global‐local search algorithm. From the calculated and reported results, the validity and applicability of four types of currently used optimization methods are analyzed, the findings of and reasons for disputable problems are elucidated. The results reveal that the objective function defined for finding a smallest ellipsoid enclosing all good solvents and having the lowest number of outliers leads to reliable results, thereby has advantages over the methods based on the data fit function. The global convergence and capability of locating multiple optima are essential for a search algorithm used for determining solubility regions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44621.     

Experimental study and thermodynamic model for respective solubilities of CO2 and ethanol for CO2‐ethanol‐polystyrene ternary system at elevated pressure and temperature

Foamed non‐Fickian diffusion (FNFD) model for a ternary system was proposed for the first time to regress the desorption data obtained by the gravimetric method. Results showed that FNFD model could accurately describe the diffusion behavior of CO₂ and ethanol out of foamed polystyrene (PS) and well predict total solubilities of CO₂ and ethanol in foamed PS. Meanwhile, Sanchez–Lacombe equation of state (S–L EoS) was adopted to calculate the respective solubilities (solubility of CO₂ in PS or solubility of ethanol in PS) and total solubilities of CO₂ and ethanol in PS for CO₂‐ethanol‐PS ternary system. Results showed that the total solubility of CO₂ and ethanol obtained from S–L EoS agreed well with values obtained by FNFD model. Furthermore, the respective and total solubilities of CO₂ and ethanol at 313.15, 338.15, and 343.15 K were calculated by S–L EoS. Results indicated that in the dissolving process, ethanol would be accelerated by CO₂ to dissolve into PS, and ethanol would compete with CO₂ to dissolve into PS, simultaneously. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46281.     

Synthesis of a polymeric sensor containing an occluded pyrylium salt and its application in the colorimetric detection of trimethylamine vapors

A dense membrane (MS) based on vinyl polymers and containing a pyrylium salt [2,6‐diphenyl‐4(p‐methacryloyloxy)phenylpyryliumtetrafluoroborate] was prepared. The MS has hydrophilic and sensory properties that make it a good material for the selective colorimetric detection of trimethylamine (TMA) vapors, a biogenic amine of great importance in food safety. The polymeric sensor changes from yellow to an intense pink color with increasing concentrations of TMA. The material could be reused in the presence of HCl vapors for at least 10 times. The detection and quantification limits were determined by ultraviolet–visible absorption spectroscopy (4.42 and 13.40 ppm, respectively) and by the RGB parameters of digital color (3.37 and10.22 ppm, respectively). © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46185.     

Electrospun polymeric membranes: Potential removal of endocrine disrupting compounds using solid membrane extraction and filtration processes

The present study aims to prepare polymeric membranes by electrospinning to apply in the removal of estrone (E1), 17β-estradiol (E2), and 17α-ethinylestradiol (EE2) in aqueous samples. Polymeric membranes of polyamide-6 (PA6), polycaprolactone (PCL), polylactic acid (PLA), and poly (butylene adipate-co-terephthalate) (PBAT) were obtained, characterized, and tested as sorbent material in processes of solid membrane extraction (SME) and membrane filtration. The efficiencies of the membranes after washing and/or conditioning processes were compared. The characterizations showed membranes with nanometer-diameter threads (between 250 and 1200 nm, on average). The four membranes' morphology, chemical composition, and thermal stability were like previous works. PBAT membranes were considered the most effective SME technique as a differential, with 44%–71% removal. For the membrane filtration process, the highest removal values were obtained for the PBAT membrane (82%–91%), which was also efficient in filtering a surface water sample from River Guaíba. PBAT polymeric membrane effectively removes and recovers the studied hormones, lowering production costs and allowing internal and external modifications. These aspects demonstrate that the obtained membranes offer an efficient material in extracting E1, E2, and EE2, of high simplicity, low cost, and green chemistry.     

Water retention in sandy substrates modified by cross-linked polymeric microgels and their complexes with a linear cationic polymer

New synthetic soil conditioners for anti-erosion protection of soils in the form of microgel copolymers of N-isopropylacrylamide and acrylic acid (PAA#) and their interpolyelectrolyte complexes (IPEC#) with different surface charges are tested for optimization of water retention and porous structure in two samples of soil substrates. Water retention curves (WRCs) are used as a fundamental thermodynamic indicator of water holding capacity in soil substrates treated by new polymeric materials. Soil-hydrological constants, as well as specific surface parameters and pore distribution curves are calculated from the WRCs using the van Genuhten model and the Voronin method in the author's modification. PAA# and anionic IPEC# with high swelling degree at a dose of 1% (by weight) increase field water capacity, available soil water range and specific surface area by 5–6 times for quartz sand, along with reorganizing its structure towards micropore dominance. For loamy sand, the same treatment was less effective with a twofold increase in field moisture capacity, double or triple increase of specific surface area, and an almost constant range of available soil water due to the strong increase of wilting point parameter. Weakly swelling linear polyacrylic acid and cationic IPEC# did not significantly affect properties of both mineral substrates.     

A low pressure SWCNT-ENM sandwich membrane system for the removal of PPCPs from water

While carbon nanotubes are known as efficient adsorbents for removal of a number of contaminants from water, the possibility of their leaching into drinking water has prevented their application in water treatment. In this study, single walled carbon nanotubes (SWCNT) were sandwiched between two electrospun nanofibre membranes (ENM). The relatively small pore size of the ENM prevented the mechanically entangled nanotubes from passing through and contaminating the water. The performance of the SWCNT-ENM was evaluated in a lab-scale setup for the removal of PPCPs. For this purpose, a feed solution spiked with known concentrations of six PPCPs was passed through the membrane system. The target substances included acetaminophen (ACT), bezafibrate (BZF), iopromide (IOP), diclofenac (DCF), carbamazepine (CBZ), and sulphamethoxazole (SMX). The same test was also conducted using a single contaminant (ACT). Results demonstrated a decrease in the overall percent removal of PPCPs as feed flow rate and PPCP concentration increased. For multi-component feeds containing equal amounts of the aforementioned PPCPs, the overall percent removal decreased from 90.8% to 71.0% when increasing the feed concentration from 30 to 600 μg/L. Experiments using sandwiched powdered activated carbon (PAC) showed that the dynamic adsorption capacity of PPCPs by SWCNT-ENM was higher than that of PAC-ENM, and remained unaffected by the feed composition. In addition, the high porosity of this novel membrane allowed for flow of water with low resistance such that the trans-membrane pressure was found to be as low as 4 kPa at a pure water flux of 330 L/m²h.     

Preparation and gas transport properties of dual‐layer polysulfone membranes for high pressure CO2 removal from natural gas

Permeability, sorption, and plasticization behaviors of dual‐layer composite membrane were studied. Polysulfone containing 10.7 wt % glycerol as additive was used for preparing a microporous membrane support. A thin top selective layer was prepared using diethylene glycol dimethyl ether as casting solvent. The overall performance of the membrane was evaluated using Scanning Electron Microscopy, and permeation and sorption tests at pressure up to 50 bar. The prepared membrane displayed high permeability at low pressure which gradually decreased with increase in pressure. Permeability of CO₂ was determined to be 84.97 Barrer at 2 bar. Membrane did not show any plasticization tendency up to the experimental pressure of 40 bar. Plasticization pressure and permeability at plasticization pressure were estimated to be 41.07 bar and 6.03 Barrer, respectively. The improved performance of the membrane is associated to the synergistic properties of the two layers prepared from different formulations of the same polymer. Thus, the dual‐layer flat sheet configuration displayed a potential in high pressure CO₂ removal from natural gas. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40924.     

Molecularly imprinted polymer prepared by Pickering emulsion polymerization for removal of acephate residues from contaminated waters

A molecularly imprinted polymer (MIP) prepared with Pickering emulsion polymerization was designed by a computational approach for removal of acephate from aqueous solution. Methacrylic acid, ethylene glycol dimethacrylate, and chloroform were screened as the optimal functional monomer, crosslinker, and porogen by the Gaussian 03 package using the density functional theory method. The polymerization was carried out in an oil‐in‐water emulsion using nano‐SiO₂ particles as stabilizer instead of a toxic surfactant. The characterization results indicated that the prepared MIP had a porous and hollow core, and the particle size was approximately 20 μm. The binding and recognition abilities of MIP for acephate were studied through equilibrium adsorption analysis and selectivity analysis. The results showed that the MIP had high binding capacity and excellent selectivity for acephate. The saturated binding amount could reach 6.59 × 10³ μg/g. The Langmuir isotherm model gave a good fit to the experimental data. Moreover, the results of a reusability analysis and practical application suggested that the prepared MIP provides the potential for removal of acephate residues from aqueous solution. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43126.     

A simple correlation to predict high pressure solubility of carbon dioxide in 27 commonly used ionic liquids

Engineers often demand the availability of easy correlations without difficult and time-consuming calculations. Up till now, there has been a lack of such correlations for mixtures of CO₂ + ionic liquids. This work proposes a correlation to predict CO₂ solubility in 27 common ionic liquids. The main advantages are its simplicity and minimal input data, namely temperature and pressure. The ionic liquids investigated ranged within a variety of families, having various anions and cations. Compared with the popular engineering models of Peng–Robinson (PR) and Soave–Redlich–Kwong (SRK), the present correlation is much easier to use, yet it is also more accurate (PR, SRK and the proposed model had AARD% values of 43.5%, 44.3% and 4.9%, respectively for a total of 3073 data), even when binary interaction coefficients of PR and SRK are optimized to experimental data (AARD% values of 17.2%, 16.9% and 4.9% for PR, SRK and the proposed model, respectively).     

Prediction of the gas solubility in polymers by a radial basis function neural network based on chaotic self‐adaptive particle swarm optimization and a clustering method

A novel model based on a radial basis function neural network (RBF NN), chaos theory, self‐adaptive particle swarm optimization (PSO), and a clustering method is proposed to predict the gas solubility in polymers; this model is hereafter called CSPSO‐C RBF NN. To develop the CSPSO‐C RBF NN, the conventional PSO was modified with chaos theory and a self‐adaptive inertia weight factor to overcome its premature convergence problem. The classical k‐means clustering method was used to tune the hidden centers and radial basis function spreads, and the modified PSO algorithm was used to optimize the RBF NN connection weights. Then, the CSPSO‐C RBF NN was used to investigate the solubility of N₂ in polystyrene (PS) and CO₂ in PS, polypropylene, poly(butylene succinate), and poly(butylene succinate‐co‐adipate). The results obtained in this study indicate that the CSPSO‐C RBF NN was an effective method for predicting the gas solubility in polymers. In addition, compared with conventional RBF NN and PSO neural network, the CSPSO‐C RBF NN showed better performance. The values of the average relative deviation, squared correlation coefficient, and standard deviation were 0.1282, 0.9970, and 0.0115, respectively. The statistical data demonstrated that the CSPSO‐C RBF NN had excellent prediction capabilities with a high accuracy and a good correlation between the predicted values and the experimental data. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3825–3832, 2013     

Thermal desorption and pyrolysis direct analysis in real time mass spectrometry of Nafion membrane

Perfluorosulfonic acid ionomer membranes have been widely used as proton conducting membranes in various electrochemical processes such as polymer electrolyte fuel cells and water electrolysis. While their thermal stability has been studied by thermogravimetry and analysis of low molecular weight products, their decomposition mechanism is little understood. In this study a newly developed methodology of thermal desorption and pyrolysis in combination with direct analysis in real time mass spectrometry is applied for Nafion membrane. An ambient ionization source and a high-resolution time-of-flight mass spectrometer enabled unambiguous assignment of gaseous products. Thermal decomposition is initiated by side chain detachment above 350°C, which leaves carbonyls on the main chain at the locations of the side chains. Perfluoroalkanes are released above 400°C by main chain scission and their further decomposition products dominate above 500 °C. DFT calculation of reaction energies and barrier heights of model compounds support proposed decomposition reactions.     

Fabrication of biocompatible monolithic microchannels with high pressure‐resistance using direct polymerization of PEG‐modified PMMA

Withstanding high pressures in polymeric microchannels is an important requirement for many biological applications. Here, a simple direct polymerization through a polyester photomask is applied to obtain monolithic polyethylene glycol (PEG)‐modified poly(methyl methacrylate) (PMMA) (PEGMA) microchannels, showing the ability to withstand pressure up to 12 MPa in burst pressure tests. The ability of withstanding high pressures is observed to increase with increasing ratio between the thickness of the cover polymer layer forming the microchannel lid and the width of the microchannel. A simplified finite element modeling model of the burst pressure test is set up to interpret the experimental findings. The outcomes of the modeling activity, along with direct scanning electron microscopy observation of the fracture surfaces, confirm the effectiveness of the polymerization method for the production of monolithic PEGMA microchannels. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41031.     

Tensile mechanical properties and constitutive model for HTPB propellant at low temperature and high strain rate

To investigate the mechanical properties and fracture mechanisms of hydroxyl‐terminated polybutadiene (HTPB) propellant at low temperature and high strain rate, uniaxial tensile tests were conducted over the range of temperatures 233 to 298 K and strain rates 0.4 to 14.14 s^?1 using an INSTRON testing machine, and scanning electron microscope (SEM) was employed to observe the tensile fracture surfaces. The experimental results indicate that the deformation properties of HTPB propellant are remarkably influenced by temperature and strain rate. The characteristics of stress–strain curves at low temperatures are different from that at room temperature, and the effects of temperature and strain rate on the mechanical properties are closely related to the changes of properties and the fracture mechanisms of HTPB propellant. The dominating fracture mechanism depends much on the temperature and changes from the dewetting and matrix tearing at room temperature to the particle brittle fracture at low temperature, and the effect of strain rate only alters the mechanism in a quantitative manner. Finally, a nonlinear viscoelastic constitutive model incorporating the damage evolution and the effects of temperature and strain rate was developed to describe the stress responses of this propellant under the test conditions. During this process, the Schapery‐type constitutive theories were applied and one damage variable was considered to establish the damage evolution function. The overlap between experimental results and predicted results are generally good, which confirms that the developed constitutive model is valid, however, further researches should be done due to some drawbacks in describing the deformation behaviors at very large strain. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42104.     

High‐resolution measurements of water permeability and solubility in microelectronic‐casing made of a hydrophobic polymeric composite

Exposing the composite polymeric casing of integrated circuits (ICs) to water results in miniscule water absorption, followed by its permeation throughout the packaging, and component damage. Studying water penetration and solubility mechanisms in the IC casing is crucial for understanding water‐related damage mechanisms and protection against them. The main analytical challenge, hereafter, stems from the need to study miniscule water amounts (<0.5 wt %) capable of penetrating the casing, despite its hydrophobic nature. In this article, a TGA has been employed to study the water uptake kinetics in the casing, and to decipher the related water penetration mechanisms. High‐resolution measurements of water adsorption and desorption profiles were performed, followed by calculations of the related activation energies and solubility enthalpies. These data were correlated with a relatively new model that assigned the primary locales of the adsorbed water to the compatible filler–polymer interface. Thus, water permeability is related to molecules hopping between these sites. Finally, we have shown that for the IC casing in our study, the activation energy of water permeation is related to the binding energy of H₂O onto the Si? O? Si groups at the fused‐silica‐filler surface, where they desorb, hop, and reabsorb. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4523–4527, 2006