The application of polyethyleneimine draw solution in a combined forward osmosis/nanofiltration system

The objective of this study is to investigate the effect of solution chemistry of branched polyethyleneimine (PEI) draw solute and to evaluate the PEI draw solute in a combined forward osmosis (FO)/nanofiltration (NF) system. Pure water was extracted from feed solution using the FO process, and the separation of pure water was achieved by the NF process. Lower molecular weight PEI showed higher water flux than higher molecular weight PEI, due to the lower internal concentration polarization caused by a higher diffusion rate and the easy permeation of pure water by lower viscosity of the draw solution (DS). The FO water flux was determined by the osmotic pressure induced by protonation/deprotonation of PEI, and the reverse draw solute flux was determined by the combination of PEI size due to the speciation and electrostatic interaction between the membrane and PEI. This study shows that the J_s/J_w value of PEI at pH 7 was smaller than those of sodium chloride and magnesium sulfate. The recovery of PEI DS using NF has a higher value (99.4%) than of sodium chloride (20.6%) and magnesium sulfate (97.0%); this means that PEI would be a promising draw solute in an FO–NF combined system for the saline water desalination. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42198.     

Diffusion behavior of poly(ethylene imine) into keratin fibers using microspectrophotometry

In order to investigate the diffusion behavior of poly(ethylene imine) (PEI) into keratin fibers, cross‐sectional samples of bleached white human hair treated with PEI were prepared. We were successful in developing a method for analyzing the diffusion behavior of PEI into human hair, which to our knowledge is a first. The diffusion pattern of PEI into human hair, which cannot be determined by optical microscopy, can be determined by our method. After the treatment, the cross‐sectioned hair samples were dyed with Orange II and the cross‐sectional intensity scans were measured at a wavelength of 487 nm (λ_max of Orange II) with a microspectrophotometer. In our method, the diffusion pattern of PEI at pH 11.1 showed Fickian type characteristics. This suggests that the diffusion coefficient of PEI is essentially independent of the PEI concentration. By calculating the diffusion coefficient from the PEI concentration profile, the diffusion coefficient of PEI [number‐average molecular weight (M_n) = 300 and 600] into the bleached human hair was found to be on the order of 10^?10 cm²/s. In addition, the diffusion coefficient of PEI (M_n = 600) with urea added increased twofold in comparison with that of PEI without urea added. This experiment demonstrated that urea acts as a penetration accelerator for PEI. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 65–71, 2005     

Moisture diffusion in epoxy resins Part I. Non-Fickian sorption processes

Diffusion of water in a glassy epoxy resin has been studied by the sorption method. Film thickness scaling is used as a diagnostic tool for non-Fickian sorption processes. A sorptiondesorption cycle effectively increases the preexisting free volume in the resin and renders the subsequent sorption process different from the original. The effect is understood by considering the time scale for diffusion and that for molecular relaxation of the glassy polymer network. A non-Fickian sorption process is observed for an insufficiently cured resin and is caused by the resin undergoing further postcuring in the sorption process. It is shown that oxidation of the resin during sorption also gives rise to non-Fickian processes previously described in the literature as diffusion anomalies for epoxies. It is further shown that the difference between sorption and resorption curves is not caused by irreversible damage to the resin but due to reversible changes in network conformations.     

Water‐transport properties in polyetherimide blends with a liquid crystal polymer

The effect of the addition of a liquid crystal polymer (Rodrun^®) on the sorption and transport properties of water through films of a polyetherimide (PEI, Ultem 1000) was investigated. A Cahn electrobalance was employed for measuring the water uptake by the polymer samples. Sorption measurements were made with films of PEI, Rodrun, and heterogeneous PEI/Rodrun blends at different water activities at 30°C. In all cases, diffusion and sorption coefficients decreased when the amount of Rodrun increased. Values of the water‐sorption isotherms were adjusted to different models. Permeabilities for the different samples were indirectly obtained using experimental values of the solubility and diffusion coefficients described above. Furthermore, permeabilities of the binary composite material were calculated on the basis of those of the pure components and some theoretical assumptions concerning blend morphology. Results were consistent with a Rodrun structure in the composite intermediate between a fibrillar and a laminar morphology. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 323–332, 1999     

Characterization of cure reactions of anhydride/epoxy/polyetherimide blends

The cure kinetics of blends of epoxy (diglycidyl ether of bisphenol A)/anhydride (nadic methyl anhydride) resin with polyetherimide (PEI) were studied using differential scanning calorimetry under isothermal conditions to determine the reaction parameters such as activation energy and reaction constants. By increasing the amount of PEI in the blends, the final cure conversion was decreased. Lower values of final cure conversions in the epoxy/PEI blends indicate that PEI hinders the cure reaction between the epoxy and the curing agent. The value of the reaction order, m, for the initial autocatalytic reaction was not affected by blending PEI with epoxy resin, and the value was approximately 1.0. The value of n for the nth order component in the autocatalytic analysis was increased by increasing the amount of PEI in the blends, and the value increased from 1.6 to 4.0. A diffusion‐controlled reaction was observed as the cure conversion increased and the rate equation was successfully analyzed by incorporating the diffusion control term for the epoxy/anhydride/PEI blends. Complete miscibility was observed in the uncured blends of epoxy/PEI at elevated temperatures up to 120 °C, but phase separations occurred in the early stages of the curing process. © 2002 Society of Chemical Industry     

Kinetic Model for Crystallization in White Ceramic Glazes

Theoretical equations have been developed for crystal growth rate in layers of small frit (glass) particles during firing. Throughout the process, the crystalline and the glassy phases have different compositions; therefore, the system can be considered a pseudo-two-component system consisting of a crystallizable component (structural unit) and a noncrystallizable mixture of several components. The concentration of the crystallizable component decreases in the residual glassy phase during the crystal growth process, on integrating at the surfaces of crystals having the same composition. Throughout the crystal growth process, a concentration gradient of the crystallizable component is therefore produced in the glassy phase, which results in mass transport by diffusion of this component from the bulk residual glassy phase to the surfaces of the crystals. Equations have been derived assuming that the diffusion step of the crystallizable component through the residual glassy phase is the overall crystal growth process rate-controlling step.     

Resistance of a polyetherimide to environmental stress crazing and cracking

The environmental stress crazing and cracking (ESC) behavior of an aromatic polyetherimide (PEI) has been characterized in a wide spectrum of organic liquids and compared to the behavior of several other glassy thermoplastics. PEI's response is qualitatively similar to that of the other resins for each of which ESC resistance reaches a minimum in solvents having solubility parameters close to that of the resin. Taken as a whole, the ESC resistance of PEI is found to be quantitatively superior to that of any other glassy resin for which similar data are available for comparison.     

Novel sodium alginate/polyethyleneimine polyion complex membranes for pervaporation dehydration at the azeotropic composition of various alcohols

Dense polyion complex membranes of anionic sodium alginate (NaAlg) and cationic polyethyleneimine (PEI) were prepareand crosslinked with glutaraldehyde for dehydration of alcohol–water mixtures by pervaporation (PV). The membranes were characterized by ion‐exchange capacity measurement, Fourier transform infrared spectroscopy, differential scanning calorimetry and scanning electron microscopy to investigate the extent of cross‐linking, intermolecular interactions, thermal stability, and surface and cross‐sectional morphologies, respectively. Wide‐angle X‐ray diffraction was used to investigate the crystallinity of the membranes. PV dehydration characteristics of the membranes were determined as a function of PEI content, crosslinking time as well as feed water composition. Transport parameters such as sorption, diffusion and permeability of water and alcohols through the membranes were determined. Among the four different membrane compositions, the polyion complex containing 40% PEI was found to yield optimum separation data in terms of membrane stability, selectivity and permeability. On the other hand, 10% PEI‐containing membrane gave the highest selectivity with the lowest flux at ambient temperature, but the membranes were not sufficiently stable. Copyright © 2007 Society of Chemical Industry     

Water penetration in glassy polymers: Experiment and theory

We describe the design and implementation of a method based on infrared monitoring of the OD stretch mode which permits measurement of the diffusion profiles of water permeating glassy polymers for the first time. Results for several glassy polymers are compared with a theory of trapping diffusion which leads to a nonlinear diffusion problem in which the trapped water penetrates the polymer as a sharp front if there is a large amount of trapping. In the case of two of the polymers studied, the trapping model describes the data, very well (much better than a simple diffusion model) and permits determination of parameters related to the free volume and the residence time of the water on traps in the model. © 1993 John Wiley & Sons, Inc.     

Pervaporation performance and Transport phenomenon of PVA blend membranes for the separation of THF/water azeotropic mixtures

Summary Dense polymer membranes were made by mixing aqueous solutions of hydrophilic polymers poly(vinyl alcohol) (PVA) and polyethyleneimine (PEI) in different ratios for investigating the separation of Tetrahydrofuran (THF)/water azeotropic mixtures by pervaporation (PV). In order to gain a more detailed picture of the molecular transport phenomenon, we have performed sorption gravimetric experiments at 30 °C to compute diffusion, swelling, sorption and permeability coefficients of PVA/PEI membranes in the presence of THF and water. The membranes were found to have good potential for breaking the azeotrope of THF at 6% concentration of water. An increase in PVA content in the blend caused a reduction in the flux and an increase in selectivity. Among the blends tested in the study, the 5:1 PVA/PEI blend membrane showed the highest separation factor of 181.5, exhibited a flux of 1.28 kg/m²h for THF respectively at azeotropic feed composition.     

Probing the nonequilibrium nature of polymer glasses by Fickian diffusion of alkane permeants

Volume relaxation of glassy polymers has been followed by diffusion of simple alkane permeants. The changes in diffusion rates allow direct monitoring of changes in segmental mobilities of the polymers. In general, the diffusion rates decrease linearly with annealing time on double-logarithmic plots and then level off as equilibrium is reached. The reduction in diffusion rates, however, can be recovered by raising the temperature above the glass transition temperature and then cooling to the same annealing temperature. Such behavior indicates that the predominant molecular process responsible for changes in mechanical properties of glassy polymers that accompany volume relaxation is not “structure formation” but is the loss of segmental mobilities arising from a reduction of the total free volume in the polymers.     

Water sorption kinetics in poly(aryl ether ether ketone)

The kinetics of diffusion of water from different activity vapors and liquid phase have been investigated in glassy amorphous poly(aryl ether ether ketcne) (PEEK) films at the temperature of 60°C and in glassy semicrystalline PEEK sheets at different temperatures, respectively. In the case of the amorphous PEEK films (250 μm thick) the data at low activity levels were interpreted by means of a purely Fickian mechanism. At higher activity levels the material has shown the presence of a relaxation process; in this case the data have been interpreted using a model proposed by Berens and Hopfenberg. Equilibrium sorption isotherm is also reported. Liquid water sorption in semicrystalline (30%) PEEK sheets (2 mm thick) has been determined to follow the classical Fickian mechanism. The water uptake values obtained for both amorphous and semicrystalline PEEK, confirm the good moisture and liquid water resistance of this kind of high performance thermoplastic polymer.     

STUDY OF BONDED PLASMA-TREATED POLYETHERIMIDE COMPONENTS FOR POWER INTEGRATION: DURABILITY IN A HOT/WET ENVIRONMENT

This work deals with the study of the durability, in a hot/wet environment, of structural adhesively bonded polyetherimide (PEI) assemblies used in power electronics packaging technology. An overall approach is proposed, for which the epoxy joint-PEI substrates assembly on the one hand, and the adhesive system components (substrate surface and bulk adhesive) on the other hand, are studied separately with different analytical techniques. The first part of this work was devoted to the substrate surface state and to its modification using a cold plasma treatment of the PEI surface. Then for chosen parameters (power, duration) contact angle measurements indicated an increased surface tension resulting from surface decontamination (removal of release agent and carbon contaminants) and from the creation of polar species, such as esters or carboxylic acid groups, on the PEI surface (XPS analyses). The second part of this study concerned the bulk adhesive ageing in an ethylene glycol-water solution at 70°C. Mass uptake measurements versus time showed the liquid diffusion in the bulk adhesive associated with a microscopic damage of the epoxy system. An overall plasticizing of the adhesive with a considerable decay of the α-transition temperature of one of the two adhesive epoxy-amine networks (TGDDM-BAPP) was also highlighted using rheometry. However, in these ageing conditions, the adhesive glassy modulus decreases slighty because of the thermomechanical stability of the other epoxy network. In the third part, the asymmetric wedge test showed the beneficial effect of the cold plasma treatment on the epoxy/PEI interface durability in the aggressive medium.     

A deformation model for Case II diffusion

Case II diffusion in glassy polymers is considered in terms of a deformation model. The process is controlled by the mechanical response of the glass just ahead of the sharp front to an osmostic swelling stress. The important factor governing the establishment of the sharp solvent front is taken to be the concentration dependence of the creep response time. These ideas are set in the context of existing models for diffusion in glassy polymers, and experimental evidence is presented to support the deformation mechanism.     

Reaction Kinetics and Phase Transformations During Cure of a Thermoplastic‐Modified Epoxy Thermoset

A comprehensive thermal and rheological characterisation of a commercially important aerospace resin system modified with a thermoplastic toughener is presented here. The primary focus has been the understanding of how the cure kinetics and mechanism relate to other processes such as phase separation during cure. Differential scanning calorimetry has shown that thermoplastic modification does not affect the cure mechanism significantly and that the process was dominated by an autocatalytic process up to vitrification after which diffusion‐controlled processes dominate regardless of thermoplastic concentration. Thermoplastic addition at 10 wt.‐% PEI was found to increase the final cure conversion compared with the neat resin and inhibit the onset of diffusion control below a cure temperature of 160 °C. At 20 wt.‐% PEI concentration the final conversion and the onset of diffusion control were similar until 150 °C, after which they displayed lower values than the neat resin. Rheological analysis showed that the phase separation process could be followed conveniently through the changes in viscosity and exhibited effects consistent with expected variations in morphology. The 10 wt.‐% PEI system displayed abrupt increases in viscosities which were indicative of a dispersed particulate morphology, while the 20 wt.‐% PEI system displayed more complex behaviour consistent with a phase‐inverted or co‐continuous structure. The gelation process was shown to obey a power law model although the local environment or morphology of the reactive epoxide group at higher PEI concentrations was shown to affect the fit to the model.

     

Water in epoxy resins Part II. Diffusion mechanism

A model is proposed for the diffusion mechanism of water in glassy epoxy resins. The polymer network is assumed to consist of two regions in which water molecules possess different mobilities. By considering the distribution of water molecules among these regions it is possible to describe the concentration dependency of the diffusion coefficient in the sorption and resorption processes. The diffusion coefficient becomes constant when the sorption temperature is close to the effective glass transition temperature of the epoxy-water binary mixture. An explanation of this effect is also provided by the model.     

INFLUENCE OF RHEOLOGICAL PROPERTIES IN MASS TRANSFER PHENOMENA: SUPER CASE II SORPTION IN GLASSY POLYMERS

The sorption rate of swelling penetrants in glassy polymers has been considered as controlled both by the swelling kinetics and the penetrant diffusion through the swollen layer. The stress exerted on the glassy core at the moving boundary is the driving force for the swelling, and results from an osmotic stress and a differential swelling stress contribution. During the sorption process, the osmotic stress at the moving boundary decreases, due to the increasing diffusion resistance; the differential swelling stress, on the contrary, increases giving rise to an acceleration of the front velocity (Super Case II).

The particular case of negligible diffusion resistance in the swollen region is here considered in more detail. It is shown that the rheological properties of both swollen and glassy phases crucially enter the mass transport problem; thestress relaxation in the swollen region must be taken into account in order to obtain a thickness dependent Super Case 11 effect     

Combined experimental and computer simulation study of the kinetics of solute release from a relaxing swellable polymer matrix. I. Characterization of non‐Fickian solvent uptake

This article is concerned with a combined experimental and computer modeling study aimed at the characterization of the non‐Fickian absorption of liquid water by cellulose acetate (CA) matrices (in the form of thin films) on the basis of a strictly limited number of parameters. The observed kinetics exhibited two distinct non‐Fickian features, resulting from short‐term and long‐term viscous structural relaxations of the swelling glassy polymeric matrix. These relaxation processes were modeled by the extension of a previous model of micromolecular diffusion in a polymer subject to a single relaxation process. The successful simulation of the experimental kinetic curves then enabled the determination and cross‐checking of the relevant model parameter values. This work had the dual purpose of providing (1) input related to solvent absorption for the quantitative computer simulation (in part II of this series) of a model monolithic, solvent‐activated, controlled‐release device, consisting of a swellable glassy polymeric matrix (CA) loaded with an osmotically active solute (NaCl), and (2) an example of a general strategy of extracting meaningful values of micromolecular diffusivity in glassy polymers from non‐Fickian absorption kinetic data. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2458–2467, 2004