Errors associated with swelling in the analysis of polymer-solvent diffusion measurements

Sorption curves are generated from a mathematical model which includes the influence of the polymer swelling for unsteady-state sorption of a vapor or liquid by a polymer. To investigate the simultaneous effects of the specific volumes of the polymer-penetrant pair and the difference between the final and initial equilibrium concentrations on the sorption curves, statistical experimental design approach is used. Simulation results obtained from the numerical solution of model equations are utilized to estimate the error that would occur if one simply evaluates the diffusion coefficient using the traditional formulas derived from the analytical solution of the sorption equation. An empirical expression is developed that describes the effects of the difference between the final and initial equilibrium concentrations and the specific volumes of the polymer and the penetrant on the magnitude of error in diffusivity associated with the use of one of these traditional formulas so called the initial slope method. The predictive ability of the regression model is tested by performing additional simulations not used in the regression analysis.     

Surface modification of polysulfone based hemodialysis membranes with layer by layer self assembly of polyethyleneimine/alginate-heparin: a simple polyelectrolyte blend approach for heparin immobilization

This study intends to improve blood compatibility of polysulfone (PSF) membranes by generating a nonthrombogenic surface through heparin immobilization. To achieve this task, the support membrane prepared from a blend of PSF and sulfonated polysulfone (SPSF) was modified with layer by layer (LBL) deposition of polyethyleneimine (PEI) and alginate (ALG) and heparin blended with ALG was immobilized only on the outermost surface of the LBL assembly. The results have shown that the adsorption of human plasma proteins and platelet activation on the LBL modified membranes decreased significantly compared with the unmodified PSF and PSF-SPSF blend membranes. Furthermore, blending ALG with a small amount of heparin remarkably prolonged the APTT values of heparin free PEI/ALG coated membranes. It is envisaged that the use of a blend of HEP and ALG only in the terminating layer of the LBL assembly can be an economical and alternative modification technique to create nonthrombogenic surfaces.     

The influence of binder content on the water transport properties of waterborne acrylic paints

Diffusion coefficients and sorption isotherms of water in waterborne acrylic paint films and in the pure binder of the paints have been measured by gravimetric sorption. Solubility of water was found to enhance with the increased binder content in the paint films while the diffusivity of water decreased significantly. Sorption isotherms in the paint and pure copolymer films were correlated with the Flory Huggins theory and ENSIC model, respectively. Fickian diffusion was observed in both types of films and the kinetic data were best correlated with a numerical model which takes into account the concentration dependency of the diffusion coefficient and the dimensional change of the film due to sorption. It was concluded that the utilization of a simplified analytical solution may lead to significant errors in the estimation of diffusivities.     

DRYING OF SOLVENT COATED POLYMER FILMS

The ability to predict the drying behavior of coating is of great importance to the coating industry. For this purpose, the model developed by Vrentas and Vrentas has been used to predict the concentration profile as well as the thickness and the temperature change of the polymer film as a function of time. The model incorporates the coupling between heat and mass transfer and diffusion induced convection which occurs when a single layer of a binary polymer solution is dried in a convection heated oven.

The model was solved numerically by using the finite difference approximation and it was applied to the well characterized polyvinylacetate(PVAC)-toluene system. The effects of operating conditions on     

Modeling educational usage of Facebook

The purpose of this study is to design a structural model explaining how users could utilize Facebook for educational purposes. In order to shed light on the educational usage of Facebook, in constructing the model, the relationship between users' Facebook adoption processes and their educational use of Facebook were included indirectly while the relationship between users' purposes in using Facebook and the educational usage of Facebook was included directly. In this study, data is collected from Facebook users with an online survey developed by the researchers. The study group consists of 606 Facebook users whose answers were examined by using a structural equation model. The analyses of the 11 observed and 3 latent variables provided by the model showed that 50% of educational usage of Facebook could be explained by user purposes along with the adoption processes of Facebook. It was also found that Facebook adoption processes could explain 86% of all user purposes. Finally, while Facebook adoption processes explained 45% of its educational usage, it could explain 50% of variance in educational usage of Facebook when the user purposes were added into the analyses.     

Development of antioxidant food packaging materials with controlled release properties

In this study, cellulose acetate (CA) films with different morphological features were prepared in order to control the release rates of low molecular weight natural antioxidants, L-ascorbic acid and L-tyrosine. Increasing CA content in the casting solution decreased the average pore size and porosity of the films, thus, reduced the diffusion rates of both antioxidants through the films. Although both antioxidants have similar molecular weights, L-tyrosine released into water much more slowly than L-ascorbic acid. The highest antioxidant activity in release test solutions was observed with highly porous L-tyrosine containing films. However, when the porosity of the films reduced, the antioxidant activity of L-ascorbic acid released into solution was found to be higher due to trapping of significant amount of L-tyrosine in dense films. The use of different antioxidants caused different changes in morphological and mechanical properties of the CA films. Varying the structural features of the films with the preparation conditions or using different surfaces of the films allowed the controlled release of each antioxidant.     

The effect of mass transfer resistance and nonuniform initial solvent concentration on permeation through polymer membranes

A numerical simulation model has been developed which enables one to examine the effects of surface mass transfer resistance on the evaluation of permeation (P*), diffusion (D), and solubility (S) coefficients from unsteady‐state mass transfer experiments as well as the transmission rate. A complementary analytical expression has been developed which validates the numerical model and facilitates the evaluation of the concentration dependence of P*, D, and S from sequential step‐change experiments, under experimental conditions when the surface mass transfer resistance can be neglected. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46126.     

St. Lucie cherry,yellow jasmine,and madder berries as novel natural sensitizers for dye‐sensitized solar cells

Natural dyes extracted from fruits, vegetables, flowers, and leaves are considered as promising alternative sensitizers to replace synthetic dyes for dye‐sensitized solar cells (DSSCs). Generally, solar activity of natural dyes stem from anthocyanin pigment. Carbonyl, carboxyl, and hydroxyl groups present in the anthocyanin molecule improve the adsorption ability of dye on TiO₂ and therefore facilitate charge transfer. Here, for the first time, novel natural dyes extracted from St. Lucie cherry, yellow jasmine, and madder berries are reported to act as sensitizer in DSSCs. These novel natural dye extracts are prepared by dissolving related fruits in ethanol. The ingredient of the dyes is identified by FT‐IR spectroscopy. Accordingly, FT‐IR spectrum reveals that novel natural dye extracts exhibit all the characteristic peaks of anthocyanin pigment. Specifically, St. Lucie cherry consists of more distinct carbonyl group than other sources. Also, photoanodes composed of three TiO₂ layers are prepared by using a spin‐coating method. Then, they are immersed into natural dyes and analyzed by conducting UV‐Vis spectroscopy. Compared with bare TiO₂, natural dye–loaded photoanodes demonstrate far higher absorption ability in the visible region. After fabrication of devices with different novel natural dye sensitizers, current‐voltage characteristics and electrochemical impedance spectroscopy measurements are performed. The best power conversion efficiency (PCE) of 0.19% is obtained by sensitization of St. Lucie cherry with an open‐circuit voltage (V_oc) of 0.56 V, short‐circuit current density (J_sc) of 181 μA cm^?2, and fill factor (FF) of 0.55. Furthermore, St. Lucie cherry–sensitized devices show the lowest charge transfer and highest recombination resistances. This result can be attributed to the obvious carbonyl group exhibited by St. Lucie cherry.     

Facile fabrication of low-cost low-temperature carbon-based counter electrode with an outstanding fill factor of 73% for dye-sensitized solar cells

Developing chemically inert, electrically conductive, and catalytically active counter electrodes (CEs) to replace conventional Pt-based ones is highly desirable for dye-sensitized solar cells. Herein, we reported a facile, cost-effective, and low-temperature synthesis pathway to develop carbon-based CEs. The performance of homemade carbon paste (H-CP)–based CE (H-CE) was compared with that of commercial carbon paste (C-CP)–based CE (C-CE) and Pt-based CE (Pt-CE). The scanning electron microscope (SEM) results showed that H-CE demonstrated a penetrable surface structure which facilitates the diffusion of electrolyte through the carbon electrode. This phenomenon enhanced the triiodide reduction with respect to C-CE having a compact structure that limits the electrolyte diffusion. The charge transfer properties and catalytic activities of the investigated devices were explored using electrochemical impedance spectroscopy and Tafel polarization measurements; the obtained results indicated that the device based on H-CE revealed relatively lower charge transfer resistance and higher exchange current density compared with C-CE-based device. The current-voltage measurements showed that the device based on H-CE has a power conversion efficiency of 2.70%, which was about 1.6 times higher than that of the device based on C-CE (1.68%). Furthermore, a fill factor of 73% was achieved for the device based on H-CE, which outperformed the Pt-based device (69%) and was among one of the highest values obtained in the literature. Also, a tape adhesion test performed on H-CP-coated glass substrate displayed its excellent robustness.     

Multi-Zone Drying Schemes for Lowering the Residual Solvent Content during Multi-Component Drying of Semicrystalline Polymers

The development of a glassy skin in multicomponent semicrystalline polymer systems limits the diffusion of solvents out of the system and increases residual solvent levels. Based on the results of a mathematical model that we had previously developed, we have proposed a multi-zone drying scheme aimed at lowering the residual solvent levels by taking into account the effect of interactions between the various solvents as predicted by the model. This article focuses on the application of this model to develop optimal drying schemes and to verify the effectiveness of these predictions using experimental techniques. The mathematical model developed previously to study the diffusion of multiple solvents and changes in the crystallinity of semicrystalline polymer systems during drying incorporates many features including Vrentas-Duda diffusion theory, solvent-induced crystallization kinetics, as well as glass transition effects and skinning of the film. The multi-zone drying system was developed by varying the drying temperature in each zone as well as changing the partial pressure of individual solvents during the drying process. The effectiveness of the multi-zone drying schemes predicted by the model was validated experimentally using thermogravimetric methods. The polymer-solvent system chosen was a poly(vinyl alcohol)-water-methanol system. Our experimental data suggested that the multi-zone drying schemes were superior to a single-zone drying system through direct comparison. Further examination of the mathematical model yielded individual solvent profiles and these data reaffirmed our conclusions that a multi-zone drying scheme has the ability to reduce the effect of solvent trapping and thus lower the overall residual solvent content.