Prediction of solvent‐diffusion coefficient in polymer by a modified free‐volume theory

Several versions of free‐volume theory have been proposed to correlate or predict the solvent diffusion coefficient of a polymer/solvent system. The quantity of free volume is usually determined by the Williams–Landel–Ferry (WLF) equation from viscosity data of the pure component in these theories. Free volume has been extensively discussed in different equation‐of‐state models for a polymer. Among these models, the Simha–Somcynsky (SS) hole model is the best one to describe the crystalline polymer, because it describes it very approximately close to the real structure of a crystalline polymer. In this article, we calculated the fractions of the hole free volume for several different polymers at the glass transition temperature and found that they are very close to a constant 0.025 by the SS equation of state. It is quite consistent with the value that is determined from the WLF equation. Therefore, the free volume of a crystalline polymer below the glass transition temperature (T_g) is available from the SS equation. When above the T_g, it is assumed that the volume added in thermal expansion is the only contribution of the hole free volume. Thus, a new predictive free‐volume theory was proposed. The free volume of a polymer in the new predictive equation can be estimated by the SS equation of state and the thermal expansion coefficient of a polymer instead of by the viscosity of a polymer. The new predictive theory is applied to calculate the solvent self‐diffusion coefficient and the solvent mutual‐diffusion coefficient at different temperatures and over most of the concentration range. The results show that the predicted values are in good agreement with the experimental data in most cases. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 428–436, 2000     

Modelling of alcohol and water diffusion in fuel cell membranes—Experimental validation by means of in situ Raman spectroscopy

In this work a multi-component transport model has been set up to describe the diffusion driven mass transport of water and methanol in fuel cell membranes. For a membrane in contact with liquid methanol and water on one side and conditioned air on the other, the corresponding differential equations and boundary conditions were derived in a polymer-related coordinate system taking into account the polymers three-dimensional swelling. Phase equilibrium parameters and unknown diffusion coefficients for Nafion^® 117 were obtained by comparing the simulation results to water and methanol concentration profiles measured with confocal Raman spectroscopy. The influence of methanol concentration, temperature and air flow rate was predicted by the model with a maximum relative mean deviation between measurement and simulation of 8.6% for methanol and 3.4% for water.     

Preparation and characterization of micron‐sized non‐porous magnetic polymer microspheres with immobilized metal affinity ligands by modified suspension polymerization

A novel preparation method of micron‐sized non‐porous magnetic polymer microspheres with immobilized metal affinity ligands was developed. A modified suspension polymerization of methacrylate (MA) and divinylbenzene (DVB) was performed in the presence of oleic acid‐coated magnetic Fe₃O₄ nanoparticles to obtain magnetic poly (methacrylate‐divinylbenzene) (mPMA‐DVB) microspheres. Through ammonolysis using ethylenediamine (EDA) and subsequent carboxymethylation with chloroacetic acid, magnetic polymer microspheres with chelate ligands of iminodiacetic acid (IDA) were obtained. Charging with copper ions resulted in magnetic polymer microspheres capable of binding proteins that display metal affinity. The morphology, magnetic properties, and composition of magnetic polymer microspheres were characterized with scanning electron microscopy (SEM), vibrating sample magnetometer (VSM), and Fourier transform infrared spectroscopy (FTIR), respectively. Bovine hemoglobin (BHb) was adopted as a model protein to investigate their affinity adsorption capacity. It was found that the adsorption capacity was as high as 168.2 mg/g microspheres and with rather low non‐specific adsorption. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2174–2180, 2005     

Prediction of diffusion in a ternary solvent–solvent–polymer blend by means of binary diffusion data: Comparison of experimental data and simulative results

Multicomponent diffusion of solvents in polymeric systems is not completely understood, despite many scientific contributions to the topic. Literature scarcely offers measurement data on diffusion for model validation in such systems. In this work, the ternary systems consisting of poly(vinyl acetate) and the solvents toluene and methanol was investigated experimentally and numerically. By means of inverse micro Raman spectroscopy (IMRS) concentration gradients in drying thin films have been measured. Initial composition of the samples has been varied systematically in order to detect mutual influence of the solvents' diffusive behavior. It was shown that the mobility of the different species is increased in the presence of other solvents as predicted by theory. This experimental data is provided for model validation. A new expression to calculate the diffusion coefficients in ternary mixtures is proposed which only requires binary data. This expression is tested by means of a model‐based simulation to predict the drying of ternary polymer solutions in terms of concentration profiles and residual solvent content. The results are in very good agreement with the experiments. Cross terms diffusion coefficients and thermodynamic factors were not found to be necessary for a satisfying prediction. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43899.     

Water diffusion and permeability in unsaturated polyester resin films characterized by measurements performed with a water‐specific permeameter: Analysis of the transient permeation

A water‐specific permeameter was developed to study water diffusion in an unsaturated polyester; these polyesters are often used as high‐barrier materials. Low water enrichment of a dry sweeping gas is measured via the dew point temperature, with two hygrometers, one of which is used because of its fast response and the other because of its accuracy. This high‐performance device is just as suited to pervaporation as to permeation tests and allows the transient and stationary fluxes to be characterized. At first sight, the experimental data seem in good agreement with D = D₀e^γC. However, a more thorough study has shown a time‐dependence of D. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3380–3395, 1999