Analysis of polymer membrane formation through spinodal decomposition

A phenomenological model used in a previous work for spinodal decomposition of polymer-solvent systems is further analyzed. From the dimensionless form of the nonlinear Cahn-Hilliard equation, the dimensionless induction time is found to be a constant number for suddenly quenched systems. Computer simulation is carried out for prediction of early stage behavior with thermal history corresponding to a linear temperature drop followed by a constant temperature vs. time. In the areas of polymer membrane formation and phase separation studies, the universality of the constant dimensionless Induction time for suddenly quenched systems allows the determination of the minimum time needed for phase separation via spinodal decomposition. Also, simulation results for the double linear temperature history allows the convenient prediction of early stage spinodal decomposition behavior at every point of a membrane cross section undergoing thermal inversion phase separation.     

Analysis of polymer membrane formation through spinodal decomposition. Part 4: Computer simulation of early-stage coarsening

In a previous work, an early-stage coarsening mechanism was proposed, whereby continued growth of structure (via spinodal decomposition) in a polymer-solvent system will occur because some of the polymer-rich domains are being depleted. Such a mechanism was explained based on the situation wherein portions of the solvent-rich domains have already reached their binodal composition while the polymer-rich domains are still on their way to their corresponding binodal composition. In this work. we have simulated the nonlinear version of the Cahn-Hilliard theory to verify this phenomenon. Moreover, we have observed that the depleted polymer-rich domains seem to be uniformly distributed in space. Finally, as a validation of the proposed mechanism, we did not observe this uniform depletion of the domains when portions of the solvent-rich and polymer-rich domains reach their respective binodal compositions almost simultaneously.     

Analysis of polymer membrane formation through spinodal decomposition. II: Effect of Flory-Huggins enthalpic and entropic contributions

The phenomenological analysis of the thermal inversion membrane formation through spinodal decomposition was further developed to include enthalpic and entropic contributions to the Flory-Huggins interaction parameter. We found that material and processing conditions can be lumped into two parameters. One is the Deborah Number, De, which takes into account the thermal quenching relative to the phase separation induction time. The other one, designated as an ε-parameter, takes into account the quenching temperature relative to the spinodal temperature and the ratio of the enthalpic to the entropic contributions to the Flory-Huggins interaction parameter. From the model system, we found that the dimensionless interdomain distance, δ, as a function of 1/De (which is proportional to the cooling rate) falls in a relatively narrow banded region for all practical values of ε. As 1/De approaches infinity, δ is asymptotic up to maximum value of 3.5. This means that membranes made under applicable conditions will have a ratio of pore sizes of no more than 3.5. Other assumptions of the model are: (1) the mobility is temperature-independent; (2) the mutual diffusivity is a linear function of temperature; and (3) the thermal history (Temperature vs. Time), can be represented as two successive linear functions.     

Fractal behavior of spinodal decomposition in polymer blends

Summary Fractal behaviour of ramified domains in the late stage of spinodal phase separation in a binary polymer blend of poly(vinyl acetate) with poly(methyl methacrylate) was investigated by optical microscopic method. In the late stage of the spinodal decomposition, the fractal dimension D is about 1.64. It implies that some anomalous properties of irregular structure probably may be explained by fractal concepts.     

Photocrosslinking kinetics of polymer blends undergoing spinodal decomposition process

Photocrosslinking reaction kinetics of poly(2-chlorostyrene) performed inside the spinodal region of poly(2-chlorostyrene)/poly(vinyl methyl ether) (P2CS/PVME) blends was investigated by means of ultraviolet (UV)-visible absorption spectroscopy. The reaction was performed via photodimerization of anthracene moieties chemically labeled on the P2CS chains. The crosslinking kinetics of (P2CS/PVME) blends submitted to a temperature jump from the one-phase into the spinodal regions was observed by monitoring the irradiation time dependence of the absorbances of anthracene as well as of the blend in two regions of wavelengths. One is inside and the other is outside the absorption range of anthracene. The contribution of the sample cloudiness to the absorbance of anthracene was subtracted from the absorption data by using an empirical power law experimentally established between the incident wavelengths and the absorption of the blends. It was found that the reaction kinetics approximately follows the mean-field kinetics inside the spinodal region, resembling the behavior of the crosslinking reaction performed in the miscible region at relatively low crosslinking densities. On the other hand, the method described here fails to estimate the crosslinking densities when the phase separation proceeds rapidly, overcoming the reaction. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:885–893, 1998     

Crystallization of polycarbonate induced by spinodal decomposition in polymer blends

We found that amorphous polycarbonate (PC) can be crystallized in several minutes by blending poly(ethylene oxide) (PEO). When the blends were annealed in the two-phase region below the upper critical solution temperature, highly interconnected two-phase structure characteristic of the spinodal decomposition was developed and then the crystallization occurred in the PC-rich phase during the spinodal decomposition. As the molecular weight of PEO decreased, the crystallization rate decreased and the crystallizable temperature became narrower in spite of the acceleration of the polymeric segmental motion. These results suggest that the crystallization of the PC is not induced by the acceleration of the polymeric segmental motion, but by the up-hill diffusion of the liquid-liquid phase separation via spinodal decomposition. Owing to the competitive progress of the crystallization and the spinodal decomposition, the melting peak of the PC crystallites shifted to lower temperature with increasing annealing temperature.     

Computer vision methods for the study of spinodal decomposition in polymer blends

We demonstrate the use of computer vision techniques and optical microscopy to follow the kinetics and microstructure during spinodal decomposition of a polymer blend. Among other features, the mean of the population of the local maxima of the gradients in each image is computed; this global feature is shown to co-develop with the phase separation of the blend. An algorithm is presented which employs the gradient magnitude technique to analyze optical images of spinodally decomposing polymer blends. This algorithm has been used to extract the Cahn-Hilliard spinodal growth rates for a binary blend of polystyrene with poly(vinyl methyl ether). We show that the spinodal temperature can be found from the temperature dependence of this growth rate. We also show how additional shape features such as compactness might be used to study, the same binary blend.     

Membrane transport of organics. III. Permeation of some carboxylic acids through bipolar polymer membrane

The permeation of acetic (AA), propionic (PA), lactic (LA), oxalic (OA), citric (CA), and tartaric (TA) acids through the bipolar ion‐exchange membrane Neosepta BP‐1 (Tokuyama Corp.) was studied. It was found that the fluxes (J, mol cm^?2 s^?1) and mass‐transfer coefficients (k, cm s^?1) increase in the following order: CA < OA < LA < TA < PA ≤ AA. The transport processes in the Neosepta BP‐1 membrane are concentration‐dependent and can be described phenomenologically using I‐Fick's law for diffusion. The permeation phenomena correspond to the solution–diffusion model similarly as to the permeation of carboxylic acids through strongly acidic cation‐exchange membranes. However, in competitive AA–PA transport experiments, typically for strongly basic membranes, the separation ability of the BP‐1 membrane with a preference toward AA was observed. The selectivity coefficients α calculated as the ratio of the respective mass‐transfer coefficients vary in the range from 1.31 ± 0.2 to 2.1 ± 0.6. These values depend on the feed composition and the system arrangement, which means that α is always higher for the system with the anion‐exchange layer is in contact with a feed solution. Rather low fluxes of PA, AA, and other acids, as compared to some monopolar membranes (Neosepta AFN‐7, Nafion‐120, Flemion), are promising for the application of the bipolar membrane in an electrodialytic separation of carboxylic acids from their aqueous solutions or mixtures. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2705–2717, 2001     

Numerical simulation of substrate effects on spinodal decomposition in polymer binary mixture: morphology and dynamics

The characteristic features of the morphology and dynamics of binary mixture for substrate-directed spinodal decomposition (SDSD) in three dimensions have been studied using numerical simulations. The simulation results show that the formation of the wetting layer on the substrate interface follows the power-law growth. It is found that the continuous influence of anisotropic diffusive behavior arose by wetting of substrate induces the wetting component spreading onto the interface of the substrate randomly. The phase morphology and averaged size in the vicinity of the substrate fluctuate greatly due to the wetting of the substrate. The self-similar evolution of the cross-sections parallel and perpendicular to the substrate interface is discussed by relevant scale law functions, respectively. And the mechanisms of the growth in both the parallel and perpendicular directions are also investigated.     

Studies of polymer electrets. III. Charge decay behavior in polar polymer homoelectrets

Charge stabilities of various polar polymer homoelectrets were determined. Although these electerts are reasonably stable in dry environments, they rapidly discharge when exposed to humidity. The rate of charge decay was found to depend directly on the ability of these polymers to absorb water under equilibrium conditions. Protection from humidity is obtained if these polar polymers are coated on both sides with nonpolar polymers. If, however, two different polymer films are laminated, the electret behavior follows a pattern that can be explained on the basis of charging at the interface. Difference in stabilities of the electrets of polar and nonpolar polymers is attributed to the differing natures of the charge traps present in these two classes of polymers.     

Numerical simulation of substrate effects on spinodal decomposition in polymer binary mixture: Effects of the surface potential

The surface-directed spinodal decomposition (SDSD) of polymer binary mixture with different values of surface potential is numerically simulated in three-dimension (3D) by cell dynamic systems (CDS). Furthermore, the growth laws of the wetting layer are theoretically analyzed by the current equation and the dynamical scaling. The results show that the thickness of the wetting layer increases with the increasing surface potential. The crossover, which is later for larger values of surface potential, appears in the evolution curve of the wetting layer. Before the crossover, the growth law is the surface potential dependant growth law. Subsequently, the growth law is the typical Lifshitz-Slyozov (LS) growth law. The results indicate that the surface potential can result in the mutual transformation between completely wetting and partially wetting for the substrate interface. It can be found that the higher surface potential leads to the faster and stronger transmission of the effect of the substrate on the spinodal decomposition in the bulk.     

Thermal decomposition behavior of miscible cellulose/synthetic polymer blends

The thermal decomposition behavior of the miscible cellulosic blends cellulose(Cell)/poly(N-vinyl-2-pyrrolidone) (PVP), Cell/poly(ethylene glycol) (PEG), and Cell/poly(vinyl alcohol) (PVA) was investigated by thermogravimetry. The thermal stability of Cell in the Cell/PVP blends decreased but that of Cell in the Cell/PEG and Cell/PVA blends was hardly influenced. The thermal stability of synthetic polymers in the blends was little affected. The difference in thermal decomposition behavior was correlated to the difference in miscibility. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2133–2137, 1998     

Separation of liquid mixtures by using polymer membranes. III. Water–alcohol separation by pervaporation through modified PAN membrane

The modification of polyacrylonitrile membrane with ethanolamine was carried out, and the permeation characteristics in pervaporation were examined using the aqueous alcohol solutions. In pervaporation of a water/alcohol solution, preferential permeation of water was observed for all these membranes because of the hydrogen-bonding interaction. The selectivity of the modified polyacrylonitrile (PAN) membrane depended on operating temperature, but was independent on the thickness of the membrane. Furthermore, it was found that the membrane with more ethanolamine content had a higher affinity to water. The effect of feed concentration and the molecular size of the permeating species on the separation factor and permeation flux was also investigated.     

The mechanism of porous membrane formation from polymer solutions

Translated from Khimicheskie Volokna, No. 5, pp. 26–28, September–October, 1991.     

Novel phase inversion process for symmetric membrane formation through thermal quenching of polymer solution in same solvent

A new and useful form of phase inversion for the formation of porous polymeric membranes is presented herein. As in the case of thermally induced phase separation (TIPS), this new form involves only two components (polymer and solvent) and a thermal quench; here the quench is accomplished via immersion in a cold bath of the micromolecular component (solvent) of the dope. Ιn terms of a fixed‐pressure two‐component phase diagram the quench is a non‐vertical one. We will refer to the new method as cold‐solvent induced phase separation (CIPS). In the present work we study mainly the poly(ethylene‐co‐vinyl alcohol)/1,3‐propanediol system which leads to bi‐continuous structures stemming from a combination of liquid‐liquid demixing and crystallization. In addition, we compare with the case of the Nylon‐l2/formic acid system that we have briefly considered before and study further herein; the consequences of the TIPS to CIPS shift of method are different for the two systems, and the two situations are representative of two general possibilities. We also report general properties such as porosity, tensile strength, water permeation flux, and crystallinity of the produced poly(ethylene‐co‐vinyl alcohol) membranes. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42282.     

Antimony polymers. III. Flame retardant behavior of chloroprene and natural rubber vulcanizates with antimony polymer

The antimony-containing polymer of bisphenol-A (BPA) and triphenyl antimony dinitrate was used as a flame retardant (FR) for chloroprene rubber (CR) and natural rubber (NR). The flame retardancy of this additive was monitored by the limiting oxygen index (LOI) measurements of the rubber vulcanizates and compared with that for antimony trioxide used as a FR additive. The thermogravimetric analysis (TGA) of the vulcanizates has also been studied. A structure flammability relationship has been established. The effect of this FR additive on physical properties of the vulcanizates undergoing heat aging and solvent leaching has also been evaluated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 927–935, 1998     

Brownian dynamics simulations of the effects of hydrodynamic interactions on the polymer viscoelastic behavior

Brownian dynamics simulation is used to investigate the viscoelastic response of the Gaussian chain to a step shear deformation in both the linear and non-linear regions under the influence of hydrodynamic interactions. Both the preaveraged Oseen tensor and the Rotne-Prager tensor are used in the study. In the former case, the simulation results are shown to be in agreement with the expected results calculated using the eigenvalues of the normal modes of motion obtained numerically. It is shown that an initial state with zero second normal-stress difference is generated by the step shear deformation. The subsequent rise of the second normal-stress difference as revealed by the simulation is shown mainly arising from the coupling of the recoil of the stretched bond in the direction of deformation and the anisotropy in the hydrodynamic interaction created by the step deformation.     

Membrane transport of organics. II. Permeation of some carboxylic acids through strongly basic polymer membrane

The permeability characteristics of the strongly basic polymer membrane Neosepta® AFN‐7, (Tokuyama Soda) have been studied for acetic, propionic, lactic, tartaric, oxalic, and citric acid. The results were interpreted by using the model of transport in reactive membranes. The specific constants, that is, the maximum flux J_max, the reactivity constant K, and the permeability coefficient (P), were calculated using the experimental quasi‐stationary fluxes and the equation derived as a sum of reaction–diffusion (Michaelis–Menten‐type), and the solution–diffusion transport equation. The constants K and J_max were found to range from 0.1 to 5 dm³ mol⁻¹ and from 0.4 × 10⁻⁷ to 2.5 × 10⁻⁷ mol cm⁻² s⁻¹ depending, on the acid properties. The values of K and J_max were correlated with the dissociation constants K_dis.acid, and the diffusion coefficients D_aq.acid in aqueous media, respectively. It was found that the reaction–diffusion flux is predominating for all acids, except for the lactic one, when the feed concentration is lower than 0.5 mol dm⁻³. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2179–2190, 1999     

Studies of porous polymer gels. III. Swelling behavior of porous poly(methacrylic acid) gels

Further studies of porous suspension copolymers of methacrylic acid and divinylbenzene (DVB) are reported. The qualitative structure model of the copolymers proposed previously is used to interpret the ion-exchange properties, sorption of water and aqueous sodium chloride solution, swelling, and neutralization rate. It is proposed that the close to ideal NON-SOL methacrylic acid–divinylbenzene copolymers are composed of rigid microgels and lightly crosslinked poly(methacrylic acid). The latter swollen in water gives the gel, which tends to occupy the accessible space in the copolymer bead together with macropores detectable in the dry state. For the copolymers studied, the DVB content, 5.0 and 9.1% by weight, affects the rigid portion dimension and the extent of swelling of the whole bead, while the expansion of linear chains is determined by the distance between microgels.