Phase separation mechanism during membrane formation by dry‐cast process

Phase separation mechanisms during the membrane formation by dry‐cast process were investigated by light scattering in the cellulose acetate/dimethylformamide (DMF)/2‐methyl‐2,4‐pentanediol system. Phase separation occurred by spinodal decomposition (SD) when paths of the composition changes due to the evaporation of DMF were close to the critical point in the phase diagram. Characteristic properties of the early stage of SD such as an apparent diffusion coefficient and an interface periodic distance were obtained from the Cahn theory. Phase separation occurred by nucleation and growth (NG) when paths of the composition changes were far from the critical point. SEM observation confirmed that the membrane formed by the SD mechanism had interconnected structure, whereas that by the NG mechanism had the closed cell porous structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 776–782, 2000     

Studies on phase separation rate in porous polyimide membrane formation by immersion precipitation

Phase separation rate during porous membrane formation by immersion precipitation was investigated by light scattering in a polyimide/N‐Methylpyrrolidone (NMP)/water system. In the light scattering measurement, plots of scattered intensity against scattered angle showed maxima in all cases, which indicated that phase separation occurred by a spinodal decomposition (SD). Characteristic properties of the early stage of SD, such as an apparent diffusion coefficient D_app and an interphase periodic distance Λ, were obtained. The growth process of Λ was also followed by light scattering. The growth rate had the same tendency as D_app when water content in the nonsolvent bath and the polymer concentration in the cast solution were changed. The pore size of the final membrane increased with decreasing water content, which was opposite to the tendency of Λ growth rate. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 292–296, 2003     

Study of the nonlinear phase‐separation behavior of a polystyrene/poly(vinyl methyl ether) blend using small‐angle light scattering

The thermally induced phase‐separation behavior of a polystyrene/poly(vinyl methyl ether) (PS/PVME) blend was studied mainly using time‐resolved small‐angle light scattering, as a function of temperature and heating rate. Under a non‐isothermal field, the dependence of the critical temperature on heating rate deviated obviously from linearity, even at very low heating rates. Such a nonlinear dependence was consistent with the deviation from linearity of the temperature dependence of the isothermal phase‐separation behavior in a wider temperature range from 100 to 140 °C. It was also found that a Williams–Landel–Ferry (WLF)‐like equation could be employed to describe the temperature dependence of the apparent diffusion coefficient (D_app) and the relaxation time (τ) of normalized scattering intensity at the early stage of spinodal decomposition (SD), as well as τ of phase behavior at the late stage of SD for the PS/PVME blend. The equilibrium phase‐separation temperature could hardly be established through the conventional linear extrapolation of heating rate or D_app to zero at the early stage of SD. The successful use of the WLF‐like function for PS/PVME blends extends the applicability of the time–temperature superposition principle for describing the phase‐separation behavior of binary polymer mixtures over a relatively large temperature range. Copyright © 2010 Society of Chemical Industry     

Light‐scattering study on porous membrane formation by dry‐cast process

The phase‐separation mechanism during porous membrane formation by the dry‐cast process was investigated by the light‐scattering method in poly(methyl methacrylate)/ethyl acetate (EA)/2‐methyl‐2,4‐pentanediol system. The evaporation of EA from the cast solution induced the phase separation and thus the porous membrane was obtained. By the light‐scattering measurement on the phase‐separation kinetics, the phase separation was found to occur by a spinodal decomposition mechanism. As the amount of nonsolvent in the cast solution decreased, the structure growth rate decreased and the growth stopped soon. The obtained porous structure was isotropic rather than asymmetric. The average interpore distances obtained from the SEM observation roughly agreed with the final constant interphase periodic distances measured by the light‐scattering method. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 10: 3205–3209, 2002     

Structure development via reaction-induced phase separation in tetrafunctional epoxy/polysulfone blends

For the cure process of tetrafunctional epoxy resin/polysulfone(EP/PSF) blends, we investigated the effect of cure temperature and blend composition on the phase separation behavior by light scattering and the structure development during cure by an optical microscope. The EP/PSF blend without the curing agent was shown to exhibit an LCST-type phase behavior (LCST = 241°C). At the early stage of curing, the EP/PSF blend was homogeneous at the cure temperature. As the cure reaction proceeded, the blend was thrust into a two-phase regime by the LCST depression caused by the increase in a molecular weight of the epoxy-rich phase, and the phase separation took place via a spinodal decomposition (SD) or nucleation and growth (NG) mode, depending on the blend composition and the cure temperature. When cured isothermally at 220°C, the blend exhibited a sea-island morphology formed via the NG mode below 5 wt % PSF content, while the SD mode prevailed above 20 wt % PSF content. At the intermediate composition range, combined morphology with both sea-island and cocontinuous structure was observed. On the other hand, by lowering the cure temperature and/or increasing the content of PSF component, a two-phase structure with a shorter periodic distance was obtained. It seems that the rate of the phase separation is considerable reduced, while that of the cure reaction is not as much. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2233–2242, 1997     

Effects of the molecular weight of poly(ether imide) on the viscoelastic phase separation of poly(ether imide)/epoxy blends

The phase separation of diglycidyl ether of bisphenol A/methyl tetrahydrophthalic anhydride blends modified with three poly(ether imide)s (PEIs) of different molecular weights was investigated with scanning electron microscopy (SEM) and time‐resolved light scattering (TRLS). The morphologies observed by SEM for the three blends were all close to a cocontinuous structure with different periodic distances. The results of TRLS indicated that the phase separation for the PEI‐modified epoxy blends took place according to the spinodal decomposition mechanism and the onset time of phase separation, with the periodicity of the phase structure depending on the PEI molecular weight and cure temperature. The time‐dependent peak scattering vector was simulated with a Maxwell‐type viscoelastic relaxation equation, indicating that the coarsening process of epoxy droplets was mainly controlled by the viscoelastic flow. Relaxation times obtained at different temperatures for the three blends could be described by the Williams–Landel–Ferry equation. The effects of the PEI molecular weight on the processes of viscoelastic phase separation were investigated, and the observed trends could be explained qualitatively through thermodynamic analysis. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Kinetics of phase separation of poly(styrene‐co‐methyl methacrylate) and poly(styrene‐co‐acrylonitrile) blends

The phase behavior and kinetics of phase separation for blends of the random copolymer poly(styrene‐co‐methyl methacrylate) (SMMA) and poly(styrene‐co‐acrylonitrile) (SAN) were studied by using small‐angle laser light scattering. The partially miscible SMMA/SAN blends undergo spinodal decomposition (SD) and subsequent domain coarsening when quenched inside the unstable region. For blends of SMMA and SAN, the early stages of the phase separation process could be observed, unlike a number of other blends where the earliest stages are not visible by light scattering. The process was described in terms of the Cahn–Hilliard linear theory. Subsequently, a coarsening process was detected and the time evolution of q_m at the beginning of the late stages of phase separation followed the relationship q_m∝t^?1/3, corresponding to an evaporation–condensation mechanism. Self‐similar growth of the phase‐separated structures at different timescales was observed for the late stage. Copyright © 2004 Society of Chemical Industry     

Nonlinear phase‐separation behavior of poly(methyl methacrylate)/poly(styrene‐co‐maleic anhydride) blends

The nonlinear phase‐separation behavior of poly(methyl methacrylate)/poly(styrene‐co‐maleic anhydride) (PMMA/SMA) blends over wide appropriate temperature and heating rate ranges was studied using time‐resolved small‐angle laser light scattering. During the non‐isothermal process, a quantitative logarithm function was established to describe the relationship between cloud point (T_c) and heating rate (k) as given by T_c = Alnk + T₀, in which the parameter A, reflecting the heating rate dependence, is much different for different compositions due to phase‐separation rate and activation energy difference. For the isothermal phase‐separation process, an Arrhenius‐like equation was successfully applied to describe the temperature dependence of the apparent diffusion coefficient (D_app) and the relaxation time (τ) of the early stage as well as the late stage of spinodal decomposition (SD) of PMMA/SMA blends. Based on the successful application of the Arrhenius‐like equation, the related activation energies could be obtained from D_app and τ of the early and late stages of SD, respectively. In addition, these results indicate that it is possible to predict the temperature dependence of the phase‐separation behavior of binary polymer mixtures during isothermal annealing over a range of 100 °C above the glass transition temperature using the Arrhenius‐like equation. © 2012 Society of Chemical Industry     

Phase separation and dewetting in polystyrene/poly(vinyl methyl ether) blend thin films in a wide thickness range

Phase separation and dewetting processes of blend thin films of polystyrene (PS) and poly(vinyl methyl ether) (PVME) in two phase region have been studied in a wide film thickness range from 65 μm to 42 nm (∼2.5R_g, R_g being radius of gyration of a polymer) using optical microscope (OM), atomic force microscope (AFM) and small-angle light scattering (LS). It was found that both phase separation and dewetting processes depend on the film thickness and were classified into four thickness regions. In the first region above ∼15 μm the spinodal decomposition (SD) type phase separation occurs in a similar manner to bulk and no dewetting is observed. This region can be regarded as bulk. In the second region between ∼15 and ∼1 μm, the SD type phase separation proceeds in the early stage while the characteristic wavelength of the SD decreases with the film thickness. In the late stage dewetting is induced by the phase separation. In the third region between ∼1 μm and ∼200 nm the dewetting is observed even in the early stage. The dewetting morphology is very irregular and no definite characteristic wavelength is observed. It is expected that the irregular morphology is induced by mixing up the characteristic wavelengths of the phase separation and the dewetting. In the fourth region below ∼200 nm the dewetting occurs after a long incubation time with a characteristic wavelength, which decreases with the film thickness. It is considered that the layered structure is formed in the thin film during the incubation period and triggers the dewetting through the capillary fluctuation mechanism or the composition fluctuation one.     

Analysis of unsaturated polyester-polyurethane interpenetrating polymer networks II: Phase separation behavior

The phase separation behavior of unsaturated polyester (UPE)-polyurethane (PU) interpenetrating polymer networks (IPNs) was investigated by light scattering measurements during simultaneous polymerization. The scattered light intensity change with time showed the formation of the dispersed domains, and the average domain correlation length could be calculated from the angle of maximum scattering intensify. It was noted that the dominant phase separation process was spinodal decomposition due to fast reaction. The morphology observed by the transmission electron micrographs for various process conditions showed similar results as obtained from the light scattering experiment.     

Phase separation and crystallization behavior in extruded polypropylene/ethylene–propylene rubber blends

Liquid–liquid (L–L) phase separation and its effects on crystallization in polypropylene (PP)/ethylene–propylene rubber (EPR) blends obtained by melt extrusion were investigated by time‐resolved light scattering (TRLS) and optical microscopy. L–L phase separation via spinodal decomposition (SD) was confirmed by TRLS data. After L–L phase separation at 250°C for various durations, blend samples were subjected to a temperature drop to 130°C for isothermal crystallization, and the effects of L–L phase separation on crystallization were investigated. Memory of the L–L phase separation via SD remained for crystallization. The crystallization rate decreased with increasing L–L phase‐separated time at 250°C. Slow crystallization for the long L–L phase‐separated time could be ascribed to decreasing chain mobility of PP with a decrease in the EPR component in the PP‐rich region. The propylene‐rich EPR exhibited good affinity with PP, leading to a slow growth of a concentration fluctuation during annealing. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 695–700, 2001     

Gelation mechanism of agarose and κ-carrageenan solutions estimated in terms of concentration fluctuation

The gelation mechanism of agarose and κ-carrageenan aqueous solutions was investigated by using polarized light scattering and X-ray diffraction techniques in terms of the liquid-liquid phase separation. When an incident beam of He-Ne gas laser was directed to the gel prepared by quenching the agarose solution, the logarithm of scattered intensity increased linearly in the initial stage and tended to deviate from this linear relationship in the latter stage. If the linear increase in the initial stage could be analyzed within the framework of the linear theory of spinodal decomposition proposed by Cahn, the phase diagram indicated that the gelation is attributed to the phase separation due to the concentration fluctuation of solution. Furthermore, in the later stage showing the deviation of the linear relationship, light scattering under Hv polarization condition showed a X-type pattern indicating the existence of optically anisotropic rods, the optical axes being parallel or perpendicular with respect to the rod axis. In spite of the existence of the rods, no crystallites were confirmed by the corresponding X-ray diffraction and DSC measurements. For κ-carrageenan solutions, the logarithm of scattered intensity against time showed a constant value. This indicated that the gelation of κ-carrageenan solutions is independent of liquid-liquid phase separation but is due to the rapid formation of cross-linking points. Accordingly it turns out that the small difference of chemical structure between agarose and κ-carrageenan causes quite different gelation mechanism.     

Dynamic interplay between phase separation and crystallization in a poly(?-caprolactone)/poly(ethylene glycol) oligomer blend

We have investigated the crystallization effect on the phase separation of a poly(?-caprolactone) and poly(ethylene glycol) oligomer (PCL/PEGo) blending system using simultaneous small-angle light scattering and differential scanning calorimetry (SALS/DSC) as well as simultaneous small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), and DSC (SAXS/WAXS/DSC). When the PCL/PEGo system, of a weight ratio of 7/3, is quenched from a melt state (160 °C) to temperatures below the spinodal point and the melting temperature of PCL (63 °C), the structural evolution observed exhibits characteristics of (I) early stage of spinodal decomposition (SD), (II) transient pinning, (III) crystallization-induced depinning, and (IV) diffusion-limited crystallization. The time-dependent scattering data of SALS, SAXS and WAXS, covering a wide range of length scale, clearly show that the crystallization of PCL intervenes significantly in the ongoing viscoelastic phase separation of the system, only after the early stage of SD. The effect of preordering before crystallization revives the structural evolution pinned by the viscoelastic phase separation. The growth of SAXS intensity during the preordering period conforms to the Cahn-Hilliard theory. In the later stage of the phase separation, the PCL-rich matrix, of spherulite crystalline domains developed due to the faster crystallization kinetics, traps the isolated PEGo-rich domains of a slower viscoelastic separation.     

Structure development in the phenolic resin/poly(methyl methacrylate-co-ethyl acrylate) copolymer blends

Single-phase mixtures of phenolic derivatives with three poly(methyl methacrylate-co-ethyl acrylate) copolymers [P(MMA-co-EA)s] were cured in the presence of hexamethylenetetramine and the reaction kinetics and phase-separation processes during cure were investigated by differential scanning calorimetry (DSC), light scattering, and optical microscopy (OM). DSC measurements revealed that the higher the fraction of multifunctional phenols in the total phenols the lower the conversion at gelation in the phenolic-rich phase. The time variation of the light-scattering profile during cure demonstrated the characteristic feature for spinodal decomposition. OM observation revealed that a cocontinuous two-phase structure appeared after a certain time lag and coarsened to a spherical domain structure consisting of phenolic resin particles dispersed in the P(MMA-co-EA)s matrix. The periodic distances, Λ_m, in the phase-separated structure changed with curing time: (1) The higher the component of MMA in P(MMA-co-EA)s and (2) the higher the fraction of multifunctional phenols in the total phenols, the smaller the Λ_m. These results may imply that the phase separation is suppressed by the faster gelation in the phenolic-rich phase so that the phase-separated structure can be fixed by the network formation in the phenolic-rich phase at the early stage of spinodal decomposition. This results in a two-phase structure with a shorter periodic distance. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1829–1837, 1998     

Thermoset/(Thermoplastic elastomer) blends: Epoxy/EVA

Phase separation behavior and phase morphology of mixtures of methylene dianiline (MDA)‐cured diglycidyl ether of Bisphenol A (DGEBA) epoxy oligomer and 0–30 wt % of ethylene‐(vinyl acetate) copolymer (70% vinyl acetate content) were investigated by means of small angle light scattering (SALS), optical microscopy, and scanning electron microscopy (SEM). Epoxies with EVA modified were also characterized by tensile, flexural, thermal, and hardness properties. Epoxy/EVA blend compositions, during isothermal curing, showed a ring pattern of light scattering, an increase of intensity, and a shift of peak angle to smaller scattering angle, all of which are hallmarks of spinodal decomposition. Optical microscopy studies revealed a two‐phase structure with unique periodicity and phase connectivity. Physical property measurements indicated that there was no toughening achieved by EVA modification of epoxy, and this result was explained with morphological information obtained by SEM.     

Phase morphology and mechanical properties of a poly(ether sulfone)‐modified bismaleimide resin

The polymerization‐induced phase‐separation behavior of a thermoplastic [poly(ether sulfone) (PES)]‐ modified thermosetting bismaleimide resin during isothermal curing was investigated with differential scanning calorimetry, time‐resolved light scattering, and scanning electron microscopy with various contents and molecular weights of PES. The results suggested that the phase structure changed from a dispersed structure to a bicontinuous structure to phase inversion with an increase in the PES content. Three kinds of PES with different molecular weights were used to study the effects of the molecular weight on the phase structure and mechanical properties of modified systems. With higher molecular weight PES, a phase‐inversion morphology could be obtained at lower PES contents. The curing conversion of bismaleimide was affected by the composition of the blend. The curing rate decreased with an increase in the PES content. A blend with 15 wt % PES of a suitable molecular weight had a higher tensile strength and elongation at break than that without PES. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Monodisperse‐porous poly(styrene‐co‐divinylbenzene) beads providing high column efficiency in reversed phase HPLC

A multistage polymerization protocol, the so‐called “modified seeded polymerization,” was developed for the production of monodisperse‐porous poly(styrene‐co‐divinylbenzene) providing high column efficiency as a packing material in reversed phase high performance liquid chromatography (RPLC). In the first stage of the multistage production, uniform polystyrene seed particles, produced by dispersion polymerization, were swollen by an organic agent (i.e., the diluent) and then by a monomer mixture containing styrene and divinylbenzene. The final porous particles were obtained in the monodisperse form by the polymerization of monomer mixture in the seed particles. By the use of a small size seed latex with low molecular weight and by the selection of the appropriate diluent, relatively small monodisperse‐porous particles with suitable pore structure could be achieved. In the reversed phase separation of alkylbenzenes, under isocratic conditions, theoretical plate numbers up to 40,000 plates/m were achieved by using 5.2 μm porous particles, obtained by a toluene‐dibutyl phthalate mixture as the diluent. No significant decrease in the resolution power was observed by the fourfold increase in the mobile phase flow rate. The column efficiency and the resolution observed with 5.2 μm monodisperse‐porous particles were significantly higher with respect to the currently available polymer based packing materials used in the reversed phase HPLC. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1430–1438, 2005     

Phase‐separation mechanism and corresponding final morphologies of thermoset blends based on unsaturated polyester and low‐molar‐weight saturated polyester

The final morphology of cured blends based on unsaturated polyester, styrene, and low‐molar‐weight saturated polyester as a low profile additive (LPA) was investigated with atomic force microscopy and scanning electron microscopy. The observed structure was compared to those obtained with widely used poly(vinyl acetate) (PVAc). On the surface and in the bulk, a network of particles, ranging in size from 50 to 60 nm, was observed with saturated polyester as an LPA. The influence of the molar weight and LPA content was investigated. To determine the mechanism of formation of such a morphology, in situ experiments were carried out to elucidate the phase‐separation mechanism. Small‐angle laser light scattering and small‐angle neutron scattering experiments were performed on ternary blends containing PVAc and saturated polyester, respectively. The first stage of spinodal decomposition was observed in both cases. Within our experimental conditions, gelation froze further evolution and led to a two‐phase cocontinuous structure that imposed the final morphology characteristics. In particular, the period and amplitude of the concentration fluctuations generated during the phase separation played essential roles. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1459–1472, 2005     

Effect of an organoclay on the reaction‐induced phase‐separation kinetics and morphology of a poly(ether imide)/epoxy mixture

Organically modified layered silicates with a hydroxyl‐substituted quaternary ammonium surfactant as the modifier were incorporated into a mixture of poly (ether imide) and epoxy with 4,4′‐diaminodiphenyl sulfone as the hardener. The influence of the organically modified layered silicates on the reaction‐induced phase‐separation kinetics and morphology of the poly(ether imide)/epoxy mixture was investigated with time‐resolved small‐angle light scattering, phase‐contrast microscopy, and scanning electron microscopy. The phase‐separation kinetics were analyzed by means of the temporal evolution of scattering vector q _m and scattering intensity I_m at the scattering peak. The organically modified layered silicates obviously facilitated an earlier onset of phase separation but reduce the phase‐separation rate and greatly retarded the domain‐coarsening process in the late stage of spinodal decomposition. The temporal evolution of both q _m and I_m followed the power law q _m ～ (t ? t_os)^?α and I_m ～(t ? t_os)^?β, where t is the reaction time, t_os is the onset time of phase separation, and α and β are growth exponents. For the samples filled with organically modified layered silicates, α crossed over from 0 to about 1/3, following Binder–Stauffer cluster dynamics, and an interconnected phase structure was observed for cure temperatures ranging from 120 to 230°C. For the unfilled samples, the interconnected phase structure was observed only at cure temperatures below 140°C. At temperatures above 150°C, α crossed over from 0 to 1/3 < α ≤ 1 under the interfacial tension effect, following Siggia's theory, and the domain‐coarsening rate was very fast; this resulted in macroscopic epoxy‐rich domains. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1205–1214, 2007     

Dependence of morphological changes of polymer particles on hydrophobic/hydrophilic additives

Fairly uniform microspheres of poly(styrene‐co‐methyl methacrylate) were prepared by employing a microporous glass membrane [Shirasu porous glass (SPG)]. The single‐step SPG emulsification, the emulsion composed mainly of monomers, hydrophobic additives, and an oil‐soluble initiator, suspended in the aqueous phase containing a stabilizer and inhibitor, was then transferred to a reactor, and subsequent suspension polymerization followed. The droplets obtained were polymerized at 75°C under a nitrogen atmosphere for 24 h. The uniform poly(styrene‐co‐methyl methacrylate) microspheres with diameters ranging from 7 to 14 μm and a narrow particle‐size distribution with a coefficient of variation close to 10% were prepared by using SPG membrane with a pore size of 1.42 μm. The effects of the crosslinking agent and hydrophobic additives on the particle size, particle‐size distribution, and morphologies were investigated. It was found that the particle size decreased with a narrower size distribution when the additives were changed from long‐chain alkanes to long‐chain alcohols and long‐chain esters, respectively. Various microspheres with different morphologies were obtained, depending on the composition of the oil phase. The spherical poly(styrene‐co‐methyl methacrylate) particles without phase separation were obtained when using an adequate amount of the crosslinking agent and methyl palmitate as an additive. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1013–1028, 2000