Polymer blends with spatially graded structures prepared by phase separation under a temperature gradient

Phase separation of poly(2-chlorostyrene)/poly(vinyl methyl ether) (P2CS/PVME) blends driven by a temperature gradient was investigated by phase-contrast optical microscopy combined with digital image analysis. The samples were set in a temperature gradient in such a way that the two ends of the gradient cover both sides of the critical point. When the high-temperature side of the gradient is increased with a constant rate, the interface that divides the miscible and the phase separated regions of the blend moves toward the low temperature side, leaving the phase separating region behind. It was found that in the vicinity of this interface, the phase separation takes place slowly via the spinodal decomposition process, giving interconnecting structures. In the region far from the newly growing interface, the droplet morphology appears as a result of the late stage of the spinodal decomposition. These droplets grow with time according to the power law ξ ∝ tβ, with β increasing from 0.30 to 0.44 along the temperature gradient. The phase separated blends with these graded morphologies show the broadened mechanical tanδ due to the graded structures distributed along the temperature gradient.     

Multilayer formation via spinodal decomposition in TiO2-VO2 epitaxial films on sapphire substrates

We present multilayer formation via spinodal decomposition in rutile TiO₂-VO₂ (TVO) epitaxial films on sapphire substrates. (001)- and (101)-oriented TVO solid-solution films are grown epitaxially on TiO₂/Al₂O₃ using a pulsed laser deposition technique and annealed inside the spinodal region. X-ray diffraction measurements and scanning transmission electron microscopy (STEM) observations show that the films are phase-separated along the [001] direction and lamellar structures are formed in a parallel or slanted direction to the sapphire substrates depending on the film orientation. The results indicate the multilayer formation via spinodal decomposition in the TVO films. STEM investigations also reveal a relatively high Ti concentration in the decomposed phases, reflecting the influence of lattice deformation on the phase decomposition in the films. Our work shows that spinodal decomposition is a promising approach for the formation of a multilayer structure in TVO films and helps deepen understanding the spinodal decomposition in TVO system.     

Morphology development and characterization of the phase-separated structure resulting from the thermal-induced phase separation phenomenon in polymer solutions under a temperature gradient

This paper studied the morphological development during the fabrication of anisotropic polymeric materials using the thermal-induced phase separation phenomenon (spinodal decomposition) in a model binary polymer solution under a linear spatial temperature gradient using mathematical modeling and computer simulation. The model incorporated the non-linear Cahn-Hilliard theory for spinodal decomposition and the Flory-Huggins theory for polymer solution thermodynamics. Moreover, the slow mode theory and Rouse law were used to account for polymer diffusion. The two-dimensional numerical results showed that an anisotropic morphology was developed when a temperature gradient was imposed along the polymer solution sample. The droplet size and droplet density decrease as temperature increases during the intermediate stage of spinodal decomposition. The spatial temperature gradient, however, had insignificant effect on the droplet shape.     

Phase changes during solution casting of polymer blends containing cellulose

Summary Morphological control of polymer solutions containing cellulose and synthetic polymers through spinodal decomposition was studied by optical microscopy inspection. The evolution of phase-separated structures depends highly on the ratio of the evaporation rate and the growth rate of concentration fluctuations. Regular bicontinuous structures result only when this ratio is sufficiently high. Then, the regular morphology develops at relatively high polymer concentration and is maintained as a whole in the course of evaporation.     

Bicontinuous porosity in ceramics utilizing polymer spinodal phase separation

This paper demonstrates how the combination of inorganic and organic polymers can be used to form bicontinuous porosity in ceramics with pore sizes larger than 5 μm. Spinodal phase separation of pseudo-binary polymer mixtures allows to form larger bicontinuous pore structures than spinodal phase separation of inorganic glasses. Addition of salts allows even more complex compositions of ceramics and glasses to be formed. Here, bioactive glasses are presented that were produced via sol–gel processing of a pseudo-binary mixture of an inorganic and an organic polymer. Due to the addition of an organic polymer to the gelling sol and the spinodal phase separation at a specific equilibrium temperature, both an inorganic polymer ceramic phase and organic polymer-rich phase are formed. The evaporation of the solvent and the burnout of the organic polymer produce a microstructure of interconnected and nearly uniform porosity, which can be controlled by several processing parameters. The dependency of pore size and connectivity is best predicted by polymer phase separation rather than glass melt separation. Results suggest that polymer spinodal phase separation could be useful for the manufacture of a variety of porous ceramics.     

Morphological studies of late-stage spinodal decomposition in polystyrene–cyclohexanol system

We studied the late-stage spinodal decomposition of the polystyrene–cyclohexanol system in relation to membrane formation. Phase separation was effected by the removal of thermal energy from the homogeneous polymer solution. The ultimate morphology of the phase-separated systems has been studied using electron microscopy and has been found to be strongly affected by the quenching time. A shift from a highly interconnected open-cell structure to a closed-cell structure has been observed, indicating the transition of the spinodal decomposition from early to late stages. The cell growth in the late stage has been quantitatively analyzed and a power-law relationship between the cell size and quenching time has been found. The resulting exponent of 0.61 is consistent with literature values from light-scattering measurements, as well as from theoretical derivations. © 1995 John Wiley & Sons, Inc.     

Organically modified layered-silicates facilitate the formation of interconnected structure in the reaction-induced phase separation of epoxy/thermoplastic hybrid nanocomposite

We incorporated organic modified layered silicates (OLS) into the mixture of epoxy and poly(ether imide) (PEI) to obtain a ternary hybrid nanocomposite and investigated its reaction-induced phase separation behavior. We found that OLS had dramatic impact to the phase separation process and the final phase morphology. The onset of phase separation and the gelation or vitrification time were greatly brought forward and the periodic distance of phase-separated structure was reduced when OLS was incorporated. Phase separation of the unfilled specimens was greatly suppressed at temperatures higher than 190 °C, and no etch hole of PEI-rich phase could be observed in the SEM images. An interconnected, or bicontinuous morphology could only be observed at cure temperatures lower than 140 °C. On the contrary, the OLS-filled hybrid nanocomposites carried out obvious phase separation at cure temperatures ranging from 120 to 220 °C. Even at cure temperatures higher than 190 °C, the hybrid nanocomposites had an interconnected phase-separated microstructure. These phenomena were related to the preferential wettability, chemical reaction of OLS with epoxy oligomer and the enhanced viscosity of the mixture.     

Spinodal Decomposition in a K2O-Al2O3-CaO-SiO2 Glass

Diffuse interfaces are observed in the interconnected structure of a phase-separated K₂O-Al₂O₃-CaO-SiO₂ glass. With continued electron irradiation in the scanning transmission electron microscope, the interfaces are observed to sharpen with little attendant change in phase morphology, indicating that the as-cooled microstructure is formed through spinodal decomposition .     

Liquid-liquid phase separation in a polyethylene blend monitored by crystallization kinetics and crystal-decorated phase morphologies

A series of polyethylene (PE) blends consisting of a linear high density polyethylene (HDPE) and a linear low density polyethylene (LLDPE) with an octane-chain branch density of 120/1000 carbon was prepared at different concentrations. The two components of this set of blends possessed isorefractive indices, thus, making it difficult to detect their liquid-liquid phase separation via scattering techniques. Above the experimentally observed melting temperature of HDPE, T_m = 133 °C, this series of blends can be considered to be in the liquid state. The LLDPE crystallization temperature was below 50 °C; therefore, above 80 °C and below the melting temperature of HDPE, a series of crystalline-amorphous PE blends could be created. A specifically designed two-step isothermal experimental procedure was utilized to monitor the liquid-liquid phase separation of this set of blends. The first step was to quench the system from temperatures of known miscibility and isothermally anneal them at a temperature higher than the equilibrium melting temperature of the HDPE for the purpose of allowing the phase morphology to develop from liquid-liquid phase separation. The second step was to quench the system to a temperature at which the HDPE could rapidly crystallize. The time for developing 50% of the total crystallinity (t_1/2) was used to monitor the crystallization kinetics. Because phase separation results in HDPE-rich domains where the crystallization rates are increased, this technique provided an experimental measure to identify the binodal curve of the liquid-liquid phase separation for the system indicated by faster t_1/2. The annealing temperature in the first step that exhibits an onset of the decrease in t_1/2 is the temperature of the binodal point for that blend composition. In addition, the HDPE-rich domains crystallized to form spherulites which decorate the phase-separated morphology. Therefore, the crystal dispersion indicates whether the phase separation followed a nucleation-and-growth process or a spinodal decomposition process. These crystal-decorated morphologies enabled the spinodal curve to be experimentally determined for the first time in this set of blends.     

Effects of bath temperature on the morphology and performance of EVOH membranes prepared by the cold‐solvent induced phase separation (CIPS) method

The development and characteristics of porous EVOH membranes by cold‐solvent induced phase separation (CIPS) process were investigated. Binary dopes of 1,3‐propandiol/EVOH prepared at 80 °C were immersed in 1,3‐propandiol at a lower temperature to engender polymer precipitation. The quench temperature affects phase separation modes, and hence structure and performance of resulting CIPS membranes. When the bath temperature was set below the crystallization line and above the binodal (e.g. 45 °C), the formed membrane was dominated by a packing of semicrystalline EVOH globules. When the bath was set at a temperature just below the spinodal (e.g. 20 °C), spinodal decomposition (SD) dominated the precipitation process to give a lacy‐like bicontinuous structure; yet there is also a clear imprint from polymer crystallization. When the bath temperature was set deeply within the spinodal dome (e.g. 5 °C), polymer crystallization affected only little the SD‐derived bicontinuous morphology. Water permeation flux, wettability, tensile strength, and ultra‐filtration experiments of the membranes were conducted. The results indicated that those properties were closely correlated with the porosity level, pore size, and membrane morphology. Moreover, X‐ray diffraction and DSC analyses indicated that the formed membranes had a crystallinity of 38 to 42%, consistent with the literature data. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44553.     

Kinetics of phase separation and crystallization in poly(ethylene-ran-hexene) and poly(ethylene-ran-octene)

The kinetics of phase separation and crystallization in the blends of poly(ethylene-ran-hexene) (PEH) and poly(ethylene-ran-octene) (PEOC) at several compositions were studied using phase contrast optical microscopy and time-resolved simultaneous small-angle X-ray scattering and wide-angle X-ray diffraction. The phase contrast optical microscopy showed the interconnected bicontinuous structure during phase separation process, which is characteristic of a spinodal decomposition. During isothermal crystallization, the average lamellar spacing increases with time for blends at all concentrations. The crystallinity and crystal growth rate depend on the PEH concentration. At dilute PEH concentrations, crystallization of PEH chains is difficult because they are surrounded by many non-crystallizable PEOC chains. On the other hand, at higher PEH concentrations, crystallization processes are similar to pure PEH. For example, the spherulitic growth rates are similar for a PEH/PEOC=50/50 blend and pure PEH.     

Reaction-induced phase separation during the formation of a polyurethane-unsaturated polyester interpenetrating polymer network

In this study, an interpenetrating polymer network (IPN) based on a polyurethane (PU) and a partially end-capped unsaturated polyester (UPE) was prepared. The reaction-induced phase separation process of the IPN was studied using a phase contrast optical microscope and a transmission electron microscope (TEM), while reaction kinetics and onset of gelation were determined by a differential scanning calorimeter and a rheometer respectively. Except at low temperatures, the phase separation patterns were found to follow the spinodal decomposition mechanism. An interconnected phase developed quickly and was followed by coalescence of the periodic phase to form droplet/matrix type of morphology. A second level of phase separation also occurred within both the droplet and the matrix phases in some cases. The domain sizes resulting from both levels of phase separation gradually increased until the structure was locked by chemical gelation. Reaction temperature, PU reaction rate, and UPE reaction rate all had significant effects on the final morphology of the formed IPNs.     

Morphology control in symmetric polymer blends using spinodal decomposition

This paper studied, through modeling and computer simulation, the thermal-induced phase separation phenomenon in a symmetric polymer blend via spinodal decomposition. The one-dimensional model consisted of the Cahn–Hilliard theory for spinodal decomposition, and incorporated the Flory–Huggins–deGennes free energy equation, the slow mode mobility theory and reptation model for polymer diffusion. The numerical results replicated frequently reported experimental observations published in the literature for the early and intermediate stages of spinodal decomposition for symmetric polymer blends. Furthermore, the numerical results indicate that a dimensionless diffusion coefficient may be used as a parameter to control the formation and evolution of the phase-separated regions during spinodal decomposition as a means to customize functional polymeric materials with predefined material properties.     

Effects of spinodal decomposition on mechanical properties of a polyolefin blend from high to low strain rates

The effects of spinodal decomposition, a typical type of liquid-liquid phase separation (LLPS), on the mechanical properties of a pretreated statistical copolymer blend of poly(ethylene-co-hexene) (PEH) and poly(ethylene-co-butene) (PEB) were characterized by tensile testing under different strain rates. An important finding was that the strain rate and the crystallization temperature had to be considered as independent variables in analyzing the effects of spinodal decomposition on the tensile behaviors. At the high strain rate, the stress-strain curves kept irrespective of LLPS time, in which the interfacial relaxation between phase domains could not be detected, except the case crystallizing at 120 °C for 10 min. This was explained in terms of the distribution of the crystals elaborated by differential scanning calorimetry (DSC) results. However, when a relatively low strain rate was employed, a clear deterioration of tensile properties with LLPS proceeding was observed for the cases with low crystallization temperature because of its detection ability for large scale structural information, such as the phase boundary; unexpectedly, the effect of LLPS on the tensile properties was found to disappear in the high crystallization temperature cases which was due to the cooperative functions of the phase boundary and the internal structures of the phase domains. These abundant results provided a novel and indispensable instruction for the processing of polymer blends from the theoretical viewpoint.     

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.     

Morphology and properties control on rubber-epoxy alloy systems

Morphology and properties of polymer alloys can be controlled by thermody-namlcally reversible (structure freeze-in) or irreversible (structure lock-in) processes by simultaneously manipulating miscibility, mechanisms of phase separation, glass transition temperature (structural relaxation), and cure kinetics of polymer systems. Using phase diagrams consisting of binodal and spinodal curves, the morphology of epoxy/CTBN (carboxyl-terminated butadiene acryloni-trile copolymer) systems can be controlled by the mechanism of nucleation and growth or by spinodal decomposition via simultaneously manipulating the kinetic processes of phase separation and curing reactions. We have found that the particle size of the rubber reinforcement in epoxies is affected by the mechanisms of phase separation. Phase separation by nucleation and growth gives larger rubber particles than the corresponding phase separation by spinodal decomposition. This contrast in the morphology development is the consequence of controlling phase separation through chemorheological behavior. Medication of the phase separation kinetics in epoxy/CTBN systems was extremely effective at altering both morphology and properties of these alloys. This technique offers a means to shift the glass transition temperature of the rubber-rich phase drastically without reducing the glass transition temperature of the epoxy-rich phase significantly. Such control over morphology is the key to ultimately controlling material properties. This morphology manipulation allows us to tailor the mechanical properties of alloy systems.     

Phase Separation in Sol–Gel Process of Alkoxide-Derived Silica-Zirconia in the Presence of Polyethylene Oxide

Phase separation in a sol–gel process of SiO₂–ZrO₂ in the presence of polyethylene oxide is investigated. An amorphous gel with interconnected macroporous morphology is obtained when phase separation and sol–gel transition concur to fix a transitional structure of spinodal decomposition. Macropore size, together with connectivity of the pores and gel skeleton, can be controlled precisely by selecting an appropriate starting composition for preparation at a zirconium content ≤11.7 mol%. The macroporous gel retains additional mesopores <4 nm and exhibits typical bimodal pore size distribution. The addition of ZrO₂ in SiO₂ improves the thermal stability of both macroporous and mesoporous structures.     

Formation of microporous polymer fibers and oriented fibrils by precipitation with a compressed fluid antisolvent

Polymer morphology is controlled over a continuum from microspheres to interconnected bicontinuous networks to fibers with a versatile new process: precipitation with a compressed fluid antisolvent. The results are explained qualitatively as a function of phase behavior, mass-transfer pathways, and the formation rates of skin on the flowing jet. By spraying dilute polystyrene in toluene solutions into liquid carbon dioxide, extremely small 100 nm microspheres are formed. For concentrations above the critical composition, fibers are produced that are not only microcellular, but, in some instances, even hollow. Mass-transfer pathways that cross the binodal near the critical composition produce interconnected networks, likely due to spinodal decomposition. In this region, fibers composed of highly oriented microfibrils are produced at high shear rates. Preaddition of CO₂ influences the morphology because of dilution, in a similar manner as a liquid antisolvent, except that the viscosity reduction is larger due to added free volume. Because CO₂ diffuses through the glassy polystyrene skin faster than does a conventional liquid antisolvent such as methanol, it produces more porous fibers, which are also more cylindrical. © 1993 John Wiley & Sons, Inc.     

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.     

Phase Diagram for Liquid Crystalline Polymer/ Polycarbonate Blends

A novel mechanism to form binary polymer blends is through phase separation by spinodal decomposition in the unstable region of the phase diagram. The present work investigates the effects of thermally‐induced phase separation by spinodal decomposition on the morphology development of liquid crystalline polymer/polycarbonate blends. Moreover, a thermodynamic binary phase diagram is obtained using a twin‐screw extruder at various processing melt temperatures. Differential scanning calorimetry and scanning electron microscopy were used to study the miscibility of the blends and the resulting morphology. A thermodynamic binary phase diagram exhibiting a lower critical solution temperature was obtained. The droplet size distribution of the blend was also obtained and discussed in light of the Cahn‐Hilliard theory.