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.     

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.     

Morphology of a hydrogen-bonded LC polymer prepared by photopolymerization-induced phase separation under an isotropic phase

A hydrogen-bonded LC polymer was prepared by photopolymerization of an LC blend composed of 4-(6-acryloyloxyhexyloxy)benzoic acid (A6OBA) and 4-hexyloxy-4′-cyanobiphenyl (6OCB), containing small amounts of an inhibitor and photoinitiator, at two different temperatures in an isotropic phase. To elucidate the factors determining the morphology of the obtained polymer (poly(A6OBA)), we chose two irradiation temperatures: one in the LC temperature range of the polymer, the other in the isotropic range. We investigated structures of the polymers by optical microscopy and scanning electron microscopy. SEM images showed that the film obtained at the lower temperature consisted of randomly extended fibers having a diameter of ca. 1.0 μm and some branches, whereas the film prepared at the higher temperature was composed of polymer particles with a diameter ca. 1.5 μm. By comparing these results with those of an earlier experiment in which we obtained macroscopically oriented LC fibers by photopolymerization under the LC phase of the blend, we infer the following; (i) the presence of an LC phase in the resulting polymer itself during photopolymerization is necessary for it to form fibrous morphology and (ii) the LC ordering field present prior to photopolymerization is not indispensable for the fibrous morphology but it is for the macroscopic orientation and reduction of the branches in the fibers.     

Morphology development in photopolymerization-induced phase separated mixtures of UV-curable thiol-ene adhesive and low molecular weight solvents

The influence of photopolymerization rate, solvent quality, and processing parameters on the photopolymerization-induced phase separated morphology of mixtures of thiol-ene based optical adhesive with mixed solvents of diglyme and water or acetone and isopropanol is described. Upon exposure to UV radiation (∼50 mW/cm², 365 nm) for periods of 10-90 s, homogeneous solutions of 5-10 wt% NOA65 and NOA81 adhesive formed phase separated structures with characteristic sizes ranging from 400 nm to 10 μm, with increased photopolymerization rates leading to smaller feature sizes. In the systems containing diglyme and water, morphologies formed by phase separation at a lower degree of photopolymerization were characteristic of spinodal decomposition, while morphologies formed by phase separation at a higher degree of photopolymerization exhibited characteristics of viscoelastic phase separation. In the systems containing acetone and isopropanol, interactions between evaporation and photopolymerization-induced phase separation led to the development of more complicated morphologies, including three-dimensional sparse networks. These morphologies provide a combination of connectivity and low overall volume fraction that can significantly enhance the performance of many multi-functional structures.     

Spinodal decomposition as a probe to measure the effects on molecular motion in poly(styrene-co-acrylonitrile) and poly(methyl methacrylate) blends after mixing with a low molar mass liquid crystal or commercial lubricant

The effects on molecular motion observed through early stage phase separation via spinodal decomposition, in melt mixed poly(styrene-co-acrylonitrile) (SAN) containing 25% by weight of acrylonitrile (AN) and poly(methyl methacrylate) (PMMA) (20/80 wt%) blends after adding two low molar mass liquid crystals (CBC33 and CBC53) and two lubricants (GMS and zinc stearate) were investigated using light scattering techniques. The samples were assessed in terms of the apparent diffusion coefficient (D_app) obtained from observation of phase separation in the blends. The early stages of phase separation as observed by light scattering were dominated by diffusion processes and approximately conformed to the Cahn-Hilliard linearised theory. The major effect of liquid crystal (LC) was to increase the molecular mobility of the blends. The LC generally increased the Cahn-Hilliard apparent diffusion coefficient, D_app, of the blend when added with concentrations as low as 0.2 wt%. GMS and zinc stearate can also improve the mobility of the blend but to a lesser extent and the effect does not increase at higher concentration. On the other hand, the more LC added, the higher the mobility. In all systems the second derivative of the Gibbs free energy becomes zero at the same temperature. The improved mobilities therefore seem to arise from changes in dynamics rather than thermodynamic effects.     

Morphology development in immiscible polymer blends during crystallization of the dispersed phase under shear flow

Crystallization under shear of dispersed polybutylene terephthalate (PBT) fibers in copolymer polyethylene-methyl acrylate matrix (EMA) was investigated using a hot optical shear device. Crystallization during isotherm and cooling process was studied. Static crystallization experiments were carried out for comprehension purpose. Differential scanning calorimetry (DSC) analysis was performed in order to predict the crystallization behavior of PBT. Shear enhancement of its crystallization was thus demonstrated from rheological experiments. Interfacial tension of EMA/PBT blend was experimentally measured using the hot optical shear device. Theoretical break-up times of PBT fibers were also calculated. Control of the morphology through shear rate and crystallization time balance was demonstrated. Static crystallization experiments show that decreasing crystallization time favor fibrillar morphology. Breaking up of fibers was brought to the fore during dynamic crystallization experiments due to heterogeneous development of the crystallization along the fiber. During the dynamic crystallization, rapid quenching enables fibrillar morphology. Long crystallization times associated with low shear rates allow nodular morphology.     

Filler effect on polymerization kinetics and phase separation in polymer blends formed in situ

The kinetics of formation of a mixture of two polymers [poly(methyl methacrylate) and polyurethane] in situ in the course of two simultaneously proceeding reactions was studied in the presence of various amount of a filler (fumed silica). It was shown that the filler affects the rates of both reactions. In addition, the filler exerts an influence on the phase separation induced by the chemical reaction increasing the amount of a filler increases the time for the onset of phase separation. The effects observed may be explained both by the increase in the viscosity of the reaction system due to introduction of a filler and by selective adsorption of reaction system components at the interface with filler particles. In all cases, phase separation in the early stages of reaction proceeds in a four‐component system (two polymers formed and two initial compounds) and obeys the spinodal mechanism. It is also shown that the final morphology is determined far from the end of the reaction and before establishing the equilibrium state. © 2003 Society of Chemical Industry     

Computer simulation study on the shear-induced phase separation in semi-dilute polymer solutions by using Ianniruberto-Marrucci model

In our previous study, a computer simulation scheme based on Doi-Onuki theory is proposed to simulate the dynamics of the shear-induced phase separation in semi-dilute polymer solutions [KOBUNSHI RONBUNSHU 2007, 64, 324]. The scheme employs Ianniruberto-Marrucci model as a constitutive equation to express the viscoelastic behavior of the solution explicitly. The scheme enables us to simulate the time-evolution of stress as well as that of shear-induced structure upon shear-jump. In this study, we focus on the conformation of polymer chains. The dynamics of the polymer chains agrees with those in the “solvent squeeze” model which interprets the shear-induced phase separation phenomena in semi-dilute polymer solutions by Saito et al. [Macromolecules 1999, 32, 4879].     

Computer simulation study on the shear-induced phase separation in semidilute polymer solutions in 3-dimensional space

We investigated the shear-induced phase separation and/or concentration fluctuation phenomena in semidilute polymer solution by using computer simulation in 3-dimensional space with Doi-Onuki theory. The enhancement of the concentration fluctuations occurs under shear flow and the scattering function in q_x-q_z plane exhibits the so-called butterfly pattern as observed experimentally, where q_x and q_z are the components of the scattering vector for flow direction and neutral direction, respectively. The time changes in the peak position and the intensity at peak position in the scattering function in q_x-q_z plane can be divided into two regions: the peak position becomes smaller and the peak intensity increases with t, and then the peak position and intensity become constant and the system reaches its steady state. These agree with the experimental results qualitatively. However, the computer simulation results indicate that the peak position at the steady state is almost independent of the shear rate, while the decrease in the peak position at steady state with shear rate has been observed experimentally. This disagreement originates from the use of the simplest constitutive equation in the computer simulation.     

Effect of polymer-filler surface interactions on the phase separation in polymer blends

For the blends of chlorinated polyethylene and copolymer of ethylene with vinyl acetate, the effect of the introducing filler (fumed silica) on the phase behavior of the blends was investigated. It was found that introducing filler in polymer blends depending on its amount lead either to the increase or to the decrease in the temperature of phase separation. At the filler concentration where both components transit into the state of a border layers, the phase separation temperature increases. This effect was explained by the change of the total thermodynamic interaction parameter in the ternary system polymer-polymer-filler. At lower concentration of a filler, the possible effect is the redistribution of the blend components according to their molecular masses between filler surface (in the border layer) and in the bulk that may diminish the phase separation temperature.Effect of the filler on the phase behavior was explained by the simultaneous action of two mechanisms: by changing the thermodynamics of interaction near the surface due to selective adsorption of one of the components and by the redistribution of components according to their molecular masses between the boundary region (near the surface) and in the matrix.The measurements of the kinetics of phase separation and calculation of the parameters of the activation energy are in agreement with proposed mechanisms.     

Salami pattern formation during phase separation induced by polymerization of 2-chlorostyrene in the presence of polystyrene

Development of morphological structures during phase separation induced by radical polymerization of 2-chlorostyrene in the presence of polystyrene was studied with an electron microscope. No stirring of the mixture was made. Domain structure changed significantly with initial monomer composition within a narrow range. Salami domains similar to those observed in high-impact polystyrene (HIPS) formed at certain initial compositions, notwithstanding that production of graft polymers, which was known to play an essential role of the salami structure formation in HIPS, was negligible in this system. An explanation for the mechanism of salami pattern formation was proposed.     

A preliminary study of the dynamics of phase separation in oligomeric polystyrene-polybutadiene blends

We report here the preliminary results of a study of the kinetics of spinodal decomposition in an oligomeric blend, polystyrene with polybutadiene using small angle light scattering. The data are compared with the theoretical predictions of Cahn-Hilliard and van-Aartsen. The results corroborate the position of the critical point as determined by the pulse induced critical scattering technique.     

Morphology of polyvinylidene fluoride and its blend in thermally induced phase separation process

Polyvinylidene fluoride (PVDF) and its blend films were prepared by melt‐blending the binary mixture of PVDF/dibutyl phthalate (DBP) and the ternary mixture of PVDF/CaCO₃/DBP in combination of TIPS. Their morphologies were characterized by scanning electron microscope depended on preparation condition, such as the diluent and CaCO₃ weight fraction, and the cooling rate, and the crystallization information was also investigated by DSC. The results showed that CaCO₃ influenced the morphology of PVDF in the TIPS process regardless of the cooling conditions, and the formation of the spherulitic morphology can be disturbed by CaCO₃ at the quenching condition. The effect of CaCO₃ weight fraction on the tensile strength of PVDF was measured, which indicated CaCO₃ had a negative effect on PVDF tensile strength. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2944–2952, 2006     

Morphology and properties of foamed high crystallinity PEEK prepared by high temperature thermally induced phase separation

Polyetheretherketone (PEEK) is a high-performance semi-crystalline thermoplastic polymer with outstanding mechanical properties, high thermal stability, resistance to most common solvents, and good biocompatibility. A high temperature thermally induced phase separation technique was used to produce PEEK foams with controlled foam density from PEEK in 4-phenylphenol (4PPH) solutions. Physical and mechanical properties, foam and bulk density, surface area, and pore morphology of foamed PEEK were characterized and the role of PEEK concentration and cooling rate was investigated. Porous PEEK with densities ranging from 110 to 360 kg/m³ with elastic moduli and crush strength ranging from 13 to 125 MPa and 0.8 to 7 MPa, respectively, was produced.     

Layered structure formation in the reaction-induced phase separation of epoxy/polysulfone blends

In an epoxy/polysulfone blend, the reaction-induced phase separation behavior and the final morphology were investigated. Three distinct morphological structures were obtained. Sea-island and nodular structures were observed at lower and higher polysulfone contents, respectively. A three-layered structure was obtained in the middle polysulfone concentration range. In order to understand the formation of three-layered structure, phase separation process was studied using time-resolved light scattering, phase-contrast optical microscope and scanning electron microscope. Bicontinuous structure formed uniformly in the whole sample at the beginning of phase separation. After the phase structure grew for a certain time, large domains formed and developed. Then, the large epoxy-rich domains gradually flew to the outer space of the sample film. This process assisted the formation of the three-layered structure. The mechanism of the formation of the three-layered structure was discussed based on the different viscoelastic properties of the components.     

Kinetics of photopolymerization-induced phase separation and morphology development in mixtures of a nematic liquid crystal and multifunctional acrylate

Photopolymerization behavior and reaction kinetics for a series of multifunctional acrylate monomer(s) and eutectic liquid crystal blends were investigated with particular emphasis on determination of the reaction rate coefficients for propagation and termination steps of photopolymerization. Reaction rate coefficients were determined via real-time infrared spectroscopy and compared with those obtained by photo-differential scanning calorimetry. Effects of various parameters such as LC concentration, light intensity, and monomer functionality on the kinetics were investigated. Phase transition temperature versus composition phase diagrams were established by means of optical microscopy and differential scanning calorimetry for mixtures of triacrylate/liquid crystal (LC) before photopolymerization and after exposing to ultra violet (UV) irradiation under various reaction times. The snapshot phase diagram of the reacting mixtures exhibited isotropic gel, isotropic liquid + nematic, and narrow pure nematic coexistence regions. These coexistence regions were further confirmed by morphological changes of the polymer dispersed liquid crystal films as functions of temperature and concentration using polarized optical microscopy.     

湿相分离法壳聚糖膜的结构与性能研究

采用湿相分离法制备壳聚糖膜。主要研究成型条件对壳聚糖膜力学性能和膜的形态结构的影响。结果表明,用氢氧化钠和无水硫酸钠的双组分凝固浴可获得具有良好的力学性能和内部结构的壳聚糖膜。当双组分凝固浴浓度为6%NaOH-1.2%Na2SO4,凝固时间为6 h时,制得的壳聚糖膜的拉伸强度可达到12.44 MPa。经过交联改性可以进一步提高壳聚糖膜的机械性能并改善其内部结构。     

Optimization of structure and properties of polyphenylene sulfide porous membrane by controlling the process of thermally induced phase separation

Polyphenylene sulfide (PPS) porous membranes were successfully prepared from miscible blends of PPS and polyethersulfone (PES) via thermally induced phase separation followed by subsequent extraction of the PES diluent. The morphologies, crystalline structures, mechanical properties, pore structures and permeate fluxes of the PPS porous membranes obtained from different phase separation processes were characterized and are discussed. During the phase separation in the heating process, PPS and PES mainly underwent liquid–liquid phase separation, and then a nonhomogeneous porous structure with a mean pore size of 100 μm and a honeycomb‐like internal structure formed on the membrane surface. The phase separation of PPS/PES occurring in the cooling process was easier to control and the related pore diameter distribution was more regular. In the process of direct annealing, as the phase separation temperature decreased, the pore size distribution became more homogeneous and the mean diameter of the pores also decreased gradually. When the phase separation temperature decreased to 200 °C, PPS membranes with a network structure and a uniform as well as well‐interconnected porous structure could be obtained. In addition, the maximum permeation flux reached 1718.03 L m^–2 h^–1 when the phase separation temperature was 230 °C. The most probable pore diameter was 6.665 nm, and the permeate flux of this membrane was 2.00 L m^–2 h^–1; its tensile strength was 17.07 MPa. Finally, these PPS porous membranes with controllable pore structure as well as size can be widely used in the chemical industry and energy field for liquid purification. © 2020 Society of Chemical Industry     

The external electric field effects on the morphology of phase separation in a mixture of liquid crystal/flexible polymer

In this article, the morphologies of phase separation in the mixtures of small molecular liquid crystal and flexible polymers with or without being subjected to the external electric field are preliminarily studied by polarized light microscope. It is found that the characteristic “Swiss cheese” morphology can always be observed for the case of zero field strength. For the case of 1.2 V/μm field strength, it is found that the external electric field make the binodal curves of the phase diagrams shift to higher temperature and the “Swiss cheese” morphology can never be observed. However, the domain growth rate is highly accelerated due to the fact that the electric field oriented liquid crystal phase excludes the polymer coils strongly. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 250–258, 2002