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.     

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.     

Phase separation of poly (methyl methacrylate) / poly (styrene-co-acrylonitrile) blends in the presence of silica nanoparticles

The effects of silica nanoparticles on the phase separation of poly (methyl methacrylate)/poly (styrene-co-acrylonitrile) (PMMA/SAN) blends are studied by the rheological method. The binodal temperatures of near-critical compositions were obtained by the gel-like behavior during spinodal decomposition, which is a character of polymer blends with co-continuous morphology. The shifted Cole–Cole plot method was introduced to determine the binodal temperatures of off-critical compositions based on the appearance of shoulder-like transition in the terminal regime of blends with droplet morphology. Such method is found also applicable in nanoparticle filled polymer blends. Moreover, a new method to determine the spinodal temperature from Fredrickson-Larson mean field theory was suggested, where the concentration fluctuation's contribution to the storage modulus is used instead of the whole dynamic moduli. This method was also successfully extended to nanoparticle filled polymer blend. The influences of the concentration and the average diameter of silica particles on the phase separation temperature were studied. It was found that the small amount of the silica nanoparticles in PMMA/SAN blends will significantly change the phase diagram, which is related to the selective location of silica in PMMA. The comparisons with thermodynamic theory of particle-filled polymer blends are also discussed.     

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.     

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.     

Controlling morphology of polystyrene/poly(vinyl methyl ether) blends undergoing spinodal decomposition process by photo-crosslinks

The morphology developing during the spinodal decomposition process of polystyrene (PS)/poly(vinyl methyl ether) (PVME) blends was successfully controlled by photo-crosslink reactions between PS chains. The crosslink reaction was carried out by taking advantage of the photodimerization of anthracene moieties that are labeled on PS chains. Effects of photo-crosslinks on the morphology induced by temperature jumps (T-jump) from the one-phase region into the spinodal region were examined under several experimental conditions such as T-jump depths and irradiation times. It was found that the concentration fluctuations developing during the spinodal decomposition process were efficiently frozen upon irradiation using a XeF excimer laser as well as a mercury (Hg) lamp. Furthermore, these ordered structures are quite stable upon annealing. These results demonstrate that the morphology developing during the spinodal decomposition process can be well controlled by easily accessible light sources such as high pressure mercury lamps. Thus the photo-crosslink reaction described in this work can provide the basis for a potential technique to design multiphase polymer materials with controllable ordered structures.     

乙醇溶液液滴降压蒸发过程传热传质特性

针对单个乙醇溶液液滴在降压环境下蒸发的传热传质过程建立了数学模型。模型基于液相的能量守恒和 传质扩散理论,利用经典拓展模型计算液滴的质量蒸发率,并引入活度系数考虑液滴表面的蒸气分压。采用液 滴悬挂法进行实验,分别记录了乙醇溶液液滴和乙酸溶液液滴在降压蒸发过程中的液滴内温度变化。将实验数 据与计算结果对比,验证了模型的有效性。通过模型计算获得了液滴内部温度分布以及浓度分布随时间的变化。 结果表明:快速降压阶段空气流动较快,加之乙醇工质易挥发,液滴表面温度下降迅速,液滴内部温差和乙醇 浓度梯度较大;压力稳定后,空气流速为零,液滴内部温差和乙醇浓度梯度逐渐减小。由于液滴内部的热扩散 速率大于传质扩散系数,内部温度随时间的变化比浓度随时间的变化更快。     

Binodal and spinodal curves: a simulation for various high polymer mixtures

Flory's equation-of-state theory has been used to predict the lower critical solution temperature behaviour of polymer—polymer mixtures. The spinodal phase boundary of numbers of high molecular weight polymer mixtures have been previously simulated using this theory. In this paper a procedure for simultaneous predictions of the binodal and the spinodal curves by equating the chemical potential of each component in the mixture is presented. The method is tested for five different mixtures. The effects of the binary and pure component state parameters on the simulated curves are discussed and the simulated phase diagrams are compared with the experimental cloud point curves. It is found that in most cases the results are more consistent with the cloud point curve being closer to the spinodal curve than the binodal.     

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.     

Studies of spinodal decomposition in a ternary polymer‐solvent‐nonsolvent system

Much of the work in modeling and computer simulation of spinodal decomposition has been done for binary systems. This work attempts to carry out the analysis of spinodal decomposition in ternary polymer‐solvent‐nonsolvent systems, where the solvent is the monomer used to produce the polymer and the nonsolvent is the major component. Various experimental methods are used to determine values of the parameters of the ternary version of the Cahn‐Hilliard equation of spinodal decomposition, such as cloudpoint experiments, time‐resolved light scattering in the ternary system, and morphological development of polymer membranes formed during the early stages spinodal decomposition. The combination of these experimental methods and computer simulation work shows the validity of the assumptions made in characterizing spinodal decomposition in ternary polymer systems of interest.     

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.     

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.     

Orientational phase-separated domains in a polyolefin blend under a temperature gradient field

We investigate the effect of a temperature gradient on the orientation of phase-separated structures in a polyolefin blend system. Phase contrast optical microscopy (PCOM) has been used to measure the morphology of phase separation via spinodal decomposition as a function of phase separation time and temperature gradient. The bicontinuous and interconnected tubelike structure, the characteristic morphology of the spinodal decomposition process, exhibits a preferential alignment along the direction of temperature gradient after phase separation. The orientation of the bicontinuous and interconnected tubelike structures gradually increases with phase separation time and temperature gradients. Also the orientation of phase-separated domains can respond really quickly to the change in the direction of external temperature gradient field. The results suggest that “thermal force” induced by the temperature inhomogeneity might play an important role in aligning phase-separated domains preferentially along the temperature gradient direction.     

Elastic Effect on Domain Morphology and Kinetics of Spinodal Decomposition in the Tetragonal System

A method was proposed for calculation of the effect of elastic strain on spinodal decomposition in the tetragonal system. An effective free energy for the composition field was derived by eliminating elastic fields which are coherently induced by composition inhomogeneities It was shown that anisotropic long-range interactions between composition fields play a major role in determining both the domainmorphology and domain growth law of spinodal decomposition with the coherence of the lattice. Computers simulations were performed on the basis of a two-dimensional model by taking into account those long-range interactions. The results demonstrated the appearance of lamella structure and its coarsening in the late stage of the phase separation The calculation for the TiO₂-SnO₂ system showed slow coarsening due to the anisotropic elastic long -range interactions The asymptotic growth of the lamella size was described by λα tⁿ, where n is 0.18.     

Phase Separation in Polymer Solutions under Extension

The results obtained recently by the authors during investigation of the phase behavior of polymer solutions under uniaxial tension are reviewed. The main attention is given to the dilute solutions of unentangled semiflexible macromolecules. The effect of the solution extension rate on the coil–stretched coil transition for semiflexible chains is considered, and stability of the system of stretched coils is analyzed in terms of their segregation followed by formation of the concentrated polymer phase. The spinodal and binodal of the system are determined depending on temperature and extension rate. The kinetics of solution segregation to polymer and solvent, where three stages, namely, (i) spinodal decomposition accompanied by the formation of regions with increased and reduced polymer contents, (ii) formation of the microfibrillar network, and (iii) network collapse yielding separation of the solvent from the polymer phase are identified, is described.     

Phase behaviours of polymer solutions in high pressure system

A modified generalized lattice-fluid (MGLF) model was developed to predict and describe phase behaviours of polymer solutions under high pressure condition. To consider the specific interaction between pure components, a new parameter, κ₁₁, was introduced into the generalized lattice-fluid (GLF) model. The proposed model was compared with a phase diagram predicted by the GLF model and experimental data for polymer solution systems (polystyrene/diethylether and polystyrene/acetone) showing lower critical solution temperature (LCST) at various pressures. The MGLF model predicted remarkably well the spinodal curve of a given polymer/solvent system.     

Gas-Sensing Properties of Spinodally Decomposed (Ti,Sn)O2 Thin Films

The gas-sensing properties of spinodally decomposed (Ti,Sn)O₂ thin films on sapphire substrates were investigated for CO, C₃H₈, and C₂H₅OH, and hydrogen gases at a temperature of 500°C. The variation in the d -spacing of the (101) plane of (Ti_0.5Sn_0.5)O₂ films showed behavior that was typical of spinodal decomposition during annealing at a temperature of 900°C. Transmission electron micrographs of the spinodally decomposed (Ti,Sn)O₂ films on sapphire (0112) substrates revealed the characteristic modulated structure. The modulated lamella microstructure consisted of TiO₂- and SnO₂-rich regions at intervals of ∼10 nm. The films were very sensitive to hydrogen gas and revealed anisotropic electrical conduction that was influenced by the modulated microstructure, which is characteristic of spinodal decomposition.     

Interdiffusion in blends of polystyrene and polymethylstyrene studied by light scattering after temperature jumps across the phase boundary

We describe a simple light scattering set-up for measuring interdiffusion coefficients D in polymer blends by generating spinodal decomposition and subsequent dissolution after temperature jumps across the phase boundary. In blends of polystyrene and polymethylstyrene (random copolymer of 60% m-methylstyrene and 40% p-methylstyrene) D values were obtained between 10⁻¹¹ and 10⁻¹⁵ cm²s⁻¹ at temperatures up to 50 K above the upper critical solution temperature. The results are discussed in relation to tracer diffusion in the same system.     

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.     

Droplet evaporation and solute precipitation during spray pyrolysis

The process of spray pyrolysis was investigated theoretically using a model that describes the evolution of the droplet size, solvent vapor concentration in the carrier gas, and both droplet and gas temperatures along the reactor axis. The model also accounts for solute concentration profiles and solute precipitation in the solution droplets. The model was used to describe the evaporation of sodium chloride aqueous solution droplets in diffusion dryers and hot-wall reactors as a function of reactor residence time, droplet size (a few microns), solution molality (up to 2 M), droplet concentration (10⁶–10⁷ cm⁻³), relative humidity of the carrier gas (0–50%) and reactor wall conditions. Decreasing initial droplet size and solution molality accelerated droplet evaporation and resulted in smaller droplets at the onset of solute nucleation. Decreasing droplet concentration and carrier gas inlet relative humidity as well as increasing wall temperature (up to 350°C) or axial wall temperature gradient (up to 100°C cm⁻¹) increased the droplet evaporation rate, but did not change appreciably the droplet size at the point of precipitation for a given droplet size and solute concentration. Thus, control of droplet size at the onset of solute nucleation by varying process parameters other than the solution concentration and initial droplet size is limited.