Miscibility and phase separation in polymer blends studied by laser light scattering

In this paper major emphasis has been placed on the phase behavior of miscible polymer blends, especially on blends containing random copolymers. Blends containing random copolymers generally tend to phase separation at elevated temperatures (LCST behavior). Experimental determination of miscibility areas as a function of temperature and copolymer composition by laser light scattering provides the interaction parameters necessary for theoretical explanations and predictions of various phase separation phenomena. Just above the LCST polymer blends exhibit regular highly interconnected two-phase morphologies. The rate of decay of these structures is estimated. The phase separation kinetics can be pursued by laser light scattering and is discussed in terms of CAHN's linearized theory. It can be shown that the linear theory adequately describes the early stage of phase decomposition. The linear theory is also applicable to the reverse phenomenon, the phase dissolution below LCST. unlike the case of phase separation the diffusion-controlled regime is that in the late stage of phase dissolution.     

Phase behavior in mixtures of a homopolymer and a block copolymer. 4. SALS and SAXS studies

Phase behavior of blends of poly(vinyl methyl ether) (PVME) with four styrene-butadiene-styrene (SBS) triblock copolymers, being of various molecular weights, architecture, and compositions, was investigated by small-angle light scattering. Small-angle X-ray scattering investigation was accomplished for one blend. Low critical solution temperature (LCST) and a unique phase behavior, resembling upper critical solution temperature (UCST), were observed. It was found that the architecture of the copolymer greatly influenced the phase behavior of the blends. Random phase approximation theory was used to calculate the spinodal phase transition curves of the ABA/C and BAB/C systems; LCST and resembling UCST phase behavior were observed as the parameters of the system changed. Qualitatively, the experimental and the theoretical results are consistent with each other. © 1996 John Wiley & Sons, Inc.     

Miscibility behavior and single chain properties in polymer blends: a bond fluctuation model study

Computer simulation studies on the miscibility behavior and single chain properties in binary polymer blends are reviewed. We consider blends of various architectures in order to identify important architectural parameters on a coarse grained level and study their qualitative consequences for the miscibility behavior. The phase diagram, the relation between the exchange chemical potential and the composition, and the intermolecular pair correlation functions for symmetric blends of linear chains, blends of cyclic polymers, blends with an asymmetry in cohesive energies, blends with different chain lengths, blends with distinct monomer shapes, and blends with a stiffness disparity between the components are discussed. For strictly symmetric blends the Flory‐Huggins theory becomes quantitatively correct in the long chain length limit, when the χ parameter is identified via the intermolecular pair correlation function. For small chain lengths composition fluctuations are important. They manifest themselves in 3D Ising behavior at the critical point and an upward parabolic curvature of the χ parameter from small‐angle neutron scattering close to the critical point. The ratio between the mean field estimate and the true critical temperature decreases like √χ/(ρb³) for long chain lengths. The chain conformations in the minority phase of a symmetric blend shrink as to reduce the number of energeticaly unfavorable interactions. Scaling arguments, detailed self‐consistent field calculations and Monte Carlo simulations of chains with up to 512 effective segments agree that the conformational changes decrease around the critical point like 1/√N. Other mechanisms for a composition dependence of the single chain conformations in asymmetric blends are discussed. If the constituents of the blends have non‐additive monomer shapes, one has a large positive chain‐length‐independent entropic contribution to the χ parameter. In this case the blend phase separates upon heating at a lower critical solution temperature. Upon increasing the chain length the critical temperature approaches a finite value from above. For blends with a stiffness disparity an entropic contribution of the χ parameter of the order 10^–3 is measured with high accuracy. Also the enthalpic contribution increases, because a back folding of the stiffer component is suppressed and the stiffer chains possess more intermolecular contacts. Two aspects of the single chain dynamics in blends are discussed: (a) The dynamics of short non‐entangled chains in a binary blend are studied via dynamic Monte Carlo simulations. There is hardly any coupling between the chain dynamics and the thermodynamic state of the mixture. Above the critical temperatures both the translational diffusion and the relaxation of the chain conformations are independent of the temperature. (b) Irreversible reactions of a small fraction of reactive polymers at a strongly segregated interface in a symmetric binary polymer blend are investigated. End‐functionalized homopolymers of different species react at the interface instantaneously and irreversibly to form diblock copolymers. The initial reaction rate for small reactant concentrations is time dependent and larger than expected from theory. At later times there is a depletion of the reactive chains at the interface and the reaction is determined by the flux of the chains to the interface. Pertinent off‐lattice simulations and analytical theories are briefly discussed.     

剪切流动对聚合物共混物相行为影响的研究进展

剪切流动对聚合物共混物相行为影响的研究进展;综述     

Miscibility studies on blends of polycarbonate with syndiotactic polymethyl methacrylate

Miscibility of bisphenol-A polycarbonate (PC) and syndiotactic polymethyle methacrylate (sPMMA) blends was investigated by differential scanning calorimetry (DSC) and small-angle light scattering. Cloud-point measurements indicated the existence of both a lower critical solution temperature and an upper critical solution temperature, forming an immiscibility loop. This immiscibility gap was observed for PC blends with sPMMA of various molecular weights ranging from 8,300 to 55,000. The DSC study on solvent-cast and coprecipitated PC/sPMMA blends from tetrahydrofuran solutions showed a single glass transition, shifting regularly with composition. The annealing of the 50/50 composition within the immiscibility loop exhibited dual glass transitions, but the system reverted to a single phase upon annealing above the loop. Phase dissolution took place during annealing above the loop, followed by thermoxidative branching (cross-linking) reaction. Dry pellets of PC and sPMMA were melt mixed above the loop in a Mini-Max mixer/molder; these molded blends exhibited a single phase. © 1993 John Wiley & Sons, Inc.     

Upper critical solution temperature type phase behavior of poly(styrene‐co‐acrylonitrile) blends with poly(styrene‐co‐n‐phenyl maleimide) and their interaction energies

To enhance the heat resistance of poly(styrene‐co‐acrylonitrile‐co‐butadiene), ABS, miscibility of poly(styrene‐co‐acrylonitrile), SAN, with poly(styrene‐co‐n‐phenyl maleimide), SNPMI, having a higher glass transition temperature than SAN was explored. SAN/SNPMI blends casted from solvent were immiscible regardless of copolymer compositions. However, SNPMI copolymer forms homogeneous mixtures with SAN copolymer within specific ranges of copolymer composition upon heating caused by upper critical solution temperature, UCST, type phase behavior. Since immiscibility of solvent casting samples can be driven by solvent effects even though SAN/SNPMI blends are miscible, UCST‐type phase behavior was confirmed by exploring phase reversibility. When copolymer composition of SNPMI was fixed, the phase homogenization temperature of SAN/SNPMI blends was increased as AN content in SAN copolymer increased. To understand the observed phase behavior of SAN/SNPMI blend, interaction energies of blends were calculated from the UCST‐type phase boundaries by using the lattice‐fluid theory combined with a binary interaction model. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1131–1139, 2008     

线性和非线性聚合物的相分离

分子共混物从20世纪60年代开始,引起很多科学家的兴趣.加工过程中,聚合物相分离过程中的热力学和动力学起了重要的作用,赋予了共混物一定的形貌,提供了很多人们需要的功能.关于聚合物的相分离问题,近年来无论在实验还是在理论上都得到了很大的发展.聚合物相分离的热力学是以Flory-Huggins的平均场理论为基础,动力学以CHC(Cahn-Hilliard-Cook)的线性理论为基础.在本文中,我们对亚稳相分离SD(Spinodal Decomposition)的热力学和动力学都进行了考察.描述了测量二元共混物的浓度涨落的静态散射实验,给出了在二元共混物体系的SD的近期理论计算.首先,从普适的Langevin方程推导CHC理论,从而给出CHC的唯象的平均场理论的微观图象.然后介绍模式耦合计算,从而将SD理论扩展到非线性区域.通过将短期SD分解与高分子共混物的对比揭示了定量计算的本质.最后,讨论了一些近年来在剪切场下相行为的研究以及该领域可能的发展方向.     

Phase behavior of polymer/diluent/diluent mixtures and their application to control microporous membrane structure

Rechargeable battery separators containing controlled pores were fabricated via the thermally-induced phase separation (TIPS) process. Based on the idea that pores could be manipulated by controlling the liquid–liquid phase separation temperature in the TIPS process, phase boundaries of the polymer–diluent systems were controlled by using diluent mixtures. Phase behaviors of the polymer/diluent/diluent ternary blends consisting of polyethylene (PE) as polymer, and soybean oil (SBO) and dioctyl phthalate (DOP) as diluents were explored. PE/SBO and PE/DOP binary blends, and PE/SOB/DOP ternary blends exhibited typical upper critical solution temperature (UCST) type phase behaviors, and the phase separation temperatures of the PE/SBO blends were higher than those of the PE/DOP blends. When the mixing ratio of the polymer and diluent-mixture was fixed, the phase separation temperature of the PE/SBO/DOP blend initially increased with increasing SBO content in the diluent-mixture passing through a maximum centered at about 80 wt% SBO and decreased beyond this point. Furthermore, the phase separation temperature of the PE/diluent-mixture blend was always higher than that of the PE/SBO blend when the diluent-mixture contained more than or equal to 50 wt% SBO. To understand the observed phase behavior of the blends, thermodynamic analyses based on the lattice-fluid theory were performed. Larger pore membranes were fabricated from the blend when higher phase separation temperatures of the blend were exhibited.     

Modeling of thermodynamic behavior of PVT properties and cloud point temperatures of polymer blends and polymer blend + carbon dioxide systems using non-cubic equations of state

In recent years, many factors influencing phase behavior of polymer blends have been studied because of their widely technological importance, as a simple method of formulating new materials with tailored properties which make them suitable for a variety of applications. This work has three main goals which were reached by using the Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT) and the Sanchez–Lacombe (SL) non-cubic equations of state (EoS), which in previous works have shown their ability to handle long chain and associating interactions. First, both equations of state were tested with the correlation of the specific volumes of pure blends (PBD/PS, PPO/PS, PVME/PS, PEO/PES) and the prediction of the specific volumes for blends; second, the modeling of blend miscibilities in the liquid–liquid equilibria (LLE) of PBD/PS, PPG/PEGE, PVME/PS, PEO/PES, and PnPMA/PS blends; third, the modeling of the phase behavior of PS/PVME blends at various compositions in the presence of CO₂. PC-SAFT and SL pure-component parameters were regressed by fitting pure-component data of real substances (liquid pressure–volume–temperature, PVT, data for polymers and vapor pressure and saturated liquid molar volume for CO₂) and the fluid phase behavior of blend systems were simulated fitting one binary interaction parameter (k_ij) by regression of experimental data using the modified likelihood maximum method. Results were compared with experimental data obtained from literature and an excellent agreement was obtained with both EoS, which were also capable of predicting the fluid phase behavior corresponding to the critical solution temperatures (LCST: lower critical solution temperature, UCST: upper critical solution temperature) of blends.     

Effect of aromatic substitution on phase behavior of blends of halogenated polystyrene and conventional polystyrene

Miscibility phase behavior in blends of poly(bromostyrene) with polystyrene (PS) has been investigated by means of time‐resolved light scattering, optical microscopy, and DSC. Cloud point phase diagrams of blends of conventional PS with poly‐(2‐bromostyrene) (P2BrS), poly‐(3‐bromostyrene), and poly‐(4‐bromostyrene) of comparable molecular weights were established by light scattering. Of particular interest is the fact that ortho, meta, and para substitutions in the styrenic aromatic rings of poly(bromostyrene) show profound effects on the composition–temperature phase diagrams of their blends with PS, exhibiting a lower critical‐solution temperature (LCST), an upper critical solution temperature (UCST), and combined LCST/UCST diagrams, respectively. Poly‐(2‐chlorostyrene) exhibits an LCST behavior very close to that of the P2BrS blend, suggesting that these types of halogen atoms may be inconsequential to phase behavior. A similar study has been extended to a PS blend containing commercial brominated PS (66 mol % bromine substitution) to determine what location of bromine substitution is crucial for miscibility enhancement in the flame‐retardant brominated PS blends. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1605–1615, 2001     

Monte Carlo simulation of polymeric materials: Recent progress

Monte Carlo simulations are presented, dealing with phase diagrams of block copolymer melts and polymer blends, including the unmixing kinetics of the latter systems. The theoretical background is briefly reviewed: Ginzburg-type criteria reveal that in mixtures of long flexible polymers a “crossover” occurs from mean-field behavior (as described by Flory-Huggins theory) to nonclassical Ising-type behavior, and spinodal curves can be unusually sharp. This crossover is demonstrated by large scale simulations of the bond fluctuation model, and it is also shown that for symmetric mixtures the critical temperature scales with chain length as T_c α N. The prefactor in this relation is distinctly smaller than predicted by Flory-Huggins, but the Curro-Schweizer integral equation theory prediction T_c α √N is clearly ruled out. Tests of the Cahn theory on the initial stages of spinodal decomposition of polymer blends will also be reported. To conclude, the mesophase formation in block copolymers is discussed, and it is shown that the simulations agree very well with experiment. The pronounced chain stretching that already occurs in the disordered phase is compelling evidence against the validity of simple random phase approximation concepts for these systems. This shows how Monte Carlo simulations can assist in better understanding large classes of polymeric materials.     

Miscibility of bisphenol-A polycarbonate with poly(methyl methacrylate)

The miscibility of bisphenol-A polycarbonate (PC) with poly(methyl methacrylate) (PMMA) has been reexamined using differential scanning calorimetry (DSC) and optical indications for phase separation on heating, i.e., lower critical solution temperature (LCST) behavior. Various methods have been used to prepare the blends including methylene chloride (CH₂Cl₂) and tetrahydrofuran (THF) solution casting, melt mixing, and precipitation of PC and PMMA simultaneously from THF solution by using the nonsolvents methanol and heptane. It is shown that the resulting phase behavior for PC/PMMA blends is strongly affected by the blend preparation method. However, these blends are miscible over the whole blend composition range (unambiguous single composition-dependent T_g's and LCST behavior) when prepared by precipitation from solution using heptane as the nonsolvent. To the contrary, solution-cast and melt-mixed PC/PMMA blends were all phase separated, which may be attributed to the “solvent” effect and LCST behavior, respectively, not discovered in previous reports. Methanol precipitation does not lead to fully mixed blends, which demonstrates the importance of the choice of nonsolvent when using the precipitation method.     

Interactions in SMA-SAN blends

Styrene/maleic anhydride (SMA) and styrene/acrylonitrile (SAN) copolymers have previously been shown to form miscible blends when the MA and AN contents do not differ too greatly. It is shown here that this is the result of a weak exothermic interaction between the MA and AN units by measuring the heats of mixing for appropriate liquid analogs of the various monomer units. The region of copolymer compositions for miscibility of SMA-SAN blends is predicted from the Sanchez-Lacombe mixture theory using net interaction parameters calculated from the analog calorimetry results via a simple binary interaction model for copolymers. Lower critical solution temperature behavior was observed for blends of copolymers having compositions near the edge of the miscibility region. Various glass transition, volumetric, and FTIR results are discussed in terms of the interactions observed.     

Miscibility of polysulfone blends with poly(1‐vinylpyrrolidone‐co‐styrene) copolymers and their interaction energies

The miscibility of polysulfone (PSf) with various hydrophilic copolymers was explored. Among these blends, PSf gave homogeneous mixtures with poly(1‐vinylpyrrolidone‐co‐styrene) [P(VP–S)] copolymers when these copolymers contained 68–88 wt % 1‐vinylpyrrolidone (VP). Miscible PSf blends with P(VP–S) copolymers underwent phase separation on heating caused by lower critical solution temperature (LCST)‐type phase behavior. The phase behavior depended on the copolymer composition. Changes in the VP content of P(VP–S) copolymers from 65 to 68 wt % shifted the phase behavior from immiscibility to miscibility and the LCST behavior. The phase‐separation temperatures of the miscible blends first increased gradually with the VP content, then went through a broad maximum centered at about 80 wt % VP, and finally decreased just before the limiting content of VP for miscibility with PSf. The interaction energies of binary pairs involved in PSf/P(VP–S) blends were evaluated from the phase‐separation temperatures of PSf/P(VP–S) blends with lattice‐fluid theory combined with a binary interaction model. The decrease in the contact angle between water and the membrane surface with increasing VP content in P(VP–S) copolymers indicated that the hydrophobic properties of PSf could be improved via blending with hydrophilic P(VP–S) copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1401–1411, 2003     

Crystallization and melting behavior of poly(ethylene oxide)/poly(n-butyl methacrylate) blends

The phase diagram, crystallization and melting behavior of poly(ethylene oxide) (PEO)/poly(n-butyl methacrylate) (PnBMA) blends have been investigated using differential scanning calorimetry and optical microscopy. The results show that the blends are miscible up to 85 °C and show an lower critical solution temperature-type demixing at a higher temperature. The isothermal crystallization studies of the blends indicate a reduction in the overall rate of crystallization. Analysis of isothermal crystallization data by means of Avrami equation leads to average values of the Avrami index of 2.5 for pure PEO and 3.0 for the different blend compositions. The melting behavior of the blends reveals double endotherms, which is ascribed to both secondary crystallization and recrystallization. The melting point depression study yielded χ₁₂=0, indicating a relatively low interaction strength.     

Immiscibility,upper critical solution temperature,and miscibility in blends of poly(vinyl ether)s with polyacrylics: Effects of pendant groups

Various phase behavior of blends of poly(vinyl ether)s with homologous acrylic polymers (polymethacrylates or polyacrylates) were examined using differential scanning calorimetry, optical microscopy (OM), and Fourier‐transformed infrared spectroscopy. Effects of varying the pendant groups of either of constituent polymers on the phase behavior of the blends were analyzed. A series of interestingly different phase behavior in the blends has been revealed in that as the pendant group in the acrylic polymer series gets longer, polymethacrylate/poly(vinyl methyl ether) (PVME) blends exhibit immiscibility, upper critical solution temperature (UCST), and miscibility, respectively. This study found that the true phase behavior of poly(propyl methacrylate)/PVME [and poly(isopropyl methacrylate)/PVME)] blend systems, though immiscible at ambient, actually displayed a rare UCST upon heating to higher temperatures. Similarly, as the methyl pendant group in PVE is lengthened to ethyl (i.e., PVME replaced by PVEE), phase behavior of its blends with series of polymethacrylates or polyacrylates changes correspondingly. Analyses and quantitative comparisons on four series of blends of PVE/acrylic polymer were performed to thoroughly understand the effects of pendant groups in either polyethers (PVE's) or acrylic polymers on the phase behavior of the blends of these two constituents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1521–1534, 2007     

High-temperature fourier transform infrared study of polystyrene/poly(vinyl methyl ether) blends

Fourier transform infrared (FTIR) studies of polystyrene (PS)/poly(vinyl methyl ether) (PVME) miscible blends as a function of temperature are presented. Below the lower critical solution temperature (LCST) little change is observed in the interaction spectrum obtained via digital subtraction techniques. Once above the LCST, the magnitude of the interaction spectrum decreases as a result of the phase separation process. Comparison of the behavior of the ether C? O stretching band in the reference PVME and in the blends has yielded a lower limit estimate for the interaction energy of about 0.15 kcal/mol.     

Blends of poly(vinyl methyl ether) with styrenic copolymers

Blends of poly(vinyl methyl ether) (PVME) with styrene/acrylonitrile (SAN), with styrene/maleic anhydride (SMA), and with styrene/acrylic acid (SAA) copolymers were examined for glass transition and lower critical solution temperature behavior. These copolymers were found to be completely miscible with PVME at levels of 3% or less of AA; below 10–11% AN, and below 15% MA (w%). Small amounts of the comonomers raised the temperature at which blends with PVME undergo phase separation on heating. This effect was greatest in the order AA > AN > MA. An interpretation of these results is given in terms of recent theories for homopolymer-copolymer blends, and the extent to which solubility parameter theory can be useful is considered.     

Crystalline-amorphous interaction in relation to the phase diagrams of binary polymer blends containing a crystalline constituent

The present article describes an equilibrium theory for determining binary phase diagrams of various crystalline-amorphous polymer blends by taking into account the contributions from both liquid-liquid phase separation between the constituents and solid-liquid phase transition of the crystalline component. An analytical expression for determining a crystal-amorphous interaction parameter is deduced based on the solid-liquid transition, involving the solidus and liquidus lines in conjunction with the coexistence curve of an upper critical solution temperature type. Of particular importance is that the crystalline-amorphous interaction parameter can be determined directly from the melting point depression data. The present analysis is therefore different from the conventional Flory-Huggins interaction parameter, which is associated with the liquid-liquid phase separation. The validity of the present theory is tested with the experimental phase diagrams of blends of poly(ethylene oxide)/diacrylate and poly(vinyl alcohol)/cellulose.     

Shear flow effect on phase behavior and morphology in polymer blends

The effect of simple shear flow on the phase behavior and morphology was investigated for both polystyrene/poly(vinyl methyl ether) (PS/PVME) and poly(methyl methacrylate)/poly(styrene‐co‐acrylonitrile) (PMMA /SAN‐29.5) blends, which have LCST (lower critical solution temperature)‐type phase diagram. The measurements were carried out using a special shear apparatus of two parallel glass plates type. The PS/PVME blends showed shear‐induced demixing and shear‐induced mixing at low and high shear rate values, respectively. In addition, the rotation speed and the sample thickness were found to have a pronounced effect on the phase behavior under shear flow. On the‐other hand, PMMA/SAN blend showed only shear‐induced mixing and the magnitudes of the elevation of the cloud points were found to be composition and molecular weight dependent. The morphology of the PMMA/SAN=75/25 blend indicated that shear‐induced mixing occurred at a critical shear rate value, below which the two phases were highly oriented and elongated in the flow direction.