Hidden minima of the gibbs free energy revealed in a phase separation in polymer/surfactant/water mixture

We observed a very unusual kinetic pathway in a separating C(12)E(6)/PEG/H(2)O ternary mixture. We let the mixture separate above the spinodal temperature (cloud point temperature) for some time and next cool it into a metastable region of a phase diagram, characterized by two minima of the Gibbs potential, one corresponding to the homogeneous mixture and one to the fully separated PEG-rich and C(12)E(6)-rich phases. Despite the fact that in the metastable region the thermodynamic equilibrium corresponds to the separated phases (global minimum of the Gibbs free energy), we observe perfect mixing of the initially separated phase. The homogeneous state, obtained in this way, does not separate, if left undisturbed. However, many cooling-heating cycles or full separation with visible meniscus above the cloud point temperature induce the phase separation in the metastable region. The metastable region can exist tens of degrees below the cloud point temperature. This effect is not observed in the binary mixture of C(12)E(6)/H(2)O.     

Phase separation during synthesis of polyetherimide/epoxy semi-IPNs

The phase separation behavior and the morphology of polyetherimide (PEI)-modified diglycidyl ether of bisphenol A (DGEBA) epoxy resin were studied using scanning electron microscopy and light scattering. Reaction kinetics, cloud point and onset of gelation were determined by differential scanning calorimeter, optical microscope and physica rheometer, respectively. The mixture of partially cured epoxy and PEI showed bimodal upper critical solution temperature (UCST) behavior. For PEI content smaller than 10 wt%, the blends exhibited a sea-island morphology formed via nucleation and a growth mechanism. Above 25 wt% PEI content, the phase separation proceeded via a spinodal decomposition mechanism and a nodular structure was formed. With PEI content between 15 and 20 wt%, dual phase morphology was observed. This morphology was formed via primary spinodal decomposition and secondary phase separation within the dispersed phases and the matrix phases formed by the primary phase separation. This morphology was presumed to be formed in the reaction-induced phase separation mechanism with the mixture showing bimodal UCST behavior. The curing temperature had an effect on the final morphology, and the modulus of PEI-modified epoxy was influenced by the phase separation.     

Macroporous Morphology of the Titania Films Prepared by a Sol-Gel Dip-Coating Method from the System Containing Poly(ethylene glycol): Effects of Molecular Weight and Dipping Temperature

Macroporous morphology has been examined for the titania (TiO₂) films prepared by a sol-gel dip-coating method from the system containing poly(ethylene glycol) (PEG) under the variations of molecular weight of PEG and dipping temperature. The macroporous morphology is observed only within the limited range of molecular weight because the compatibility between PEG and the solvent mixture is quite sensitive to the molecular weight. The macroscopic domain formation is enhanced at higher withdrawal speed when the dipping temperature is raised, suggesting that the fluidity reduction and the phase separation are more accelerated than the polycondensation due to the enhanced solvent evaporation.     

Reaction-induced phase separation in polyethersulfone-modified epoxy-amine systems studied by temperature modulated differential scanning calorimetry

In epoxy-amine systems with a thermoplastic additive, the initially homogeneous reaction mixture can change into a multi-phase morphology as a result of the increase in molecular weight or network formation of the curing matrix. Temperature modulated DSC (TMDSC) allows the real-time monitoring of this reaction-induced phase separation. A linear polymerizing epoxy-amine (DGEBA–aniline) and a network-forming epoxy-amine (DGEBA–methylene dianiline), both with an amorphous engineering thermoplastic additive (polyethersulfone, PES), are used to illustrate the effects of phase separation on the signals of the TMDSC experiment. The non-reversing heat flow gives information about the reaction kinetics. The heat capacity signal also contains information about the reaction mechanism in combination with effects induced by the changing morphology and rheology such as phase separation and vitrification. In quasi-isothermal (partial cure) TMDSC experiments, the compositional changes resulting from the proceeding phase separation are shown by distinct stepwise heat capacity decreases. The heat flow phase signal is a sensitive indication of relaxation phenomena accompanying the effects of phase separation and vitrification. Non-isothermal (post-cure) TMDSC experiments provide additional real-time information on further reaction and phase separation, and on the effect of temperature on phase separation, giving support to an LCST phase diagram. They also allow measurement of the thermal properties of the in situ formed multi-phase materials.     

Unmixing of polymer blends confined in ultrathin films: crossover between two-dimensional and three-dimensional behavior

The interplay between chain conformations and phase separation in binary symmetric polymer mixtures confined into thin films by "neutral" hard walls (i.e., walls that do not preferentially attract or repel one of the two components of the mixture) is studied by Monte Carlo simulations. Using the bond fluctuation model on a simple cubic lattice in the semi grand canonical ensemble, we locate the critical temperature of demixing via finite size scaling methods for a wide range of chain lengths (16 infinity, and hence T(c) proportional, variant N. However, strong deviations from the Flory-Huggins theory occur as long as the unperturbed chain dimension exceeds D, and the critical behavior falls in the universality class of the two-dimensional Ising model for any finite value of D.     

Relaxations and nano-phase-separation in ultraviscous heptanol-alkyl halide mixture

To gain insight into the effects of liquid-liquid phase separation on molecular relaxation behavior we have studied an apparently homogeneous mixture of 5-methyl-2-hexanol and isoamylbromide by dielectric spectroscopy over a broad temperature range. It shows two relaxation regions, widely separated in frequency and temperature, with the low-frequency relaxation due to the alcohol and the high-frequency relaxation due to the halide. In the mixture, the equilibrium dielectric permittivity epsilon(s) of the alcohol is 41% of the pure state at 155.7 K and epsilon(s) of isoamylbromide is approximately 86% of the pure state at 128.7 K. The difference decreases for the alcohol component with decreasing temperature and increases for the isoamylbromide component. The relaxation time tau of 5-methyl-2-hexanol in the mixture at 155.7 K is over five orders of magnitude less than in the pure state, and this difference increases with decreasing temperature, but tau of isoamylbromide in the mixture is marginally higher than in the pure liquid. This shows that the mixture would have two T(g)'s corresponding to its tau of 10(3) s, with values of approximately 121 K for its 5-methyl-2-hexanol component and approximately 108 K for its isoamylbromide component. It is concluded that the mixture phase separates in submicron or nanometer-size aggregates of the alcohol in isoamylbromide, without affecting the latter's relaxation kinetics, while its own epsilon(s) and tau decrease markedly.     

Rational Fabrication of Multiple Dimensional Assemblies from Tryptophan-Based Racemate

Fabricating structural complex assemblies from simple amino acid-based derivatives is attracting great research interests due to their easy accessibility and preparation. However, the morphological regulation of racemates (an equimolar mixture of enantiomers) were largely overlooked. In this work, through rational modulation of kinetic and thermodynamic parameters, we achieved multiple dimensional architectures employing tryptophan-based racemate (RPWM). Upon assembling, 1D bundled nanofibers, 2D lamellar nanostructure and 3D urchin-like microflowers could be obtained depending on the solvents used. The corresponding morphology evolutions were successfully illustrated by changing the enantiomeric excess (ee) value. Moreover, for RPWM, uniform 0D nanospheres were formed in H₂O under 4 °C, which could spontaneously convert into lamella under ambient temperature. Taking advantages of its temperature-responsive phase change behavior, RPWM assemblies exhibited excellent removal efficiency for organic dye RhB, and could be reused for several consecutive cycles without significant changes in its removal performance. Taken together, it's rational to envision that the engineering of racemates assembly pathways can greatly increase the robustness in a wide variety of supramolecular materials and further lead to their blooming versatile applications.     

Designing a Polymer Blend with Phase Separation Tunable by Visible Light for Computer‐Assisted Irradiation Experiments

Summary: A mixture of poly(vinyl methyl ether) (PVME) and a polystyrene derivative bearing cinnamate groups (PSC) was chemically designed so that its phase separation can be tunable by visible light for computer‐assisted irradiation (CAI) experiments. This PSC/PVME blend exhibits a lower critical solution temperature (LCST) and undergoes phase separation upon irradiation with 405 nm visible light. The phase separation was induced by photodimerization of the cinnamate moieties in the presence of 5‐nitroacenaphthene used as a photosensitizer. It was found that for visible light with high intensity, phase separation process was almost frozen by photodimerization of the cinnamate groups which act as a photo‐cross‐linker for the PSC component. It is demonstrated in this work that by using this PSC/PVME blend, phase separation restricted to the micrometer scales can be induced and manipulated by irradiation using a computer‐controlled digital projector. These preliminary results open a new route for spatio‐temporal manipulation of phase separation in photo‐reactive polymer blends.

Computer‐assisted irradiation method for a polymer blend with phase separation drivable by visible light.     

A Computational Study into Thermally Induced Phase Separation in Polymer Solutions under a Temperature Gradient

The influence of spatial temperature gradients on the morphological development in polymer solutions undergoing thermally induced phase separation was studied using mathematical modeling and computer simulation. The one‐dimensional mathematical model describing this phenomenon incorporates the nonlinear Cahn‐Hilliard theory for spinodal decomposition (SD), the Flory‐Huggins theory for polymer solution thermodynamics, and the slow‐mode theory and Rouse law for polymer diffusion. The resulting governing equation and auxiliary conditions were solved using the Galerkin finite element method. The temporal evolution of the spatial concentration profile from the computer simulation illustrates that an anisotropic morphology (see Figure) results when a temperature gradient is maintained along the polymer solution sample. The final anisotropic morphology depends on the overall phase separation time. If phase separation is terminated at very early stages, smaller (larger) droplets are formed in the lower (higher) temperature regions due to the deep (shallow) quench effect. On the other hand, if phase separation is allowed to proceed for a long period of time, then larger droplets are formed in the low‐temperature regions, whereas smaller droplets are developed at higher temperatures. This is due to the fact that the low‐temperature regions have entered the late stage of SD, while the high temperature regions are still in the early stage of SD. The presence of a temperature gradient during thermally induced phase separation introduces spatial variations in the change of chemical potential, which is the driving force for phase separation. These numerical results provide a better understanding of the control and optimization during the fabrication of anisotropic polymeric materials using the thermally induced phase separation technique.

     

Effect of packing parameter on phase diagram of amphiphiles: an off-lattice Gibbs ensemble approach

We determine the phase diagram of several amphiphilic molecules as a function of the amphiphilic parameter alpha defined as the ratio of the volume of hydrophilic to hydrophobic segments using the Gibbs ensemble Monte Carlo method supplemented by configurational bias scheme. Specifically, we study amphiphilic molecules h(1)t(7), h(2)t(6), and h(3)t(5), for which alpha=0.14, 0.33, and 0.60 respectively, and demonstrate that the former two exhibit phase separation while h(3)t(5) forms micelles, supporting the contention that alpha=0.5 is the border line for phase separation and micellization, as observed in previous lattice Monte Carlo studies [Panagiotopoulos et al., Langmuir 18, 2940 (2002)]. Further, we study the phase separation in amphiphilic molecules as a function of the packing parameter by varying the size of the hydrophilic head for each molecule. We find that a larger hydrophilic head lowers the critical temperature T(c), and raises the critical density rho(c).     

二元阴离子型丙烯酰胺共聚物在二价金属离子存在下相分离行为的研究

水溶性丙烯酰胺类共聚物 ,作为粘度改性剂 ,在工业上已得到广泛应用 .特别近年来 ,它们大量应用于石油工业强化采油技术 ,引起了人们很大的重视[1] .目前 ,这类用途的聚合物 ,主要在聚丙烯酰胺结构中 ,引入阴离子组分和不断增高产物分子量的方法 ,以提高聚合物溶液粘度和增粘效果 ,然而 ,在二价金属离子 (如Ｃａ2 + ,Ｍｇ2 + 等 )存在下 ,羧酸阴离子型丙烯酰胺类共聚物很容易络合发生沉淀 ,从而失去增粘作用[2 ] .同时这类聚合物中酰胺基不稳定 ,易发生水解反应转化为羧酸基 ,并随温度升高而加剧[3 ] ,因此在温度较高的应用条件下 ,二价金属…     

Interpenetrating Polymer Networks with Spatially Graded Morphology Controllable by UV-Radiation Curing

Interpenetrating Polymer Networks (IPNs) composed of polystyrene (PS) and poly(methyl methacrylate) (PMMA) were synthesized from a precursor mixture by using dissimilar photo-cross-link reactions. When the reation yields exceeded a certain threshold, the mixture was quenched from one-phase region into two-phase region, leading to phase separation. Upon irradiation with strong UV-light, an intensity gradient was formed along the propagating direction of the exciting light, generating a gradient of quench depth via the spatial inhomogeneity of the cross-link reactions. As a consequence, a gradient of the characteristic length scales was continuously generated from the top to the bottom of the mixture. The resulting three-dimensional (3-D) morphology was in-situ observed at different depths of the mixture by using a laser-scanning confocal microscope (LSCM). From this 3-D observation, it was found that phase separation was accelerated at the bottom of the mixture and proceeded in an autocatalytic fashion. The mechanism for the formation of the graded morphology was discussed in conjunction with the kinetics of the autocatalytic phase separation.     

Temperature and composition dependence of the Soret coefficient in Lennard-Jones mixtures presenting evaporation/condensation phase transition

The thermodiffusive behavior of a Lennard-Jones binary mixture has been studied by using nonequilibrium molecular dynamics. In particular, the dependence of the Soret coefficient, S(T), on the temperature and composition has been investigated, exploring a wide range of temperatures from 1000 K to the condensation temperature of the mixture. In a previous paper the dependence of S(T) on the temperature and the composition was studied for Lennard-Jones binary mixtures presenting mixing/demixing (consolute) phase transition, and the results allowed the formulation of a very simple expression with the computed values of S(T) in the one phase region outside the critical region closely fitted by the function [T - T(c)(x(1))](-1), with T(c)(x(1)) the demixing temperature of the mixture under study. The results of the present work show that the same expression of S(T) can be found for the one phase region outside the evaporation/condensation region but now with T(c) representing the condensation temperature of the mixture under study.     

EFFECT OF DILUENTS ON CRYSTALLIZATION OF POLY(VINYLIDENE FLUORIDE) AND PHASE SEPARATED STRUCTURE IN A TERNARY SYSTEM via THERMALLY INDUCED PHASE SEPARATION

The phase diagram of a ternary system of PVDF,dibutyl phthalate (DBP) and di(2-ethylhexyl) phthalate (DEHP) was determined in terms of a pseudo binary system with the same polymer concentration and different DBP content in diluent mixture.The experimental results showed that as the DBP content increased in diluent mixture,the phase separation changed from liquid-liquid phase separation to solid-liquid phase separation,and both the cloudy point for L-L phase separation and crystallization temperature shif...     

Modeling arrested cluster growth in quenched nanoparticle solutions

We have carried out numerical simulations on a model of phase separation in a binary mixture in the presence of a third, surface-active component. Based on this model we study phase separation in a quenched solution of gold nanoparticles with dodecane thiol ligands in a mixed solvent of butanone and toluene. In our model gold nanoparticles-butanone correspond to the generic binary mixture, while toluene is modeled as a surface-active third component. Our results show that the surface-active component acts as an inhibitor for the phase separation process but its effect decreases with the increase in quench temperature. Simulation results are consistent with two major findings in recent experiments: (a) growth of gold nanoparticle clusters gets arrested at late times and (b) the saturation value of the cluster size is smaller at lower temperatures of quench.     

Confined linear molecules inside an aperiodic supramolecular crystal: the sequence of superspace phases in n-hexadecane/urea

High-resolution studies of the host-guest inclusion compound n-hexadecane/urea are reported at atmospheric pressure, using both cold neutrons and x-ray diffraction. This intergrowth crystal presents a misfit parameter, defined by the ratio c(h)/c(g) (c(host)/c(guest)), which is temperature independent and irrational (γ = 0.486 ± 0.002) from 300 to 30 K. Three different structural phases are reported for this aperiodic crystal over this temperature range. The crystallographic superspaces are of rank 4 in phases I and II, whereas phase III is associated with an increase in rank to 5, with a supplementary misfit parameter (δ = 0.058 ± 0.002) that is constant throughout this phase. The superspace group of phase I is hexagonal P6(1)22(00γ) down to T(c1) = 149.5 ± 0.5 K; phase II, which persists down to T(c2) = 127.8 ± 0.5 K is orthorhombic P2(1)2(1)2(1)(00γ), and phase III is orthorhombic P2(1)2(1)2(1)(00γ)(00δ).     

双连续相微乳液辐射聚合制备多孔材料的研究

利用6 0 Co γ射线在室温下辐照双连续相微乳液体系以制备多孔聚合物材料 ,试图在控制多孔材料的微孔结构形态和减少微乳液聚合过程中的相分离方面做一些探索 .通过电导率的测量分析微乳液的结构类型 ,并确定微乳液的双连续相区域范围 .微乳液聚合后所得的样品的孔结构和聚合前的微乳液结构类型有关 ,扫描电镜和热重分析的结果表明双连续相微乳液在聚合时容易发生相分离 ,未必能够得到开孔结构的聚合物 .但适当控制聚合前微乳液的组成 ,如选择合适的水油比例、交联剂的用量和加入一些功能性单体 (如甲基丙烯酸或丙烯酸钠 ) ,可以有效地抑制相分离 ,调节所得聚合物的结构形态 .     

A study on the phase behavior of the system CO2 + CO + H2 + 1-hexene + heptanal

The phase behavior of a system of importance for the hydroformylation reaction of 1-hexene in supercritical CO₂ has been studied in the range of 303.2–348.2 K with different CO₂ mole fractions. The conversion of 1-hexene varies from 0 to 1. The density of the reaction mixture at different conditions are also determined. It is demonstrated that the phase behavior changes with conversion of 1-hexene. At zero conversion, the phase separation pressure increases with increasing concentration of the reactants in the reaction system and decreases slightly with the increase of temperature. At other conversions, the phase separation pressure increases as temperature rises. The density of the reaction mixture at phase separation point is higher at the larger conversions.     

Miscibility and morphology of poly(ethylhexylacrylate)/liquid crystal blends prepared under different conditions

A comparative study of the phase diagrams and morphology of blends of poly(2‐ethylhexylacrylate) and low molecular weight liquid crystals (LCs) prepared under different conditions is presented. Two LCs are used; one is the 4‐cyano‐4′‐n‐pentyl‐biphenyl and the other is the eutectic mixture of cyanoparaphenylenes known as E7. Two series of blends are prepared under different conditions. The first series is obtained by the polymerization induced phase separation (PIPS) process under UV‐curing starting from a monomeric mixture, while the second series is prepared by a combination of the solvent induced phase separation and the thermally induced phase separation process starting from a mixture containing a commercial polymer with known molecular weight. Using gel permeation chromatography, it is found that the polymer molecular weight of the UV‐cured systems decreases with the concentration of LC in the precursor mixture. The experimentally obtained phase diagrams of these two series of systems show a miscibility shift at the composition where the molar mass of the polymer in the PIPS/UV blend exceeds that of the commercial polymer. Data are rationalized in terms of the Flory‐Huggins theory of isotropic mixing and the Maier‐Saupe theory of nematic order. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 18–27, 2007