Effect of Polydispersity on the Phase Behavior of Polystyrene (PS)/Poly (Vinyl Methyl Ether) (PVME)

The thermodynamics and kinetics of phase separation in partially miscible blends of poly (vinyl methyl ether) (PVME) and two kinds of polystyrene (PS) with the same weight average molecular weight but different polydispersity were studied. The miscibility of PS/PVME with the monodisperse PS was better than that of PS/PVME with the polydisperse PS. Different morphology was observed for the two kinds of PS/PVME (10/90) blends during the nonisothermal phase separation process. The blend with monodisperse PS presented a co-continuous structure while the blend with polydisperse PS presented a viscoelastic phase separated network structure at a quench depth of 29°C. With increase of the heating rate, the increase of cloud point of PS/PVME (30/70) with polydisperse PS was smaller than that of PS/PVME (30/70) with monodisperse PS. During the isothermal phase separation of the critical composition (20/80) of PS/PVME with a quench depth of 30°C, it was found that the phase morphology of the two kinds of blends was nearly the same at the early stage of phase separation. However, as the dispersed phase, an approximately spherical droplet structure was observed in the blend with monodisperse PS at the late stage of phase separation, which did not appear in the blend with polydisperse PS.     

Early stages of phase separation from polydisperse polymer mixtures

We study the early stages of phase separation in a mixture of a polydisperse and a monodisperse polymer within the Cahn-Hilliard framework. We model the polydisperse component using a finite, but arbitrarily large, number of components, and show that the number of components required for convergent behaviour to be achieved is computationally undemanding. We study the growth rate of fluctuations following a quench into the two-phase region of the phase diagram. The q-dependence of the growth rate is shown to be commensurate with the behaviour of a monodisperse-monodisperse mixture, with the major difference being an effective mobility that is dependent on the quench depth. We also study the deviation of the time dependence of the scattering function from single exponential behaviour. Received 29 June 2000 and Received in final form 20 November 2000     

Similarity of the signatures of the initial stages of phase separation in metastable and unstable polymer blends

Time-resolved small angle neutron scattering was used to probe the initial stages of liquid-liquid phase separation in both critical and off-critical binary polymer blends, and the critical (q(c)) and most probable (q(m)) wave vectors were identified for several quench depths. For the critical blend, the Cahn-Hilliard-Cook theory provides a framework for analyzing the data and explains the observed decrease in q(m) with time. For the off-critical blend, q(m) is independent of quench time, regardless of whether the quench is metastable or unstable.     

Reaction‐Induced Phase Separation in Polyoxyethylene/Polystyrene Blends. I. Ternary Phase Diagram

Abstract

Reaction‐induced, phase separation has been studied in polymer blends. A model crystalline‐amorphous system consisted of semicrystalline polyoxyethylene (POE) dissolved in the monomer styrene, which was used as a reactive solvent to ease processing. When the styrene was polymerized to polystyrene (PS) in the mold, phase separation and phase inversion are induced, and a polymer blend was formed. Polyoxyethylene was selected with a molar mass, M _n  = 8578 g mol^?1 and a polydispersity of 1.19, as determined by using gel permeation chromatography. The polymerization of styrene was initiated by using 1 wt% benzoin methyl ether and 0.2 wt% 2,2′‐azobisisobutyronitrile under ultraviolet light. The polymerization kinetics were determined by monitoring the reduction in the intensity of the C?C stretching vibration band at 1631 cm^?1 in the Raman spectrum of styrene. The onset times for the liquid–solid (L–S) phase separation and crystallization of POE from styrene/PS were observed by using simultaneous small‐angle x‐ray scattering (SAXS) and wide‐angle x‐ray scattering. Onset times for L–S phase separation determined from the SAXS data were combined with the styrene polymerization kinetics to plot the L–S phase separation data onto a ternary phase diagram for the reactive system POE/styrene/PS at 45°C and 50°C.     

Reaction‐Induced Phase‐Separation in Polyoxyethylene/Polystyrene Blends. II. Structure Development

Abstract

The morphology development in model polymer blends was investigated in relation to the processing pathway. Reaction‐induced phase separation was used to make polyoxyethylene (POE) and polystyrene (PS) blends from a solution of POE/styrene. As the styrene underwent polymerization by photo‐initiation with ultraviolet light, phase separation, and phase inversion were induced, whereby the POE became the matrix phase. Optical microscopy showed that liquid–liquid (L–L) phase separation occurred soon after the styrene polymerization was initiated. Nucleation and growth was identified as the mechanism of L–L phase separation. Polystyrene/styrene‐rich domains formed in a POE/styrene‐rich matrix. The domain size developed until arrested by the POE liquid–solid phase separating and crystallizing, since the experiments were conducted below the melt temperature of POE. The POE crystal growth process also followed a nucleation and growth mechanism. The time to the onset of crystallization was observed to decrease as the POE content increased, until the POE formed a saturated solution in styrene. As the crystallization onset time decreased, the PS‐rich domain size also decreased. The phase diagram previously established can now be used to describe (and predict) the number density and size of the PS‐rich domains in the POE matrix of the blends.     

Reaction-Induced Phase Separation and Structure Formation in Polymer Blends

The peculiarities of reaction-induced phase separation and the structure formation in semi- and full interpenetrating polymer networks and in the blends of linear polymers formed in situ are analyzed. It is shown that for most of these systems phase separation proceeds viathe spinodal decomposition mechanism resulting in the formation of interconnected spatially periodic structures. The possible ways for the structure regulation of the composites produced are considered.     

具有双曲正割型折射率的线性和非线性介质中的光呼吸子

通过数值模拟研究具有横向双曲正割型折射率调制的线性和非线性介质中光的传输。结果显示光束在传输过程中有呼吸的特性,其呼吸周期可以通过折射率调制的深度和宽度加以改变。同时讨论具有不同初始相位的两相邻光束之间的相互作用。指出周期性在初始相位相同时出现,在初始相位相反时可以通过适当地选择光束间距形成束缚态。     

Influence of a continuous quenching procedure on the initial stages of spinodal decomposition

Instead of the standard assumption in the theory of phase separation where an instantaneous quench from an initial equilibrium state to the final state in the two-phase region is assumed, we consider the more realistic situation that the change of the external control parameter (e.g. temperature) can only be performed with finite rates. During the initial stages of spinodal decomposition the system then has some memory of the states intermediate between the initial and the final one. This influence of the finite quench rate in continuous quenching procedures is studied within the linearized theory of spinodal decomposition, with the Langer-Baron-Miller decoupling, and with Monte Carlo simulations. Both the case of thermally activated mobilities (applicable to solid metallic alloys) and the case of nearly temperature-independent mobilities (applicable to fluid polymer mixtures) are treated, and possible experimental applications are discussed. We find drastic deviations from the standard instantaneous quench situations in all cases of experimental interest.     

Preparation Principle of Super-Hydrophobic Surfaces by Phase Separation

The Flory–Huggins theory of polymer solutions combined with an evaporation process was employed to interpret the preparation mechanism of a super-hydrophobic surface by phase separation. The ternary phase diagram of a polymer/solvent/nonsolvent was calculated by using the solubility parameters of the components in the system. It indicated that with the increase of the nonsolvent fraction, the initial volume fraction of the polymer or the evaporation rate of the solvent, the evaporation time for phase separation would shorten and the phase separation rate would speed up. The polymer volume fraction in the dense phase would increase and the precipitating particles tended to collide and aggregate, resulting in a rough, super-hydrophobic surface. Experimental results were in agreement with this principle of phase separation for preparing super-hydrophobic surfaces. Membranes of acrylic resin and fluorinated acrylic resin with rough surfaces were successfully obtained by the phase separation method. Especially, the water contact angle of the fluorine-containing acrylic resin with the rough surface was greater than 150°, which satisfied the requirement of super-hydrophobicity.     

NMR study of liquid crystalline polymer curing in magnetic field

Effect of magnetic field on curing a cross-linked polymer based on diglycidyl ester of terephthaloyl-bis (4-hydroxy benzoic acid) in liquid crystalline (LC) state was studied using NMR. The magnetic field was shown to inhibit anionic polymerization. In the course of spontaneous curing the order degree decreased to 0.5 whereas at anionic polymerization the complete disordering was attained. The ordering of the liquid crystalline polymer can be conserved in anionic polymerization if it is performed under controlled temperature conditions.     

Dielectric and thermally stimulated discharge current studies of rubber-modified epoxy resins

Comparison is drawn between data obtained from dielectric relaxation and thermally stimulated discharge current (TSDC) measurements on blends of carboxyl-terminated butadiene acrylonitrile (CTBN) with an epoxy resin (ER) obtained by reaction of the diglycidyl ether of bisphenol A (DGEBA) with either triethylenetetramine (TETA) or diamino-diphenylmethane (DDM). The effect of varying the composition of CTBN on the nature of the phase separation was examined using electron microscopy and was also evident from changes in the dielectric spectrum and the calculated activation energy for the molecular relaxation process. The morphology consists of spherical rubber particles dispersed in an epoxy matrix at low levels of CTBN, and at higher concentrations epoxy resin is observed to be precipitated as spheres within the rubbery phase. Detailed analysis of the dipolar spectra indicates that at low concentrations there appears to be some cosolution of the epoxy in the CTBN.     

全息聚合物弥散液晶材料衍射特性的优化

研究了影响全息聚合物弥散液晶(HPDLC)衍射效率的主要因素，分析了衍射效率与聚合物单体的选择、曝光强度、曝光时间、液晶含量及温度的依赖关系，从而找到最佳条件，使衍射特性得到优化.目前测得的最大衍射效率为802%.实验中还研究了扫描电镜(SEM)观察下HPDLC的表面形貌.     

Polymer formation from aqueous solutions of α-D-glucose by ultrasound and λ-rays

The production of polymeric material from aqueous glucose solutions treated by ultrasound or λ-rays was investigated by size-exclusion chromatography (SEC). The polymers show strong electrostatic interactions with the SEC-columns and the non-ideal elution behaviour indicates that charged molecules are produced during irradiation. By optimization of the size-exclusion separation applying salt solutions in the mobile phase it was possible to determine the molecular weight (MW) as a function of irradiation dose. For both types of irradiation in the presence of oxygen, products in the molecular weight range up to 4000 dalton were formed. For sonolysis in the absence of oxygen, the same effect was observed due to the fact that small amounts of oxygen are formed by ultrasound irradiation of water. In the case of λ-irradiation in the absence of oxygen there is no inhibition of the polymerization resulting in higher molecular weights of many thousand dalton. The resulting molecular weights depend on dose and dose rate.     

Self-assembly of polymer-tethered nanorods

We present results of molecular simulations that predict the phases formed by self-assembly of nanorods functionalized by a polymer "tether." Microphase separation of the immiscible tethers and rods coupled with the liquid crystal ordering of the rods induces the formation of a cubic phase, a smectic C phase, a tetragonally perforated lamellar phase, and a honeycomb phase; the latter two have been observed experimentally but have not been predicted. We also predict a new phase--a racemic mixture of hexagonally ordered chiral cylinders that self-assemble from these achiral building blocks.     

Unusual Phase Separation Kinetics in Poly(Methyl Methacrylate)/Poly(Styrene-co-Acrylonitrile) (PMMA/SAN) Blends with PMMA of Different Molecular Weights

The influence of molecular weight of poly (methyl methacrylate) (PMMA) on the thermodynamics and dynamics of phase separation in PMMA/poly (styrene-co-acrylonitrile) (SAN) blends was investigated via optical microscopy, time-resolved small-angle light scattering (SALS), and dynamic rheological measurements. It was found that the cloud point temperature of the blends decreased with an increase in the molecular weight of the PMMA. The phase separation rates of PMMA 48K/SAN and PMMA 85K/SAN blends with the near-critical composition were almost the same at small quench depths due to the limited mobility of molecular chains at low temperatures. However, an unexpected phase separation dynamics was observed at larger quench depths. Not only the morphology evolution but also the apparent diffusion coefficient D_app calculated from SALS revealed that the phase separation rate was faster in the PMMA 85K/SAN blend than in the PMMA 48K/SAN blend. The possible reasons for this unusual rapid kinetics of phase separation observed in the higher molecular weight blend were discussed in terms of molecular mobility and viscoelasticity.     

聚合物网络稳定液晶膜的制备与研究

实验发现在液晶中添加少量的预聚物单体,利用光聚合诱导相分离的方法可以形成反型显示模式的聚合物网络稳定液晶膜。该膜在平时呈现透明态,在电场的调节下呈散射态。本文观察了在不同光照时间、不同光强下制得样品的聚合物网络织构,分析了在聚合过程中形成网络的形状、大小与致密程度,并对实验结果进行了相关的讨论。     

Preparation of lotus-like superhydrophobic fluoropolymer films

Styrene and 2,2,3,4,4,4-hexafluorobutyl methacrylate copolymers were synthesized by bulk polymerization, and the superhydrophobic copolymer films were prepared subsequently using phase separation technique. The copolymer was dissolved in tetrahydrofuran, and then added ethanol into the solution thereafter, to induce phase separation. The microstructures of the polymer films were controlled by the degree of phase separation, which was enhanced properly by the concentration of ethanol. The surface morphology of the films, observed by environmental scanning electron microscope, is similar to that of the lotus leaf. The contact angle and sliding angle were measured as 154.3° and 5.8°, respectively. The excellent superhydrophobic property demonstrated that the phase separation technique is useful for preparing lotus-like fluoropolymer films.     

Distortion and unwinding of the helical structure in polymer-stabilized short-pitch ferroelectric liquid crystal

We report the effect of an anisotropic polymer network formed from an achiral photoreactive monomer in a short-pitch chiral SmC* phase on the distortion and the unwinding of the helical structure of the ferroelectric phase. The electro-optical behaviour and ferroelectric properties were experimentally determined for films containing various polymer concentrations. The critical field, E_u, for the transition from the distorted structure to the homogeneous state was measured as a function of polymer concentration. A linear increase of E_u versus polymer concentration was observed, showing that the helical structure of the short-pitch SmC* phase was stabilized by the polymer network. This behaviour was expected to be a consequence of the increase of the apparent elastic constants of the ferroelectric liquid crystal stabilized by the anisotropic polymer network films. The polymer network morphology was investigated using atomic-force microscopy, revealing a twisted structure of the polymer fibers. This twisted structure was transferred onto a polymer network during the polymerization process within a short-pitch SmC* phase. The increase of the apparent elasticity can then be interpreted by a strong interaction between polymer network and the liquid-crystal molecules. From our experimental data, the coupling coefficient, W_p, characterizing this interaction was evaluated for all studied polymer concentrations.