Isotope and pressure effects in polymer solutions. Demixing of polystyrene(h/d) poly-2-chlorostyrene blends

Liquid-liquid demixing, following spinodal quenches of poly-2-chlorostyrene/polystyrene blends, was followed by light scattering at 632.8 nm. The dependences of demixing on H/D substitution and molecular weight of the polystyrene, and on pressure, are reported. In the region of interest, the phase diagram is of the lower critical solution (LCS) type, and demixing is induced by raising the temperature. The transition temperature is lowered by deuterium substitution. At constant quench depth the transition proceeds more rapidly at elevated pressure. © 1995 John Wiley & Sons, Inc.     

Phase separation by continuous quenching: similarities between cooling experiments in polymer blends and reaction-induced phase separation in modified thermosets

Small angle light scattering (SALS) has been applied to study the phase separation kinetics in a binary polymer mixture of poly(ethyl methyl siloxane) (PEMS) and poly(dimethyl siloxane) (PDMS). The phase separation was induced by cooling an initially homogeneous mixture with well defined cooling rates. The results have been compared to time resolved SALS and microscopy in the course of reaction-induced phase separation in mixtures of an epoxy resin and polysulfone (PSU). For the critical PEMS/PDMS mixture with an upper critical point it was found in a continuous quenching experiment that the time evolution of the scattered light intensity I(q,t) scales with the cooling rate. The similarity to the scaling behavior of I(q,t) in isothermal experiments after fast quenches (scaled by the quench depth) is discussed. A secondary phase separation was found and has been explained by the competition between the growth of the two phase structure during cooling and the mutual diffusion without the assumption of gelation or vitrification. For the epoxy/PSU mixture with 15% PSU, after the appearance of a bicontinuous structure a secondary phase separation was observed. Mixtures with higher PSU-contents formed epoxy-rich droplets in the PSU-rich matrix by nucleation and growth mechanism. The frustration of the structure growth can be explained by approaching vitrification of one or both phases. The similarity between continuous cooling experiments in blends and the reaction-induced phase separation have been discussed in the generalized χN vs. composition phase diagram (N: degree of polymerization, χ: Flory-Huggms interaction parameter).     

聚甲基丙烯酸甲酯/聚醋酸乙烯酯共混分相过程结构函数的标度分析和相凝聚

高分子共混体系相分离动力学研究已取得了很大的进展。Cahn理论可很好地描述相分离初期过程,de Gennes的蛇行理论可较好地描述相分离初期大分子扩散。在相分离后期,人们已经发现动力学参量的标度行为,但实验结果不一,标度成因尚不十分清楚。本文研究了聚甲基丙烯酸甲酯(PMMA)/聚醋酸乙烯酯(PVAc)共混体系相分离后期过程。分析了结构函数的标度行为,初步讨论了相凝聚特征。     

嵌段共聚物苯乙烯-丁二烯-苯乙烯(SBS)/苯酰化聚苯醚共混分相动力学

<正> 对高分子-高分子共混体系相分离动力学过程的研究,人们一般局限于均聚物-均聚物,均聚物-无规共聚物共混体系,对于均聚物-嵌段共聚物共混体系的分相过程很少涉及。原因其一是很难找到具有临界相行为的嵌段共聚物-均聚物共混体系,其二是嵌段共聚物存在微相分离,使得宏观相分离动力学过程研究变得复杂。Paul的工作似乎为这方面的研究工作开辟了道路。     

Phase separation mechanism in gelling aqueous biopolymer mixture probed by light scattering

Using time-resolved static and dynamic light scattering (DLS) we have studied the kinetics of phase separation in an aqueous gelatin/maltodextrin mixture upon fast cooling. The time evolution of the droplet radius is modelled for the monodisperse case under reaction-limited and diffusion-limited conditions and compared with the observed evolution of the mode associated with the droplet diffusion. For quenches to above the gelatin ordering temperature, nucleation and rather reaction-limited than diffusion-limited growth and late-stage coalescence of droplets with diameters up to 90 μm were concluded. Quenches to well below the gelatin ordering temperature seem to induce diffusion-limited growth or (delayed) spinodal decomposition (SD) to a phase-separated microstructure with slow late-stage coarsening. In deep quenches, a second slow SD or diffusion-limited cluster aggregation (DLCA) process becomes apparent from the evolution of the static structure factor; the process seems to be related to the maltodextrin gelation in the composite.     

Neutron scattering and monte carlo determination of the variation of the critical nucleus size with quench depth

We have used a combination of neutron scattering experiments and Monte Carlo simulations to study the initial stages of first-order phase transitions. We focus on quenches wherein the nascent phase is formed by homogeneous nucleation, and we approach the spinodal, i.e., the quench depth at which the original phase becomes unstable. In this regime, we show how critical nuclei sizes are determined from neutron scattering structure factors. Prevailing thought is that the size of the critical nucleus should increase with increasing quench depth and diverge at the spinodal. To the contrary, our experiments and simulations indicate that the critical nucleus size decreases monotonically as quench depth is increased and is finite at the spinodal.     

聚甲基丙烯酸甲酯/聚醋酸乙烯酯共混分相过程结构函数的标度分析和相凝聚

Phase separation of quenched critical and off-critical polymer blends of poly (methyl methacrylate) and poly(vinyl acetate) was studied by using light scattering technique. The results show I(q, t) - qm^-3-s(q/qm);s(X) -X²/(3 + X⁸) and X²/(2 + X⁶) for critical off-critical mixtures, respectively. In the late stage of phase separation, the self-similarity of the structure is preserved and the coarsening processes are one that the domains increase with self-similar.     

Turbidity determination of the critical exponent eta in the liquid-liquid mixture methanol and cyclohexane

The turbidity of the liquid-liquid mixture methanol-cyclohexane has been measured very near its critical point and used to test competing theoretical predictions and to determine the critical correlation-correction exponent eta. By measuring the ratio of the transmitted to incident light intensities over five decades in reduced temperature, we are able to determine that Ferrell's theoretical prediction for the turbidity explains the data with the correlation length amplitude xi0=0.330+/-0.003 nm and critical exponents eta=0.041+/-0.005 and nu=0.632+/-0.002. These values are consistent with the values measured before for xi0 in this system and with the exponents predicted by theory. The data allow five different theoretical expressions to be tested and to select two as being equivalent when very close to the critical point.     

Does coarsening begin during the initial stages of spinodal decomposition?

The initial stages of spinodal decomposition were studied by subjecting a critical blend of model polyolefins to a pressure quench and monitoring the evolution by time-resolved small angle neutron scattering. Contrary to the predictions of the widely accepted Cahn-Hilliard-Cook theory, we demonstrate that coarsening of the phase-separated structure begins immediately after the quench and occurs throughout the initial stages of spinodal decomposition.     

Molecular dynamics simulations of side chain liquid crystal polymer molecules in isotropic and liquid-crystalline melts

A detailed molecular dynamics simulation study is described for a polysiloxane side chain liquid crystal polymer (SCLCP). The simulations use a coarse-grained model composed of a combination of isotropic and anisotropic interaction sites. On cooling from a fully isotropic polymer melt, we see spontaneous microphase separation into polymer-rich and mesogen-rich regions. Upon application of a small aligning potential during cooling, the structures that form on microphase separation anneal to produce a smectic-A phase in which the polymer backbone is largely confined between the smectic layers. Several independent quenches from the melt are described that vary in the strength of the aligning potential and the degree of cooling. In each quench, defects were found where the backbone chains hop from one backbone-rich region to the next by tunneling through the mesogenic layers. As expected, the number of such defects is found to depend strongly on the rate of cooling. In the vicinity of such a defect, the smectic-A structure of the mesogen-rich layers is disrupted to give nematiclike ordering. Additionally, several extensive annealing runs of approximately 40 ns duration have been carried out at the point of microphase separation. During annealing the polymer backbone is seen to be slowly excluded from the mesogenic layers and lie perpendicular to the smectic-A director. These observations agree with previous assumptions about the structure of a SCLCP and with interpretations of x-ray diffraction and small angle neutron scattering data. The flexible alkyl spacers, which link the backbone to the mesogens, are found to form sublayers around the backbone layer.     

Nonisothermal crystallization studies on poly(4‐hydroxybutyric acid‐alt‐glycolic acid)

The crystallization behavior of a new sequential polyester constituted by glycolic acid and 4‐hydroxybutyric acid has been studied under nonisothermal conditions. Nonisothermal melt crystallization has been followed by means of hot‐stage optical microscopy (HSOM), with experiments performed at different cooling rates. Two crystallization regimes have been found, which is in good agreement with previous isothermal studies and with the different spherulitic morphologies that were observed. The kinetics of both glass and melt crystallizations has also been studied by differential scanning calorimetry (DSC) and considering the typical Avrami, Ozawa, and Cazé analyses. Only the last gave Avrami exponents, which were in good agreement with those measured under isothermal conditions, suggesting a spherulitic growth with a predetermined nucleation. Isoconversional data of melt and glass nonisothermal crystallizations have been combined to obtain the Hoffman and Lauritzen parameters. Results again indicate the existence of two crystallization regimes with nucleation constants close to those deduced from isothermal DSC experiments. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 121–133, 2008     

Modulated‐temperature differential scanning calorimetry study of temperature‐induced mixing and demixing in poly(vinylmethylether)/water

The heat capacity or reversing heat flow signal from modulated‐temperature differential scanning calorimetry can be used to measure the onset of phase separation in a poly(vinylmethylether)/water mixture, clearly showing the special type III lower critical solution temperature demixing behavior. Characteristic of this demixing behavior is a three‐phase region, which is detected in the nonreversing heat flow signal. Stepwise quasi‐isothermal measurements through the phase transition show large excess contributions in the (apparent) heat capacity signal, caused by demixing/remixing heat effects on the timescale of the modulation (fast process). These excess contributions and their time‐dependent evolutions (slow process) are useful in understanding the kinetics of phase separation and the morphology (interphase) development. Care has to be taken, however, in interpreting the heat capacity signal derived from the amplitude of the modulated heat flow because nonlinear effects lead to the occurrence of higher harmonics. Therefore, the raw heat flow signal for quasi‐isothermal demixing and remixing measurements is also examined in the time domain. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1824–1836, 2003     

Demixing and gelation behavior of ternary cellulose acetate solutions

The demixing behavior on cooling of ternary systems of cellulose acetate/solvent/water has been examined for CA concentrations up to 40 wt% CA in several solvents. Cloud points have been measured as a function of cooling rate. The rapid process of liquid—liquid demixing can be discriminated from the slow process of aggregate formation by examining the dependence of the cloud point on the cooling rate and by structure analysis of quenched solutions with scanning electron microscopy. The appearance of aggregate formation depends strongly on the type of solvent. Slow cooling of ternary solutions in which acetone is the solvent leads to aggregate formation long before liquid—liquid demixing occurs. In addition, isothermal sol—gel transitions have been measured for quenched solutions at varying gelation times. It is concluded that gelation is not always preceded by aggregate formation.     

Ion-induced multiply reentrant liquid-liquid transitions and the nature of criticality in ethanol-water mixture

We report a quite unusual feature of four liquid-liquid reentrant transitions in ethanol (E)+water (W)+ammonium sulfate mixture by meticulous tuning of the ammonium sulfate concentration in a narrow range, as a function of temperature, at atmospheric pressure. Detailed exploration of the intricate phase behavior in terms of E/W sections shows that the range of triple reentrance shrinks with increasing E/W. The behavior of osmotic susceptibility is investigated by light scattering, near the critical point, in the one-phase region by varying the temperature at fixed concentration of the components, in a particular E/W section. The critical exponent of susceptibility (gamma) and correlation length (nu) are observed to have Fisher renormalized Ising values [Phys. Rev. 176, 237 (1968)], with gamma(r)=1.41 and nu(r)=0.718. The effective susceptibility exponent, gamma(eff), exhibits a sharp, nonmonotonic crossover from Ising to mean-field critical behavior, which is completed outside the critical regime. The amplitude of the correlation length, xi(o)(=21.2+/-0.4 A), deduced from light scattering experiment, is an order of magnitude larger than the typical values in usual aqueous electrolyte systems. This value of xi(o) is further verified from small-angle x-ray scattering (SAXS) experiments and found to be consistent. SAXS experiments on the critical sample reveal the presence of long-ranged intermolecular correlations, leading to supramolecular structuring, at a temperature far away from the critical point. These results convincingly demonstrate that the finite length scale arising due to the structuring competes with the diverging correlation length of critical concentration fluctuations, which influences the nonasymptotic critical behavior in this aqueous electrolyte system. The sulphate ions play a dominant role in both structuring and the complex phase behavior.     

聚甲基丙烯酸甲酯/聚醋酸乙烯酯共混相分离过程的标度行为与逾渗结构

本文用激光光散射和光学显微镜方法研究了聚甲基丙烯酸甲酯/聚醋酸乙烯酯共混体系不稳相分离过程最大散射强度I_m(t,T)和相应波矢q_m(t,T)随时间变化规律及相区的逾渗结构.实验结果表明:I_m(T,t)和q_m(t,T)与时间t满足简单的标度关系I_m(t,T)～t~β,q_m(t,T)～t~(-α),且标度关系β=3α成立.揭示了相态结构的分维特征.给出了计算相态结构分维数的简便方法,其分维数D值约为1.64±0.03.与逾渗模型给出的D值接近.     

Kinetics of the nematic ordered phase growth during a temperature quench of an isotropic siloxane-azomethine polymer

Kinetics of the nucleus growth during a deep temperature quench across the isotropic to nematic phase transition was experimentally investigated for a siloxane-azomethine polyether at cooling rates of 10 and 20°C min^-1. Nematic droplets revealed in the optical images during the phase separation were treated statistically and the resulting statistical size distributions were described using the model of reversible aggregation. Analysis of the time-dependent distribution parameters allowed two processes involved in liquid crystal phase ordering to be identified: nucleus growth and nucleus coarsening. Both regimes are quantitatively described using the universal growth law.     

Polymerization-induced viscoelastic phase separation in polyethersulfone-modified epoxy systems

The polymerization-induced phase-separation process of polyethersulfone (PES)-modified epoxy systems was monitored in situ continuously on a single sample throughout the entire curing process by using optical microscopes, time-resolved light scattering (TRLS), scanning electronic microscopes (SEM), and a rheometry instrument. At specific PES content a viscoelastic transformation process of phase inversion morphology to bicontinuous was found with an optical microscope. The rheological behavior during phase separation corresponds well with the morphology development. Light-scattering results monitoring the phase-separation process of systems with final phase inversion morphology show a typical exponential decay procedure of scattering vector qm. The characteristic relaxation time of phase separation can be described well by the WLF equation.     

Complex coacervation between beta-lactoglobulin and Acacia gum: a nucleation and growth mechanism

Complex coacervation between proteins and polysaccharides is a demixing process mainly driven by electrostatic interactions. During this process many structural transitions occur, involving the formation of soluble complexes, aggregated complexes, and coacervates. The dynamic mechanism of complexation/coacervation was studied on beta-lactoglobulin (BLG)/Acacia gum (AG) mixed dispersions (0.1 wt% total concentration; BLG:AG ratio of 2:1) using small angle static light scattering (SALS). Acidification of BLG/AG dispersions was induced by dissolution of 0.11 wt% glucono-delta-lactone, allowing in situ SALS measurements. Time evolution of turbidity, scattered light intensity at 46 degrees scattering angle (I46) or slope of scattering functions at high q range revealed the existence of six pH-induced structural transitions. During BLG/AG complexation and before coacervation took place, scattering profiles displayed a monotonic decrease of I(q) as a function of q. A correlation peak in the scattering functions was only observed when coacervates appeared in the system. The wave vector q(max) corresponding to the maximum in scattered intensity first shifted toward larger q values, indicating an increasing number of coacervates, then shifted toward smaller q values, as a consequence of the system coarsening. The power laws q(max) approximately t(-alpha) and I(max) approximately t(-beta) gave values of 1.9 and 9.2, respectively, values much larger than those expected for intermediate and late stages of spinodal decomposition. From these results, it was concluded that complex coacervation between BLG and AG was a nucleation and growth type process. In addition, the temporal evolution of I46 followed power laws with two different exponents. First exponent corresponding to BLG/AG complexation was 3.0+/-0.3 and indicated a diffusion-controlled growth mechanism. Second exponent corresponding to the initiation of phase separation to the coacervation process was 6.5+/-0.3 and revealed an interfacially-controlled growth mechanism.     

Polymer chain conformation in the phase separation process of a binary liquid mixture

A polymer chain conformation change near the critical point of liquid-liquid phase separation was investigated. Poly(N-isopropylacrylamide) labeled with a small amount of carbazolyl group for a fluorophore (P(NIPA-Cz)) was prepared. A ternary system of P(NIPA-Cz)+cyclohexane+methanol was investigated by the fluorescence spectroscopic technique. A mixed solvent of cyclohexane+methanol (CH/MeOH) shows phase separation at the upper critical solution temperature. Light scattering intensity, fluorescence emission intensity and fluorescence anisotropy ratio, as a function of temperature, were measured with quasi statically approaching to the critical demixing point. The fluorescence intensity of the carbazolyl groups attached to the polymer chain decreases with approaching to the critical temperature. This result suggests that the radius of gyration of the polymer decreases upon approaching to the critical demixing point of the solvent. We discuss the collapse and aggregation processes of the polymer based on the fluorescence quenching method. The rotational diffusion coefficient of carbazolyl groups attached to the polymer chain was estimated by the fluorescence depolarization technique. The rotational motion of carbazolyl groups is slowed down upon approaching the critical point.     

Critical polymer-polymer phase separation in ternary solutions

We study polymer-polymer phase separation in a common good solvent by means of Monte Carlo simulations of the bond-fluctuation model. Below a critical, chain-length-dependent concentration, no phase separation occurs. For higher concentrations, the critical demixing temperature scales nonlinearly with the total monomer concentration, with a power law relatively close to a renormalization-group prediction based on "blob" scaling arguments. We point out that earlier simulations and experiments have tested this power-law dependence at concentrations outside the validity regime of the scaling arguments. The critical amplitudes of the order parameter and the zero-angle scattering intensity also exhibit chain-length dependences that differ from the conventional predictions but are in excellent agreement with the renormalization-group results. In addition, we characterize the variation of the average coil shape upon phase separation.