Interplay between gelation and phase separation in aqueous solutions of methylcellulose and hydroxypropylmethylcellulose

Thermally induced gelation in aqueous solutions of methylcellulose (MC) and hydroxypropylmethylcellulose (HPMC) has been studied by rheological, optical microscopy, and turbidimetry measurements. The structural and mechanical properties of these hydrogels are dominated by the interplay between phase separation and gelation. In MC solutions, phase separation takes place almost simultaneously with gelation. An increase in the storage modulus is coupled to the appearance of a bicontinuous structure upon heating. However, a thermal gap exists between phase separation and gelation in the case of HPMC solutions. The storage modulus shows a dramatic decrease during phase separation and then rises in the subsequent gelation. A macroporous structure forms in the gels via "viscoelastic phase separation" linked to "double phase separation".     

Microphase separation during the concurrent formation of two polymer networks

As a rule, interpenetrating polymer networks (IPNs) are multiphase systems, and the degree of microphase separation is determined by the competition between the chemical kinetics of reaction and the physical kinetics of phase separation. For semi-IPNs of crosslinked polyurethane and linear polystyrene obtained by a one-step process, the development of the morphology has been followed by light transmission measurements and by optical microscopy, and finally examined by scanning electron microscopy. When phase separation takes place after gelation, the rather short elastic chains of polyurethane limit the growth of the styrenic phase at a submicroscopic level and the materials thus formed are transparent. On the contrary, when the reaction medium can phase-separate before gelation of polyurethane, the final morphology results from a superposition of two levels of phase separation: i) a fine dispersion of the components and ii) a gross phase separation of polystyrene noduli surrounded by a polyurethane-rich shell.     

Rheological behaviors and structural transitions in a polyethersulfone-modified epoxy system during phase separation

The rheological behaviors and gelation transitions in a polyethersulfone (PES)-modified epoxy system during phase separation were studied by rheometry, time-resolved light scattering, and differential scanning calorimetry. Two separate structural transitions in the curing process of the blend were identified as the first one because of phase separation and the second one related to cross-linking reaction of epoxy resin. Both the times of the two structural transition at different temperatures could be described well by the Arrhenius type equation. The complex viscosity exhibits an exponential growing process during phase separation at various temperatures, correlating to the light-scattering results. The exponential behavior of complex viscosity could be attributed to the viscoelastic flow of epoxy-rich escaping from PES-rich during phase separation process.     

Phase separation and rheological behavior in thermoplastic modified epoxy systems

The relationship between rheological behavior and phase separation in polyesterimide modified epoxy systems was studied by rheometry, time-resolved light scattering (TRLS), and Differential Scanning Calorimetry (DSC). The rheological behaviors of blends during phase separation showed an exponential grow of complex viscosity, while the phase separation was inhibited by the vitrification of the polyesterimide-rich matrix phase rather than gelation of dispersed epoxy-rich particles. The characteristic relaxation time obtained by the simulation of complex viscosity could be described well by the Williams–Landel–Ferry equation, which corresponded well with the light scattering results. Therefore, this work would further provide the experimental proofs that the exponential relaxation behavior of complex viscosity could be attributed to the viscoelastic flow of epoxy-rich escaping from polyesterimide-rich matrix during phase separation.     

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.     

多壁碳纳米管对环氧树脂/聚醚酰亚胺体系相分离的影响

通过溶液混合的方法制备了环氧树脂/聚醚酰亚胺(PEI)/多壁碳纳米管(MWCNTs)三元复合物,并使用扫描电镜(SEM)、原位红外分析(FTIR)、流变测试和非等温DSC等手段研究了MWCNTs的存在对体系相分离形貌和固化反应的影响.扫描电镜的结果显示,在固化后的样品中MWCNTs较均匀地分散在两相中.150℃下固化,不含MWCNTs和MWCNTs含量为0.75 pbw的体系相分离形貌呈海岛状结构,而进一步增大MWCNTs含量后相分离形貌呈双连续结构,且相区尺寸随MWCNTs含量的增加而减小.120℃下固化,不含MWCNTs和MWCNTs含量为0.75 pbw的体系相分离形貌呈双连续结构,而进一步增大MWCNTs含量后,体系相分离形貌呈相反转结构.FTIR和DSC的测试结果表明,MWCNTs表面的羟基对环氧树脂的固化反应起到催化作用,使得固化反应速度加快,反应活化能降低.而流变测试的结果表明,随着MWCNTs含量增加,一方面交叉跨越多个相区的碳纳米管使得体系黏度增大,对相分离起到了一定的抑制作用;另一方面使得体系凝胶化时间提前,导致体系相分离形貌被固定在相分离的较早阶段,起到有效调控相分离形貌的作用.     

The influence of polyetherimide on gelation and phase separation in epoxy systems

In the process of curing under thermostatic conditions, the time dependence of active and reactive components of the dielectric permittivity of epoxy amine compositions that contain a thermoplastic substance is studied in a wide range of electrical frequencies. The times of gelation and vitrification are calculated from the dielectric data and the onset of the phase separation is identified. The curing behavior established by dielectric spectroscopy is confirmed by viscometry and optical microscopy. During the phase separation, the morphology of the precipitating phase differs between samples depending on the chemical nature of the curing agent.     

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.     

聚乳酸/壳聚糖纳米纤维结构形成的影响条件及其生物矿化活性

以二氧六环/冰醋酸为溶剂体系,采用相分离法制备了聚乳酸(PLA)/壳聚糖(CS)复合纳米纤维结构的组织工程支架,探讨了不同CS含量、不同凝胶温度及不同分子量对PLA/CS复合支架纳米纤维结构的影响以及支架的生物活性。结果表明,凝胶温度对PLA/CS复合材料的纳米纤维结构影响较大,且随着温度的降低,结构的微观尺寸也逐渐增大,从纳米级上升到普通的尺寸结构;CS含量对PLA/CS复合支架的基体结构影响不大;实验范围内PLA分子量对PLA/CS复合支架的纳米纤维结构有重要影响:分子量大的样品,较易得到PLA/CS复合纳米纤维结构的材料,而分子量小的样品则不能得到纳米纤维结构。另外,生物矿化实验表明CS的添加有利于PLA/CS复合材料生物活性的提高。     

Three-dimensional numerical simulation of viscoelastic phase separation under shear: the roles of bulk and shear relaxation moduli

The morphological, dynamic and rheological characteristics in the viscoelastic phase separation(VPS) of sheared polymer solutions are investigated by three-dimensional(3D) numerical simulations of viscoelastic model. The simulations are accelerated by graphic process unit(GPU) to break through the limitation of computation power. Firstly, the morphological and dynamic characteristics of VPS under shear are presented by comparing with those in classic phase separation(CPS). The results show that the phase inversion and phase shrink take place in VPS under shear. Then, the roles of bulk and shear relaxation moduli in VPS are investigated in details. The bulk relaxation modulus slows down the phase separation process under shear, but not affects the dynamic path of VPS. The dynamic path can be divided into three stages: freezing stage, growth stage and stable stage. The second overshoot phenomenon in the shear stress is observed, and explained by the breakdown and reform of string structures. The shear modulus affects morphology evolution in the late stage of VPS under shear.     

Rheology and morphology of linear polyurethane and poly(methyl methacrylate) blends formed in situ

The rheological properties and morphology of flow during the in situ formation of linear polyurethane and poly(methyl methacrylate) blends of various compositions are studied. At a certain conversion of the components, the initial homogeneous blend undergoes phase separation, as evidenced by the nonadditive dependence of the logarithm of viscosity on blend composition. For individual components, the gel points correspond to appreciably different conversions. For components in blends of various compositions, this difference is less pronounced and associated with the kinetic conditions of blend formation. The morphology of flow of the reaction blend over the time (or conversion) between the onset of phase separation and gelation during flow with a high shear rate is determined by the blend composition and the ratio between the viscosity of the dispersion phase and the matrix.     

Probing the effect of high energy ball milling on PVC through a multitechnique approach

The effects induced by ball milling treatment on PVC features and properties were deeply investigated through a multitechnique approach. SEM analysis showed a drastic change in PVC morphology; the hierarchical structure of PVC grains was partially destroyed as well as the domain size strongly reduced. A X-ray diffraction and DSC comparative study proved a structural modification in the PVC crystalline phase. Moreover, it was found that these morphological and structural changes strongly affected the gelation behavior, the microstructure and the mechanical parameters of PVC. In particular, the gelation time increased with increasing the ball milling time; the residual primary crystallite content doubled with respect to neat PVC and the toughness improved up to 25% as a function of the resulting microstructure.     

Epoxy – diamine thermoset/thermoplastic blends: thermoset reactions and rheological evolutions during curing

Isothermal rates of reaction during the cure of epoxy‐amine/thermoplastic blends were studied. Epoxy‐amine reaction induces a phase separation. Experimental results show that when TP concentration is higher than 30 wt% an increase of reaction rate is observed after phase separation. A modelling of the kinetics of each phase before and after phase separation, shows that in the epoxy‐amine rich phase, gelation occurs for a conversion close to 0.6. Rheological behaviour was studied during the cure. The viscosity was found greatly dependent of the morphology, the epoxy amine conversion and of the evolution of the phase composition. Modelling of the viscosity using simple relations gives a good fit of the experimental results during the cure.     

Viscoelastic Effects on the Dynamics of Spinodal Decomposition in Binary Polymer Mixtures

Numerical simulations based on the modified time‐dependent Ginzburg‐Landau (TDGL) equation have been performed on the domain growth dynamics of binary polymer mixtures. An elastic relaxation term was introduced into the equation to take the entanglement effects of the polymer chains into account. A cell dynamical scheme (CDS) is employed in this paper to improve the computing efficiency. The dynamics of the phase separation in polymer blends was investigated through to a very late stage. In the system without viscoelastic effects, there exists an apparent early stage, and in the late stage the modified Lifshitz‐Slyozov law and dynamical scaling law are satisfied very well. In the system with viscoelastic effects, there are some unique characteristics. A morphology with a rough interface between the domains is obtained and suppression of order‐parameter fluctuations is observed. The growth behavior of domains was altered, and there exits an intermediate stage between the early and late stage, in which the growth rate of domains slows down drastically. The intermediate stage was prolonged with enhanced entanglement effects. Entanglement effects also enhance the quench‐depth effects on the correlation and diminish the discrimination of correlation induced by criticality. After the relaxation of entanglements, the growth exponents with the model employed in this paper are independent of entanglements and are essentially consistent with the modified Lifshitz‐Slyozov law. In addition, the pair correlation function and the structure function are shown to exhibit the dynamical scaling law at the late stage.     

Effect of mixed solvent on solution properties and gelation behavior of poly(vinyl alcohol)

In this work, the static and dynamic light scattering measurements were used to investigate the solution properties and the aging effects on PVA/DMSO/water ternary system in dilute region at 25 °C. It was found that the phase separation and aggregate behavior occurs rapidly and obviously when DMSO mole fraction (X₁) in the solvent mixture is between 0.2 and 0.33, especially at 0.25. In this solvent composition range, a broad peak which indicates phase separation and chain aggregation can be observed from static light scattering measurement. However, when DMSO mole fraction is increased to 0.37, no such peak is present. For this ternary system, the gelation mechanism and the relationship between the phase separation behavior and the gelation of the formed physical gels were also investigated through the gelation kinetic analyses in the dilute and semi-dilute region. It is concluded that the cononsolvency effect in the dilute solution is not the sole origin that affects the phase separation, aggregation, and gelation behavior for the ternary system in a higher polymer concentration range. The hydrodynamic factors such as the higher viscosity and slower polymer chain diffusion that are resulted from higher polymer concentration should be also considered.     

Morphology and Dynamics of Phase‐Separating Fluids with Viscosity Asymmetry

Summary: The effects of viscosity asymmetry of the components on morphology and dynamics of phase‐separating AB fluids are investigated numerically based on a modified Model H. For critical mixtures, in the early stage of phase separation the co‐continuous morphology with droplets of A in B and B in A is observed. In the late stage of phase separation, the viscosity asymmetry leads to morphological change from co‐continuous structure to completely dispersed structure where the less viscous component forms droplet. The pathway of this transformation is accompanied by the breakdown of balance of volume fraction between droplets with different viscosity. Domain growth is characterized by a crossover from a faster growth at intermediate time under the influence of hydrodynamics to Lifshitz–Slyozov behavior at late times. For off‐critical mixture, viscosity asymmetry only plays an important role for domain growth in the intermediate stage of phase separation and the domain growth depends on whether the more viscous phase is dispersed or continuous, and the late stage of domain growth follows Lifshitz–Slyozov power law independent of which phase is dispersed.

Result for the evolution of phase‐separating domains for critical fluid mixtures = 0.5 for t = 1 500 with viscosity asymmetry: η_A = 0.8, η_B = 0.2. A‐rich regions and B‐rich regions are represented by white and black, respectively.     

Poly(chloropropylmethyl-dimethylsiloxane)–polyurethane elastomers: Synthesis and properties of segmented copolymers and related zwitterionomers

A series of polyurethane block copolymers based on hydroxybutyl terminated poly(chloropropylmethyl-dimethylsiloxane) and poly(tetramethylene oxide) soft segments of molecular weights 2100 and 2000, respectively, were synthesized. The hard segments consisted of 4,4′-methylenediphenylene diisocyanate (MDI) that was chain extended with either 1,4-butanediol (BD) or N-methyldiethanolamine (MDEA). The materials chain extended with MDEA were ionized using 1,3-propane sultone. The weight fraction of the hard segments was in the range 0.30–0.45. The effect of mixed soft segments, chain extenders, and zwitterionization on the extent of phase separation and physical properties was studied by utilizing differential scanning calorimetry and dynamic mechanical, stress-strain, and Fourier Transform Infrared spectroscopy experiments. All of these short segment block copolymers showed nearly complete phase separation. The zwitterionomer materials exhibited ionic aggregation within the hard domains. Although hard segment crystallinity or ionic aggregation did not affect the morphology, hard domain cohesion was important in determining the tensile and viscoelastic properties of these elastomers.     

Morphology development during the polymerization of styrene within a polyurethane network: Investigations by small-angle X-ray and light scattering

Phase separation that takes place during the formation of semi-interpenetrating polymer networks based on crosslinked polyurethane and linear polystyrene was studied by small-angle X-ray scattering and light scattering. The kinetics of the chemical reactions was followed by Fourier transform infrared spectroscopy. The occurrence of broad peaks in the X-ray scattering curves was interpreted in terms of distances between the urethane crosslinks. Small modulations on these curves were assigned to sphere-like structures with a diameter of around 5 nm which might be related to the urethane crosslink regions. Small modulations on the light-scattering curves at the beginning of styrene polymerization were assigned to spheres with diameters of around 4.5 μm, which can be related to the polystyrene-rich phase. These modulations disappear with time, which might indicate an increasing polydispersity of the domain sizes. The final morphology was found to depend on the time at which polymerization of styrene is initiated with respect to the time of gelation of polyurethane.     

Preparation of new membranes by complex formation of itaconic acid–acrylamide copolymer with polyvinylpyrrolidone: studies on gelation mechanism by light scattering

Mechanism of membrane formation by dipping a 10 wt% aqueous homogeneous polymer solution of poly(itaconic acid–co-acrylamide) (75:25 molar ratio)/polyvinylpyrrolidone (50/50) into acid solution was investigated by time-resolved light scattering and the pH effect of the acid solution to gelation mechanism during membrane formation was discussed. In the pH range 1.58–1.25, the gelation was governed by phase separation mechanism via the spinodal decomposition and then a membrane with regular pore size was obtained. The phase separation was caused by polymer–polymer complex formation between polymers. From an analysis based on Cahn's linearized theory of the spinodal decomposition, the apparent diffusion coefficient D_app of phase separation was smaller for lower pH. Because, at low pH there exists a lot of complex which dramatically reduces the chain mobility. The average pore size of membrane also depends on pH. When the pH was lower than 1.25, the liquid–liquid phase separation did not occur but the solution gelled homogeneously and a wrinkle-like morphology without pore was observed. FTIR analysis of the dried membranes showed that the complex formation had occurred by hydrogen bonding between the component polymers and its extent increased linearly with decreasing pH.     

Supermolecular morphology of thermoreversible gels formed from homogeneous and heterogeneous solutions

The supermolecular structures of thermoreversible gels formed from either homogeneous or heterogeneous solutions were examined by scanning electron microscopy. The morphologies of gels of polyethylene and polystyrene of various tacticities were then related to the phase diagram of the polymer–solvent system. We confirmed the morphological findings of Aubert on isotactic polystyrene gels formed either above the binodal or inside the spinodal and extended his study to gels prepared within the metastable region of the phase diagram. For polystyrenes and polyethylene, the morphology of the gels formed inside the coexistence curve differs markedly from that of gels formed outside. Inside the binodal, gels of polyethylene and polystyrenes exhibit remarkable morphological similarities, indicating a common gelation mechanism, namely, liquid-liquid phase separation. Depending on the concentration, these gels exhibit either an open strut-like network structure or smooth spherical globules. The former is attributed to gelation inside the spinodal whereas the latter is believed to result from gelation in the metastable region. For crystalline polymers, gels formed inside the coexistence curve subsequently undergo crystallization within their polymer-rich phase. The morphology of isotactic polystyrene and polyethylene gels formed outside the binodal consists of overlapping lamellar structures, whereas that of atactic and epimerized polystyrene gels is characterized by a sheet-like structure, differentiating the crystallization-based mechanism from others. © 1993 John Wiley & Sons, Inc.