The Chain Stretching Effect on the Morphology and Rheological Properties of Phase‐Separating Polymer Blends Subjected to Simple Shear Flow

Summary: The spinodal decomposition of a binary mixture subjected to simple shear flow is investigated in the framework of the modified time‐dependent Ginzburg‐Landau (TDGL) equation with an external velocity term. The domain growth and related rheological properties of a binary mixture under shear flow are simulated in three dimensions by means of the cell dynamics scheme (CDS). The simulation results show that the domain growth is anistropic and depends on the terminal relaxation time of the polymer chain. It is found that lamellae‐like domains with the normal parallel to the velocity gradient direction are observed when the terminal relaxation time is long enough. This result has also been confirmed by carefully checking the scattering functions in different incident light directions and the evolution of the domain size in different directions. In addition, when the chain stretching effect is strong, the transients of the excess shear viscosity are much higher than the case without the chain stretching effect. The terminal relaxation time of the chain also has an important effect on the first and second normal stress differences.

The time evolution of the morphology for the case with strong chain stretching effect.     

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.     

PVA/HDPE/HDPE-g-MAH共混物的相形貌与动态流变性能

采用熔融共混法制备了聚乙烯醇(PVA)/高密度聚乙烯(HDPE)共混物,引入马来酸酐接枝高密度聚乙烯(HDPE-g-MAH)对体系进行增容。利用SEM、小振幅震荡剪切、溶剂提取、拉伸测试考察组成和增容剂含量对共混物相形貌、动态流变性质、相连续性和力学性能的影响。结果表明,当HDPE质量分数达到20%~30%时,PVA/HDPE/HDPE-g-MAH共混物呈现接近共连续的结构;储能模量-频率图中观察到较为明显的第二平台;PVA相的连续度达到98%;共混物的断裂伸长率由5%显著提高到25%左右。另外,当HDPE-g-MAH的含量增大时,共混物的相界面变得模糊,力学性能也随之提高。     

Shear‐induced Apparent Shift of Phase Boundary of Binary Polymer Blends

Summary: The combined influence of the thermodynamical and hydrodynamic effects of shear was tentatively considered for the first time, in the modeling of the shear‐induced phase behavior of binary polymer blends in this paper. In this model, the original “two‐fluid” model proposed by Onuki 1 , 2 was modified by replacing the quiescent thermodynamical term with the one defined in the frame of extended irreversible thermodynamics (EIT). 3 - 5 The stress term of the polymer blend was determined by using the mixing rule of “Double Reptation” 6 , 7 along with the Graessley's 8 functions to make the model applicable in both linear and weak non‐linear regions. Then the apparent shift of phase boundary of a model blend system was computed by using this theory. It's found that this modified theory can predict both the “miscibility gap” and anisotropical phase separation of the polymer blend, while the two different previous theories, that is the pure thermodynamical one and hydrodynamic one, could only predict one but not both of them. For example, this modified “two‐fluid” model predicts that the miscibility gap can be observable not only in vorticity direction but also in the velocity gradient direction.

The calculated reduced stored energy F_s/RT as a function of Φ_A and the temperature T (shear rate: 0.5 s⁻¹).     

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     

温度梯度引起的聚合物共混物梯度相形态的研究

研究了两相不相容聚合物共混物在静态退火时,由温度梯度引起的分散相尺寸的空间分布梯度相形态,讨论了分散相体积分数和两相之间界面张力对梯度形态形成的影响.应用接触凝聚模型计算了在温度梯度作用下,分散相粒子的粗化过程.计算结果表明,界面张力越大,或者分散相体积分数越大,形成的梯度相形态越明显;并且在温度梯度存在下,分散相粒子粗化的速度加快.     

Phase Morphologies of Binary Polymer Blends Predicted by Systematically Coarse‐Grained Models

In this work, the combined iterative Boltzmann inversion/conditional reversible work scheme is extended with a little modifications to derive the systematically coarse‐grained (CG) potentials for simulating two typical atactic polymer blends composed of poly(methyl methacrylate) (PMMA) and poly(vinyl chloride) (PVC) or polystyrene (PS). Molecular dynamics simulations are extensively performed on the two blends with a wide formulation range. It is revealed by these simulations that, throughout the entire composition range, the PMMA/PVC blend is homogeneous whereas the PMMA/PS blend undergoes phase separation, which agrees well with the experimental observation that the former exhibits strong interactions that are absent in the latter. Depending upon the formulation, the immiscible PMMA/PS blend presents one single‐ or double‐continuous phase. It is further confirmed that intermolecular interactions play the key roles in forming the phase morphologies, which in turn can be inferred from only the three nonbonded CG potentials of one unlike pair and two like pairs.

     

Phase Evolution Theory for Polymer Blends with Extreme Chemical Dispersity: Parameterization of DDFT Simulations and Application to Poly(propylene) Impact Copolymers

DDFT is applied to phase formation in homopolymer/copolymer blends in which the copolymer is extremely disperse with a uniform chemical composition distribution. Such systems develop a core/shell structure with a thick interface. This study is motivated by peculiarities in the phase evolution of industrial PP high‐impact copolymers. It is demonstrated that it is possible to reach time and length scales of relevance for realistic industrial blend systems. A rational method for improving the numerical efficiency of the calculations is presented. The model can be applied to a variety of industrially relevant systems with similar “random chemistry” or extreme copolymer dispersity in coatings, crude oil recovery systems, food emulsions, and so forth.

     

HQ-PPEK/PC共混物的相容性与流变性

聚芳醚酮;聚碳酸酯;共混物;流变性能;HQ-PPEK/PC共混物的相容性与流变性     

“Volume‐Preserving” Conformational Rheological Models for Multi‐Component Miscible Polymer Blends Using the GENERIC Formalism

A family of conformational rheological models for multi‐component miscible polymer blends is developed using a modified form of the Poisson bracket formulation. Two conformation tensors called c ₁ and c ₂ are introduced to show the orientation of the first and the second components of a blend, respectively. The mobility tensor and the energy function for each blend component are expressed in terms of these conformation tensors. The interaction effects are also included by energy expressions. The predictions of this family of “volume‐preserving” models are illustrated for a Hookean‐type energy function and several expressions of the modified mobility tensors. The results are illustrated for material functions in transient (start‐up and relaxation) and steady shear flows. The predictions are compared with experimental data taken from the literature for a miscible polymer blend. Study of the model sensitivity to its parameter shows that model predictions can cover a wide range of rheological behavior generally observed for multi‐component miscible polymer blends in steady and transient shear flows.

Experimental data and model predictions for steady shear viscosity for HDPE/LDPE blends.     

Influence of Reactive Compatibilization on the Melt Flow Properties and Morphology of Polyamide 6/Styrene-Acrylonitrile Blends

Summary: In this study, we investigate the influence of reactive compatibilization on the rheological properties of polyamide 6/styrene-acrylonitrile (PA 6/SAN) blends in the melt. Linear viscoelastic shear oscillations, simple elongation to a large stretch ratio and subsequent recovery experiments were performed. The morphology of the blends was examined by atomic force microscopy. We prepared three PA 6/SAN blends with different composition ratios of PA 6 and SAN (70/30, 50/50, 30/70) and a constant concentration of the reactive agent. Our experiments revealed that reactive compatibilization significantly increases the complex modulus of PA 6/SAN blends at low frequencies. In particular, the data of the PA 6/SAN 50/50 blend and the PA 6/SAN 30/70 blend indicated that an elastic network between neighbouring PA 6 domains was formed. In simple elongation, the transient elongational viscosity of the blends exceeded the values of the single components. In recovery, the recovered stretch of all blends was larger than the recovered stretch of the pure components. The differences of the blend morphology and of the linear viscoelastic behaviour were qualitatively explained by the asymmetric properties of the reactively compatibilized interface.     

界面张力对高分子共混物梯度相形态形成的影响研究

研究了界面张力对ＰＰ／ＥＶＡ共混体系梯度相形态形成的影响。首先将ＥＶＡｃ进行皂化反应得到一系列－ＯＨ基含量不同即极性不同的ＥＶＡ，然后将这些ＥＶＡ分别与ＰＰ共混从而得到一系列相界面张力不同的共混物。说明通过对共混物相界面张力的调整，可以达到随意控制梯度相形态形成速度的目的。     

Morphology development of main‐chain liquid crystalline polymer fibers during solvent evaporation

A nonequilibrium thermodynamic approach has been developed for describing the emergence of fiber morphologies from a liquid crystalline polymer solution undergoing solvent evaporation, including fibrillar structures, concentric rings, and spiral structures. We utilized Matsuyama–Kato free energy for main‐chain liquid crystalline polymer (MCLCP) solutions, which is an extension of Maier–Saupe theory for nematic ordering and incorporates a chain‐stiffening, combined with Flory‐Huggins free energy of mixing. Temporal evolution of the concentration and nematic order parameters pertaining to the above free energy density of liquid crystalline polymer solution was simulated in the context of time‐dependent Ginzburg–Landau theory coupled with the solvent evaporation rate equation under the quasi‐steady state assumption. The emerged morphological patterns are discussed in relation to the phase diagram of the MCLCP solution and the rate of solvent evaporation. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 429–435, 2007     

Specular and Diffuse Reflectance of Phase‐Separated Polymer Blend Films

Diffuse reflectors have various applications in devices ranging from liquid crystal displays to light emitting diodes, to coatings. Herein, specular and diffuse reflectance from controlled phase separation of polymer blend films, a well‐known self‐organization process, are studied. Temperature‐induced spinodal phase separation of polymer blend films in which one of the components is selectively extracted is shown to exhibit enhanced surface roughness as compared to unextracted films, leading to a notable increase of diffuse reflectance. Diffuse reflectance of UV–visible light from such selectively leached phase‐separated blend films is determined by a synergy of varying lateral scale of phase separation (≈200 nm to 1 μm) and blend film surface roughness (0–40 nm). These critical parameters are controlled by tuning annealing time (0.5–3 h) and temperature (140, 150, 160 °C) of phase separation. Angle‐resolved diffuse reflection studies show that the surface‐roughened polymer films exhibit diffuse reflectance up to 40° from normal incident light in contrast to optically uniform as‐cast films that exhibit largely specular reflectance. Furthermore, the intensity of the diffusively reflected light can be enhanced (300–700 nm) or reduced (220–300 nm) significantly by coating the leached phase‐separated films with a thin silver over layer.

     

聚合物分散剂对氟铃脲水悬浮剂流变性质的影响

采用控制应力流变仪研究了聚合物分散剂苯乙烯丙烯酸无规共聚物（MOTAS）用量、分子量及氟铃脲质量分数等对氟铃脲水悬浮剂流变性质的影响。 结果表明,以聚合物MOTAS为分散剂制备的氟铃脲水悬浮剂的流变行为符合Herschel-Bulkley模型。 在固定氟铃脲质量分数为20%时,当分散剂质量分数≤3.0%时,流动行为指数n≤1.0,悬浮体系表现为假塑性流体,当分散剂质量分数≥3.5%时,流动行为指数n≥1.0,悬浮体系具有胀塑性流体特征。 氟铃脲水悬浮剂的流变参数屈服值τH与分散剂MOTAS和氟铃脲的加入量有关。 分散剂MOTAS质量分数≤2.5%时,分散剂在氟铃脲颗粒界面吸附很少,裸露的氟铃脲颗粒界面间相互搭接,具有较大的屈服值τH;当分散剂加入质量分数为3.0%时,分散剂可在氟铃脲颗粒界面形成饱和吸附,若再增加分散剂用量,多余分散剂在悬浮的氟铃脲颗粒间形成搭接,使其屈服值τH增大。 在MOTAS分散剂的分子量在10 000~30 000范围内时,MOTAS分子量愈大,所制得的氟铃脲水悬浮剂的表观粘度和屈服值τH愈小,流变行为指数n虽略有增加,但均小于1,没有改变“剪切变稀”的假塑性特征。     

Preparation of Core‐Sheath Nanofibers from Conducting Polymer Blends

Summary: Core‐sheath nanofibers with conductive polyaniline as the core and an insulating polymer as the sheath were prepared by electrospinning of blends of polyaniline with either polystyrene or polycarbonate. These unique core‐sheath structures offer potential in a number of applications including nanoelectronics. When polyaniline was blended with poly(methyl methacrylate) and poly(ethylene oxide), only isolated domains of polyaniline in beadlike structures were formed. The phase morphology of electrospun fibers is thought to be dependent on the high‐surface tension of the solution and the molecular weight of the polymers. Incompatibility of the polymers and low molecular weight of compositions played a key role in the formation of core‐sheath structures, as opposed to co‐continuous morphologies.

TEM image of electrospun polyaniline/polystyrene nanofiber after staining by OsO₄. The dark regions are polyaniline.     

SiO2纳米粒子对受限流场下聚异丁烯/聚二甲基硅氧烷共混物相形态的影响

利用显微-光学剪切联用系统构造受限剪切环境,探讨了少量不同表面性质的SiO2纳米粒子的加入对聚异丁烯(PIB)/聚二甲基硅氧烷(PDMS)不相容共混体系分散相形态演变过程的影响.研究结果表明,少量疏水性SiO2纳米粒子的加入可抑制分散相液滴的凝聚,从而抑制珍珠链状及纤维状等超级相形态的形成,使共混物表现为近似本体流体的...     

Dynamic Viscosity of PEG:PEG‐ran‐PPG Blends through Stress Relaxation

Densities and viscosities of a series of blends of poly(ethylene glycol) (PEG) and poly(ethylene glycol‐ran‐propylene glycol) (PEG‐ran‐PPG) were measured at a temperature above the melting point. The density and viscosity data were fitted with analytical functions involving the volume fraction of PEG, ϕ_PEG. Stress relaxation curves for the pure components and blends were obtained through Monte Carlo (MC) simulations. A typical stress relaxation curve exhibits a fast mode that represents energetic‐interactions‐driven motion and a slow mode that originates from the entropy‐driven motion. Flory–Huggins interaction parameters (χ) for the blends are much smaller than the critical values (χ_critical). The calculation of χ and χ_critical provides important clues for polymer blend processing.