Investigation of Phase Separation in a Partially Miscible Polymer Blend by Rheology

The phase boundary and phase‐separation dynamics of a binary poly(styrene‐co‐maleic anhydride)/poly(methyl methacrylate) blend have been investigated by rheological measurements and light scattering. The phase diagram was experimentally established by rheology, in which the binodal line was obtained by dynamic temperature ramps and the spinodal temperatures were quantitatively estimated on the basis of the theory developed by Ajji et al. The phase‐separation dynamics from rheological viewpoints have been further investigated on the basis of the obtained phase diagram. Rheological measurements can sensitively detect the rather early stages of phase separation compared with light scattering techniques. It was found that the dynamic storage modulus initially increases over time and subsequently decreases during nucleation and growth; on the other hand, it always decreased over time during spinodal decomposition. Compared with light scattering techniques, rheological measurements were found to be relatively reliable for probing phase‐separation mechanisms.     

Effect of Polymer-Substrate Interactions on the Surface Morphology of Polymer Blend Thin Films: Comparison between Simulation and Experiment

Microphase and macrophase separation phenomena can simultaneously appear in ABA/C copolymer blend systems due to the immiscibility among monomers A, B, and C. In this work, the surface morphologies and compositions of ABA/C blend thin films confined between two walls, which were used to mimic SEBS/PMMA films, have been simulated by a lattice Monte Carlo (MC) method. The effect of the polymer-wall interaction on the surface morphologies and compositions of thin films was investigated as a function of blend composition and film thickness. It is shown that the simulated surface morphologies of thin films resulting from the macrophase separation between copolymer ABA and homopolymer C and the microphase separation between block A and block B in ABA copolymer are similar to the experimental surface morphology of SEBS/PMMA polymer blend films observed by atomic force microscope (AFM). The effect of substrate on the surface morphologies by MC simulation is qualitatively consistent with the experimental results. The composition profiles of thin films are given to characterize the micro- and macrophase separation in thin films. It is indicated that the surface energy of the substrate (substrate/air) plays a crucial role on the surface composition. For a fixed surface, the adsorptions of polymer on the substrate and film thickness are also important.     

液晶聚合物/柔性链聚合物共混体系相分离形态

利用元胞动力学方法在二维情况下对浓度、取向序参量的含时Ginzberg Landau方程进行数值求解 ,研究了液晶聚合物 /柔性链聚合物共混体系的相分离动力学 ,考察了浓度、取向有序过程的耦合对相分离形态的影响 .结果表明 ,此耦合作用对相分离的时间进程以及相分离图样的空间排布都有影响 .液晶聚合物的取向有序相当于增加了两组分间的不相容性而促进两相分离 ;两个序参量在热力学方面的耦合使液晶聚合物趋向于沿着界面方向取向 ,而动力学方面的耦合使液晶聚合物分子沿着其取向方向扩散 ,相分离图样的空间排布由这两种效应共同决定 .通过极化率张量的定义用数值方法模拟得到了相分离体系的小角光散射图样 ,结果表明 ,散射强度分布具有方位角依赖性 ,它是由浓度、取向序参量的空间变化共同决定的 .     

Phase Separation in Poly(Methyl Methacrylate)-Epoxy Blend

Diglycidyl ether of bisphenol A (DGEBA) epoxy resin was modified with high molecular weight poly(methyl methacrylate) (PMMA). Morphological variations of a 2 wt% PMMA-modified epoxy mixture were studied by optical microscopy and scanning electron microscopy (SEM). A PMMA-epoxy blend cured at 100°C revealed that a secondary phase morphology was observed in both epoxy and PMMA phases from the early stages of the phase separation process. A morphology consisting of a rough striated continuous phase along with large smooth regions was observed by SEM, confirming the secondary phase separation. The dynamic mechanical thermal analysis showed that the PMMA modification of epoxy at such a low PMMA concentration of 2 wt% has no major influence on the glass transition temperature of the epoxy-rich phase. The PMMA-epoxy blend showed a slight increase in the flexural properties and the fracture toughness.     

Preparation of Poly(vinylidene fluoride)/Poly(methyl methacrylate) Blend Microporous Membranes via the Thermally Induced Phase Separation Process

The thermally induced phase separation (TIPS) process was employed to prepare poly(vinylidene fluoride)/poly(methyl methacrylate) (PVDF/PMMA) blend microporous membranes. The effect of PMMA content on the dynamic crystallization temperature of the PVDF/PMMA/sulfolane system was analyzed. The effects of PMMA weight fraction and cooling rate on the cross-sectional morphology, crystallinity, crystal structure, thermal stability, and porous structure of the resulting membranes were investigated using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and a mercury porosimeter, respectively. The mechanical properties of the membranes were evaluated by tensile tests. It was found that solid–liquid phase separation occurred in the PVDF/PMMA/sulfolane system. Scanning electron microscopy revealed that either increasing PMMA weight fraction or decreasing cooling rate will lead to a macroscopical phase separation between PVDF and PMMA. PMMA weight fraction and cooling rate had some influence on the crystallinity, porous structure, and mechanical properties, but no influence on the polymer crystal structure of the membranes. PMMA weight fraction influenced thermal stability of the final membranes but cooling rate did not.     

Light Diffraction of Aligned Polymer Fibers Periodically Dispersed by Phase Separation of Liquid Crystal and Polymer

We have confirmed light diffraction of aligned polymer fibers obtained by a phase separation of an anisotropic-phase solution of liquid crystal and polymer. He—Ne laser light passing through the polymer fibers was scattered in the axis vertical to the fibers, and had two peaks of light intensity symmetrical to the center of the transmitting laser spot. The two peaks were found to be caused by light diffraction due to the periodic polymer-fiber dispersion because the peaks corresponded to values calculated by intervals between the fibers. The periodical fiber networks are considered to be formed by anisotropic spinodal decomposition. This effect can be used to measure the dispersion order of the polymer fibers. © 2004 The Optical Society of Japan     

Phase Self-Assembly Driven Inverse Kinetics of Mixing in Ternary Encapsulated Polymer Blends

The influence of mixing time on the evolution of phase morphologies in poly(methyl methacrylate)/polystyrene/poly(butylene terephthalate) (PMMA/PS/PBT) and PMMA/PS/ polycarbonate (PC) immiscible ternary blends with encapsulated dispersed phases was investigated. It was found that both systems demonstrate up to a sevenfold enlargement of the phase dimensions with mixing time, that is, display an inverse kinetics of blending. In addition, three different mixing sequences (MSs) used for preparation of the compositions resulted in pronounced differences in the domain sizes, especially, at intermediate mixing times. These differences decreased gradually with further blending. The phenomena observed are explained in terms of a transition from the nonequilibrium to equilibrium encapsulated morphologies driven by interfacial forces and phase self-assembly effects.     

Hierarchic Structure Formation in Binary and Ternary Polymer Blends

The phase morphology of multi-component polymer blends is governed by the interfacial interactions of its components. We discuss here the domain morphology in thin films of model binary and ternary polymer blends containing polystyrene, poly(methyl metacrylate), and poly(2-vinylpyridine) (PS, PMMA, PVP). When sandwiched between two non-polar surfaces, characteristic lateral phase morphologies are observed after the film formation by spin-coating. We discuss here two techniques, by which hierarchical lateral structures in polymer films can be made. The first method makes use of two simultaneously occurring interfacial instabilities. The second technique employs the effect of a variation of the enthalpic interaction parameters in a ternary polymer mixture on its lateral polymer phase morphology.     

Crystallization Kinetics of Lamellar Crystals Confined in Polymer Thin Films

We used dynamic Monte Carlo simulations to investigate the crystallization kinetics of flat-on lamellar polymer crystals in variable thickness films. We found that the growth rates linearly reduced with decreasing film thickness for the films thinner than a transition thickness d_t , while they were constant for the films thicker than d_t . Moreover, the mean stem lengths (crystal thickness) we calculated decreased with film thickness in a similar way to the growth rates, and the intramolecular crystallinities we calculated confirmed the film thickness dependence of the crytsal thickness. Besides, the crystal melting rates in thin films were calculated and increased with decreasing film thickness. We proposed a new interpretation on the film thickness dependence of the crystal growth rate in thin films, suggesting that it is dominated by the crystal thickness in terms of the driving force term (l–l _min) expressed by Sadler, rather than the chain mobility based on experiments. The crystal thickness can determine whether a crystal grows or melts in a thin film at a fixed temperature, indicating the reversibility between the crystal growth and melting.     

Nonisothermal Crystallization Kinetics of Poly(Vinylidene Fluoride) in a Poly(Vinylidene Fluoride)/Poly(Methyl Methacrylate)/Dipropylene Glycol Dibenzoate System via Thermally Induced Phase Separation

The nonisothermal crystallization kinetics of poly(vinylidene fluoride) (PVDF) in PVDF/polymethyl methacrylate (PMMA)/dipropylene glycol dibenzoate (DPGDB) blends, where DPGDB served as a diluent, via solid–liquid (S-L) phase separation during a thermally induced phase separation process was investigated through differential scanning calorimetry (DSC) measurements. It was found that the Ozawa model could only describe the nonisothermal crystallization behavior of PVDF/PMMA/DPGDB system to some extent. The influence of the cooling rate and PMMA/PVDF weight ratio in the PVDF/PMMA/DPGDB system on the crystallization mechanism was also examined based on the Avrami–Jeziorny method and Mo method. Primary crystallization and secondary crystallization were observed in the Avrami–Jeziorny analysis. The analysis by the Avrami–Jeziorny and Mo models indicated that the increase of PMMA/PVDF weight ratio decreased the crystallization rate during the primary crystallization stage. The results showed that the Mo method could well explain the kinetics of the primary PVDF crystallization. The Avrami–Jeziorny method, however, could not well describe the nonisothermal crystallization process of PVDF in the primary crystallization stage. The activation energy, determined by the Kissinger method, was not suitable to reflect the PVDF crystallization process in the PVDF/PMMA/DPGDB system.     

纳米二氧化钒薄膜的电学与光学相变特性

采用双离子束溅射氧化钒薄膜附加热处理的方式制备了纳米二氧化钒薄膜。在热驱动方式下,分别利用四探针测试技术和傅里叶变换红外光谱技术对纳米二氧化钒薄膜的电学与光学半导体-金属相变特性进行了测试与分析。实验结果表明,电学相变特性与光学相变特性之间存在明显的偏差,电学相变温度为63 ℃,高于光学相变温度,60 ℃;电学相变持续的温度宽度较光学相变持续温度宽度宽;在红外光波段,随着波长的增加,纳米二氧化钒薄膜的光学相变温度逐渐增大,由半导体相向金属相转变的初始温度逐渐升高,相变持续的温度宽度变窄。在红外光波段,纳米二氧化钒薄膜的光学相变特性可以通过光波波长进行调控,电学相变特性更适合表征纳米VO₂薄膜的半导体-金属相变特性。     

Growth Rates of Edge-on Lamellar Crystals Confined in Polymer Thin Films

The growth rates of edge-on lamellar polymer crystals in variable thickness films were investigated in terms of dynamic Monte Carlo (MC) simulations. The growth rates linearly decreased with decreasing film thickness for the thinner films and were nearly constant for the thicker films. The mean stem lengths (crystal thickness) were also constant in different thickness films. The crystal widths parallel to the film thickness increased more slowly with increasing film thickness in the thinner films than that in the thicker films, indicating they were restrained by the film thickness. We propose that the growth rate of edge-on lamellar crystals in thin films is dominanted by the crystal width in the thinner films and by the crystal thickness in the thicker films; the variation of the film thickness can change the three-dimensional shape of the crystal growth front, also affecting the growth rate of the edge-on lamellar crystal.     

Phase separation of symmetrical polymer mixtures in thin-film geometry

Monte Carlo simulations of the bond fluctuation model of symmetrical polymer blends confined between two neutral repulsive walls are presented for chain lengthN _A=N _B=32 and a wide range of film thicknessD (fromD=8 toD=48 in units of the lattice spacing). The critical temperaturesT _c (D) of unmixing are located by finite-size scaling methods, and it is shown that , wherev ₃0.63 is the correlation length exponent of the three-dimensional Ising model universality class. Contrary to this result, it is argued that the critical behavior of the films is ruled by two-dimensional exponents, e.g., the coexistence curve (difference in volume fraction of A-rich and A-poor phases) scales as , where ₂ is the critical exponent of the two-dimensional Ising universality class ( ₂=1/8). Since for largeD this asymptotic critical behavior is confined to an extremely narrow vicinity ofT _c (D), one observes in practice effective exponents which gradually cross over from ₂ to ₃ with increasing film thickness. This anomalous flattening of the coexistence curve should be observable experimentally.     

Modeling of Phase Separation in Alloys with Coherent Elastic Misfit

Elastic interactions arising from a difference of lattice spacing between two coherent phases can have a strong influence on the phase separation (coarsening) behavior of alloys. If the elastic moduli are different in the two phases, the elastic interactions may accelerate, slow down or even stop the phase separation process. If the material is elastically anisotropic, the precipitates can be shaped like plates or needles instead of spheres and can arrange themselves into highly correlated patterns. Tensions or compressions applied externally to the specimen may have a strong effect on the shapes and arrangement of the precipitates. In this paper, we review the main theoretical approaches that have been used to model these effects and we relate them to experimental observations. The theoretical approaches considered are (i) macroscopic models treating the two phases as elastic media separated by a sharp interface, (ii) mesoscopic models in which the concentration varies continuously across the interface, and (iii) microscopic models which use the positions of individual atoms.     

Phase Ordering and Crystallization Kinetics in Ultrathin Poly(ethylene oxide)/Poly(methyl methacrylate) Blend Films

Crystallization in ultrathin Poly(Ethylene Oxide)/Poly(Methyl Methacrylate) (PEO/PMMA) blend films with thickness of ca. 10 nm was investigated by means of microscopic and in situ spectroscopic methods. It was revealed that the blend films undergo a phase ordering in a humid atmosphere before or during crystallization, with PEO de-mixing with PMMA and segregating to the free film interface on the PMMA layer. The de-mixed PEO chains crystallize into a fractal-like morphology by a diffusion-limited process, and the crystal growth is 1-dimensional with Avrami exponent n ≈ 1, resulting in flat-on crystal lamellae with the PEO chains oriented normal to the film plane.     

显微拉曼研究外延生长的BaTiO_(3-x)薄膜的结构相变与结构动力学(英文)

我们用显微拉曼、卢瑟福背散射谱、X射线散射和非对称摇摆等实验手段研究了在1 0 - 2 到1 0 - 5帕氧气压下用激光分子束外延技术生长的BaTiO3-x薄膜的结构动力学特性。测量结果表明生长氧压越低,晶格常数c和c/a越大,晶格常数a稍微减小,晶胞体积变大。随着生长氧压的减小,薄膜中氧含量减小。在3 0×1 0 - 5帕氧气压下生长的薄膜中氧缺陷可达0 48,但是样品的四方相结构可以很好的维持。显微拉曼研究进一步确定了样品都是四方相结构。另外,在BaTiO2 52 薄膜的拉曼光谱中发现高频段有两个新峰,其可能是由于氧缺陷导致的二级拉曼散射引起的。随着生长氧压的减小,拉曼峰向低频移动,表明薄膜中的应力减小。同时,拉曼峰变宽,这可能是由于氧缺陷导致的结构畸变引起的。由于在薄膜中存在二维张应力,BaTiO3单晶样品中的结构相变特征在我们的样品中从78到5 5 0K的温度范围内不存在。     

偶氮苯液晶薄膜相位共轭的光学记录研究

利用间并四波混频研究了一种偶氮苯液昌聚合物的相位共轭和光学记录特性，在近共振条件下，用低功率Ｎｄ：ＹＡＧ倍频激光得到高效率的相位共轭光和高阶衍射光，当光强达到１０Ｗ／ｃｍ＾２量级时，薄膜显示出光记录效应，即在撒掉写入光之后，相位共轭波并不消失，进一步大光强到１０＾３Ｗ／ｃｍ＾２量级时，出现三组分别只与前向泵浦光，后向泵浦光和信号有关的高阶衍射光。其中观察到第三阶衍射光，且在撒掉任两束光后，所剩一束     

Phase shift of polarized light through sculptured thin films: Experimental measurements and theoretical study

A slanted columnar TiO2 sculptured anisotropic thin film （ATF） is prepared via the glancing angle deposition technique and used as the phase retardation plate. The tilted nanocolumn microstructures of thin film induce the optical anisotropy. With the biaxial birefringent model, the optical constants dispersion equations of TiO2 ATF are derived by fitting the transmittance spectra for s-and p-polarized waves measured at normal and oblique incidence within 400 nm–1200 nm. The phase shift of polarized light after reflection and/or transmission through the TiO2 ATF is analyzed with the characteristic matrix employing the extracted structure parameters. The theoretical studies reasonably well accord with the experimental results measured with spectroscopic ellipsometry. In addition, the dependences of the phase shift on the coating physical thickness and oblique incidence angle are also discussed. Birefringence of the biaxial ATF provides a sophisticated phase modulation by varying incidence angles over a broad range to have a wide-angle phase shift.     

Oriented Crystallization of Polyethylene in Compatible Blends with Polyamide 11

The oriented crystallization of polyethylene (PE) in uniaxially oriented films of compatible blends with polyamide 11 (PA11) was studied. The PE sample used was a random copolymer of PE with methacrylic acid (MAA), poly(ethylene-co-methacrylic acid) (PEMAA), with 4wt% MAA units. Oriented films of PA11/PEMAA blends were prepared by uniaxial drawing of the melt-mixed blends. The drawn films with fixed lengths were heat-treated at 120°C for 3min to melt the PE component, followed by cooling the sample to room temperature at a rate of 2°C/min to recrystallize the PE (designated slowly crystallized sample). The PE component crystallized in elongated domains of PEMAA with diameters of 0.5–2 μ m and lengths of 5–10 μ m for the PA11/PEMAA = 80/20 blend, resulting in the oriented crystallization of PE crystals. The crystal b-axis of PE was highly oriented in the direction perpendicular to drawing, while the crystal a-axis was weakly oriented in the drawing direction in the slowly crystallized sample of the PA11/PEMAA = 80/20 blend. The a-axis orientation of PE crystals in the PA11/PEMAA = 80/20 blend contributes to the improvement of mechanical properties in the direction perpendicular to drawing.     

Spectral-Luminescent and Lasing Properties of Aminocoumarin Derivatives in Thin Polymer Films

The absorption and fluorescence spectra and the lasing ability of aminocoumarin derivatives in thin polymer layers (0.5–0.8 μm) based on the copolymer methylmethacrylate with a methacrylic acid and the copolymer methylmethacrylate with glycidylmethacrylate formed by coating of optically transparent glass substrates have been studied. It is found that the intensity of absorption and luminescence as well as the lasing resource of coumarins are determined by the structure of the latter and by the nature of the polymer medium. Compositions based on the copolymer methylmethacrylate with glycidylmethacrylate and aminocoumarin derivatives with a fluorized methyl group at the 4th molecular position can be of interest in optical technologies (light transformers, amplifiers). __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 464–467, July–August, 2005.