Kinetics of Formation and Evolution of Phase Structure in Multipolymer: 1. The Application of Semilogarithmic Plot Method to Early Stage of Phase Dispersion

Kinetics of phase dispersion of binary blends of polypropylene and poly(cis-butadiene) rubber during the processing in a batch mixer was investigated by a back small-angle laser scattering (BSALS) online system. It was found experimentally that the scattering intensity I(q, t) followed an exponential growth with time during the early dispersion stage from 1 s to 65 s, while at t > 65 s, the slope levels off with time. A theory in which two critical parameters, W(q) and D_d, were calculated was proposed to describe the early stage of phase dispersion; the former parameter is defined as the rate of decreasing dispersed phase dimension, and the latter, evaluated from the slope of W(q) versus q² plot, is the dispersion coefficient. W(q) remains constant with the increment of dispersed phase. W(q) has a self-similarity with q for different compositions. The slope β, defined as the dispersion acceleration evaluated by linear fit in the nonscaling interval, was determined to explain the similar evolution mechanisms for the different velocity distributions of W(q). The dispersion coefficient D_d increases with the increment of the dispersed phase, and does not vary with shear rates.     

Light Scattering Studies on Phase Behavior of PP/PcBR Blends During Melt‐Mixing

Phase formation, morphology, and their evolution of binary blends of polypropylene with poly(cis‐butadiene) rubber were investigated by a back small angle laser scattering (BSALS) on‐line system and online sampling. The morphology formation process can be divided into three stages: early stage, intermediate stage, and late stage. Phase contrast microscopy (PCM) and small angle laser scattering (SALS) measurements have been introduced to compare with the results of BSALS and the corresponding phase morphology was also observed using scanning electron microscopy (SEM). Structure parameters such as average chord length l¯₁ and integral invariant Q were calculated to describe the relationship between phase evolution and processing conditions. Furthermore the velocity constant of the dispersed phase dimension variation k=dQ/dt was calculated at the early stage to describe the relationship with different volume fractions of dispersed phase. The characteristic wavevector q _m , and its corresponding maximum intensity I _m , increase monotonically with time and vary exponentially with time at the early stage of phase dispersion; the slope yields the change rate constants of domain size for q _m and I _m , α and β, respectively. The rate constants α and β increase with increasing content of dispersed phase, and α/β ≈1.     

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.     

Study on the Mechanism of the Formation and Evolution of Phase Structure in PP/PcBR Blends

Phase dispersion theory was proposed to study the dynamic process of polymer blending with the help of mineral processing theory. Two constants, dispersion coefficient n and process coefficient b, were calculated for the early dispersion stage to describe the varying velocity of the dispersed phase dimension. In this dispersion theory, the phase dimension of binary blends of polypropylene with poly(cis‐butadiene) rubber linearly increased with blending time in the early stage on a double logarithmic scale, which suggested that phase dispersion theory was applicable to the study of polymer blending dynamics. In this study, the influence of the processing conditions, that is, composition, temperature, and shear rate, on the two constants of n and b was also studied. The results showed that n and b decreased with increasing dispersed phase, and reached a minimum when the shear rate was 60 rpm. The dispersion coefficient n first decreased with increasing temperature, reached a minimum when the temperature was 200°C, and then increased with a further increase in temperature, but there was no apparent influence of temperature on the process coefficient b. The coinfluence of blending temperature and shear rate on the dispersion coefficient n showed that the smaller the content of the dispersed phase, the more sensitive the decreasing rate of phase dimension was to the temperature and shear rate.     

Phase Structure Characterization by SALS of In Situ Compatiblized Binary Polymer Blends and Its Relation to Rheology

Phase structures of polypropylene (PP)/polystyrene (PS) blends, in situ compatiblized by a Friedel–Crafts alkylation reaction with anhydrous aluminum chloride (AlCl₃) as a catalyst, were investigated by small angle light scattering (SALS). The invariant Q, the content of compatible domain between the two phases, i.e., the interphase volume fraction, and the interphase thickness of the in situ compatiblized binary polymer blends were determined by Rayleigh scattering, as well as the phase structure parameters, such as correlation distance and average chord lengths. The results showed that the obtained blend is a partially compatible system. The invariant Q, the interphase volume fraction, and the interphase thickness all can be used to characterize the in situ interfacial compatiblization of the blends and all showed a nonlinear dependence on the in situ formed copolymer content. Further investigations revealed that the contribution of the interfacial modification to the zero shear viscosity of the in situ compatiblized blends showed exponential decay with the increasing invariant Q and showed exponential growth with the increasing volume fraction and thickness of the interphase in the blends. The nonlinear relations between the three phase structure parameters and the in situ formed copolymer content, as well as the nonlinear relations between the three phase structure parameters and the contribution of the interfacial modification to the zero shear viscosity of the blends, might be closely related to the in situ formation of the copolymer and its effect at the interfacial surface in the blends.     

Interaction of Domains in Ternary Polymer Melt Blends with Separate Dispersions of the Inner Phases

The morphology evolution in three immiscible ternary polymer systems characterized by separate dispersions of the dispersed phases (i.e., no encapsulation phenomena takes place) was characterized. The components used were three of the following: commercial atactic poly(methyl methacrylate) (PMMA) and polystyrene (PS), crystallizable poly(butylene terephthalate) (PBT) and isotactic polypropylene (PP) and glass microspheres (GMS). In System I PMMA/PS/PP (primary dispersed phase/matrix/secondary, or minor, dispersed phase), all of the components were liquid on blending at 190°C. In System II PP/PS/PBT and System III PP/PSyGMS, at 190°C, the minor PBT and GMS dispersed phases were nondeformable. It was shown that small portions (0.5–1.0 wt%) of the PP minor dispersed phase added to the binary PMMA/PS blend produced a dual action: (a) transition of the PMMA dispersed phase to a cocontinuous one and (b) simultaneous substantial (up to a 6-fold) growth of the degree of dispersion of the blend. Moreover, these effects were accompanied by about a three-fold reduction of the threshold PMMA concentration (C*) at which it formed its own co-continuous phase in the ternary blend compared to that in the PMMA/PS binary mixture. The observed phenomena took place regardless of whether the domains of the minor dispersed phase were liquid (System I) or solid (Systems II and III), and was strongly related to the domain sizes of this phase and blend composition. A mechanism underlying the outlined behavior is proposed.     

Confined Crystallization in Polymer Blends: DSC Studies of the Behavior and Kinetics of Isothermal Crystallization of Polypropylene in Poly(cis-butadiene) Rubber Blends

Thermal properties of polypropylene with poly(cis-butadiene) rubber (iPP/PcBR) blends have been measured by differential scanning calorimetry (DSC), and the melting point T_m, crystallization temperature T_c, enthalpy Δ H (melting enthalpies and crystalline enthalpies), and equilibrium melting point T⁰ _m have been measured and calculated. The variation of T_m, T_c, Δ H and T⁰ _m with composition in the blends was discussed, showing that an interaction between phases is present in iPP/PcBR blends. The degree of supercooling characterizing the interaction between two phases in the blends and the crystallizability of the blends which bears a relationship to the composition of the blends was discussed. The kinetics of isothermal crystallization of the crystalline phase in iPP/PcBR blends was studied in terms of the Avrami equation, and the Avrami exponent n and velocity constant K were obtained. The Avrami exponent n is between 3 and 2, meaning that iPP has a thermal nucleation with two dimensional growths. The variation of the Avrami exponent n, velocity constant K, and crystallization rate G bear a relation to the composition of the blends, n increases with increasing content ofPcBR. K also increased with increasing content of PcBR. All of the K for the blends are greater than for pure iPP. The crystallization rate G (t_1/2) depends on the compositions in the blends; all G of the blends are greater than for iPP.     

激光大气闪烁的分形分析

采用分形理论分析了激光大气闪烁的统计特征。研究结果表明：在弱起伏条件下,激光大气闪烁的分形维和奇异性随光强起伏的增强而增大,而其长期相关性则减小;不同Fresnel尺度下具有相同闪烁指数的激光大气闪烁的分形特征存在着明显的差别;在强起伏条件下,有限的数据中尚未发现分形维有饱和现象,因此可以用来描述激光大气闪烁的强度。     

Morphological Aspects of In-Situ Compatiblized Binary Polymer Blends With Variable Viscosity Ratios of Components

The in-situ compatiblized binary polymer blend polypropylene(PP)/polystyrene(PS)/ anhydrous aluminum chloride(AlCl₃) was selected as a model system of a reactive polymer blend to investigate the effect of viscosity ratio of components at a constant shear rate on the phase morphological behavior in in-situ compatibilized systems. The results showed that the well-known interfacial compatibilization effect was related to variations of viscosity ratios of components in the reactive PP/PS blends with different contents of AlCl₃ catalyst. The phase morphology evolution of the in-situ compatiblized reactive blend was determined by both the interfacial compatibilization and the variation of the viscosity ratio of components under the fixed mixing conditions, which showed characteristics obviously different from and much more complex than those in binary polymer blends generally compatiblized by added compatiblizers. The results implied that the variation of the viscosity ratio of components should be checked carefully and taken into account if necessary, when the phase morphology of binary polymer blends is investigated, especially in complex in-situ compatiblized reactive polymer blends.     

Percolation Thresholds in Ternary Polymer Melt Blends with Separate Dispersions of the Inner Phases: Mathematical Model

A mathematical model based on a straightforward geometrical background is developed which enables predictions of a transition of one dispersed phase to a cocontinuous one (i.e., the percolation threshold) on addition of another dispersed phase during melt mixing in ternary polymer blends. The present work concerns only ternary blends with two separate dispersions of the inner phases in which no encapsulation takes place. In addition, in order to simplify the model, one of the inner phases was represented by hard, nondeformable microspheres The expression developed describes well an experimental relationship between the percolation threshold, the concentration above which the former dispersed phase transforms to a continuous one, and concentrations of both inner phases. The results agree well with the experimental data obtained in a previous work.     

金属包覆有机聚合物波导色散特性的实验研究

采用角度扫描衰减全反射（ＡＴＲ）技术，对银金属膜包覆的ＤＲ－１／ＰＭＭＡ型有机聚合物波导的色散特性进行了实验研究，从各波长下衰减全反射共振吸收峰的位置和半宽度确定了波导相应模式的传播常数，实验结果与理论计算符合较好，说明银膜介电常数的虚部可作为微扰小量处理。     

Fractal Modeling of Polymer Plasma Laser Ablation,Plasma Plume Tsallis Entropy and Its q-Statistics Interpretation,Part I: Theory

Polymer plasma produced by laser ablation is investigated in a theoretical manner. In relation to the fact that the charge carrier circulation is assumed to take place on fractal curves, the so-called fractality type, electrical charge transport can be resolved by an extended scale relativity method. In addition, an elegant mathematical model, utilizing a conjecture of fractal space-time, is elaborated. The complete solution and its graphical representation for temperature distribution in two-dimensional and three-dimensional cases are successfully introduced. The discrete physical behavior and irrevocable transformation of nanoscale microdomain substructures by laser ablation are realistically examined. Further, benefiting from the interpretation of the fractal analysis, each of the experimental results can be fairly explained. On top of that, this paper presents a proof of Tsallis nonextensive q-statistics, especially for the plasma plume studied. Tsallis entropy in direct connection with fractal dynamics and chaotic-type mechanics of the plasma plume and time-series representation of plasma temperature is introduced for the first time in the present publication, and the q-statistics of the plume plasma temperature are also studied, among others.     

三相系统部分结晶聚合物结构参数小角X射线散射分析

使用小角X射线散射技术分析了部分结晶聚合物结构参数,结晶度和片层厚度与两相系统中的结果不一致,对一些部分结晶聚合物样品的分析表明它们的Bragg长周期接近相关函数长周期与过渡层厚度的和,这个结论也与部分结晶聚合物存在中间过渡层一致.     

多组分磷脂巨囊泡的相结构和胆固醇对微畴成长的影响

巨囊泡作为细胞的简化模型,其相分离与出芽动力学规律已引起许多领域科学家的关注.本实验采用DPPC/DOPC/Chol的三组分形成的巨囊泡作为模型,借助荧光显微镜观察该三组分体系侧向分离的相结构图,并对微畴的成长过程作了系统的观察研究和理论分析.实验发现:从高温的均相区域淬灭到低温的分相区域,膜表面发生侧向分离形成微畴.体系内胆固醇的掺入量的多少会影响磷脂膜的相结构和膜内微畴的成长,固定DOPC/DPPC为1:1的前提下,微畴尺寸随着胆固醇掺入量的增加而变大.     

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     

相位微扰法在粗糙面光散射中的应用

根据粗糙面散射理论，用相位微扰法推导出了从随机粗糙介质表面散射的激光雷达散射截面的理论计算公式，计算了几种粗糙表面样品在１．０６μｍ下的单位面积激光雷达散射截面，数值结果与实验数据基本吻合。     

分形凝聚粒子的光散射特性研究

粒子的形状和凝聚对光散射特性有着很大的影响.基于分形生长的受限扩散(DLA)模型,模拟了凝聚粒子的三维空间分形结构,并采用回转半径法计算了凝聚粒子的分形维数.利用离散偶极子近似(DDA)方法研究了纳米石墨凝聚粒子的光散射特性,对于原始粒子数不同的凝聚粒子及分形结构不同的凝聚粒子,数值计算了散射强度和偏振度随散射角的分布...     

Interaction Energy in Polymer Blends Containing N-1-Alkylitaconamic Acids Moiety

Abstract

Analysis of the interaction energy of N-1-alkylitaconamic acids to explain the miscibility behavior of polymers containing this moiety is performed. In order to calculate the interaction energy, many conformations of the N-1-alkylitaconamic acid fragments containing ethyl, propyl, butyl, hexyl, octyl, decyl, and dodecyl were selected randomly from molecular dynamic simulations. It was assumed that miscibility and other properties are determined by the enthalpy of mixing, ΔH_mix, that ΔH_mix is dominated by the local interactions between segments of the polymer chains, and, furthermore, that PΔV_mix contribution can be ignored. The polymer miscibility is discussed by using interaction energies calculated from molecular mechanics studies on pairs of small polymer fragments. By this method and by using the Blend package (Accelrys), good correlations between the interaction energy and the Gordon Taylor constant (K_GT) values for blends of poly(N-1-alkylitaconamic acids) and poly(4-vinylpyridine) previously reported are obtained. The analysis of the energies shows that Coulombic energies decay rapidly being almost “zero” as the side-chain lengths reach near eight carbon atoms. On the contrary, the van der Waals interaction (VDW) energies decay in a linear way as the length of the side chain increases. The slope of the VDW energies is an estimation of the energetic contribution per methylene unit to the blending process. The slope in this case is 570 cal/mol, which is a value very close to that experimentally reported in the literature for related systems. The blend energy was calculated, and good correlation with the experimental results is obtained.     

光纤通信系统中基于光学相位共轭和预啁啾的色散及非线性补偿研究

采用光学相位共轭补偿光纤通信系统的色散及非线性必须满足一个前提条件,即相位共轭器两边线路上的色散和非线性分布(或传输功率分布)必须严格对称,这在现有的一般传输线路（标准单模光纤加集总掺铒光纤放大器）难以实现。提出了预啁啾结合中距相位共轭的补偿方案,并进行了数值计算。结果表明,通过在发送端对输入脉冲进行预啁啾展宽,可有效地减轻非线性效应与色散的相互作用,获得理想的补偿效果;对于皮秒超短光脉冲传输,脉冲内拉曼散射相对于三阶色散对补偿结果的影响很小,因此,频域相位共轭相对于时域相位共轭具有更好的综合补偿性能。该方案简单易行,无需对已敷设好的线路作较大改动。