Electrical characteristics of copper phthalocyanine thin-film transistors with polyamide-6/polytetrafluoroethylene gate insulator

Polyamide- 6(PA 6)/polytetrafluoroethylene is studied as a potential gate dielectric for flexible organic thin film transistors. The same method used for the formation of organic semiconductor and gate dielectric films greatly simplifies the fabrication process of devices. The fabricated transistors show good electrical characteristics. Ambipolar behaviour is observed even when the device is operated in air.

Non-isothermal crystallisation kinetics of polyamide 6/mesoporous silica nanocomposites

Non-isothermal crystallisation kinetics of a polyamide 6/mesoporous silica nanocomposite (PA6-MS) has been investigated by differential scanning calorimetry (DSC) at different cooling rates. Mandelkern, Jeziorny-Ziabicki and Ozawa methods were applied to describe this crystallisation process. The analyses show that the mesoporous silica particles act as nucleating agents in the composite and that the Avrami exponent n varies from 3.0 to 4.6. The addition of mesoporous silica influenced the mechanism of nucleation and the growth of polyamide 6 (PA6) crystallites.

Compatibilization of polyamide-6/syndiotactic polystyrene blends using styrene/glycidyl methacrylate copolymers

Blends of polyamide-6 (PA6) with syndiotactic polystyrene (sPS) were prepared using a series of styrene/glycidyl methacrylate (SG) copolymers as compatibilizers. These copolymers are miscible with sPS, and the epoxide units in SG are capable of reacting with PA6 end groups. These copolymers thus have the potential to form SG-g-PA6 graft copolymers at the PA6/sPS interface during melt processing. This study focuses on the effects of functionality and concentration of the compatibilizer on the morphological, mechanical and crystallization behaviors of the blends.. In general, SG copolymers are effective in reducing the sPS domain size and improving the interfacial adhesion. About 5 wt% glycidyl methacrylate (GMA) is the optimum content in SG copolymer that produces the best compatibilization. Both the strength and modulus of the blend have been improved on addition of the SG copolymers, accompanying a loss in toughness when higher concentration copolymer is added. Incorporation of SG compatibilizers to PA6/sPS blend has little influence on the crystallization behavior of PA6 component but resulted in a steady reduction in intensity of crystallinity peak of sPS and simultaneous crystallization of sPS with PA6 is observed.

Reactive compatibilization of polyamide 6 with isocyanate functionalized ethylene-propylene copolymer

Reactive compatibilization of ethylene-propylene copolymer functionalized with allyl (3-isocyanato-4-tolyl) carbamate (TAI) isocyanate (EPM-g-TAI) and polyamide 6 (PA6) was investigated in this paper, FTIR analysis revealed the evidence of a chemical reaction between the end groups of PA6 and EPM-g-TAI. Thermal, rheological, morphological, and mechanical properties of the resultant system were examined, DSC analysis indicated that the crystallization of PA6 in Pa6/EPM-g-TAI blends was inhibited, due to the chemical reaction that occurs at the interface of PA6 and EPM-g-TAI. Rheological measurement showed that complex viscosity and storage modulus of PA6/EPM-g-TAI were both dramatically enhanced compared to those of PA6/EPM at the same blending composition. After examining the morphology of both blending systems, smaller particile sizes, more homogeneous distribution of domains and improved interfacial adhesion between matrix and domains were observed in the compatibilized system. Mechanical properties such as tensile strength. Young's modulus, flexural strength and modulus, as well as notched and un-notched impact strength of PA6/EPM-g-TAI blends were also found to improve gradually with increasing the content of grafted TAI.

Reactive blending of polyamide 6,6 and Vectra A

In this paper, blends of Nylon 6,6 with the liquid crystal polymer Vectra A950 are considered; specifically we focused our attention on Nylon 6,6 modifications by interchange reactions that can occur in the melt, as a function of mixing conditions and blend compositions. Two matrix samples have been used, characterised by a slightly different relative amount of amine and carboxylic end groups, being the latter predominant in both cases. The dried polymers Nylon 6,6/Vectra, combined in weight ratios between 95/5 and 50/50, were subjected to reactive blending with different methods (single-screw extruder, Brabender, pyrex reactor). Pure Nylon samples have been also investigated as reference materials. The soluble Nylon 6,6-rich fraction of each blend was separated from the insoluble Vectra-rich one and used for molecular and spectroscopic characterisations. Thermal and morphological analyses, as well as testing of tensile properties, were carried out on the blends. Evidences of the occurrence of interchange reactions are given and the most probable ones are suggested. (C) 2001 Elsevier Science Ltd. All rights reserved.

低分子量马来酸酐化聚丁二烯橡胶改性聚乙烯增韧尼龙6

尼龙6是世界上使用最广泛的工程塑料之一，由于尼龙6大分子链中含有酰胺键能形成氢键，使其具有强韧、耐磨、耐冲击、耐疲劳、耐腐蚀等优异的特性。但是尼龙6存在低温和干态冲击性能差，吸水性大等弱点，不能满足汽车、电子、机械等行业对材料高韧性的需求。利用橡胶和弹性体对尼龙6进行增韧已经取得了很大的成功，但无法解决成本较高且基体材料刚性损失过大这一难题。实践证明，具有硬核软壳结构核壳粒子在增韧半晶性高聚物时，可以有效提高橡胶的增韧效率，减少体系拉伸强度和模量的损失。然而具有这种结构的核壳粒子合成过程复杂，成本很高，工业应用前景很小；而用传统的反应增容方法原位制备核壳粒子时，由于橡胶分子量大，黏度高，流动性差等特点限制了在反应中原位生成核－壳结构粒子的效率，影响最终的增韧效果。本论文首次尝试用低分子量的马来酸酐化聚丁二烯橡胶通过反应挤出的方法接枝改性聚乙烯，对尼龙6进行增韧，利用聚丁二烯橡胶分子链上的马来酸酐基团和尼龙6分子链的端氨基反应，在尼龙6基体中原位形成以聚乙烯为核，聚丁二烯为壳的核壳粒子，结果得到了高韧性、良好刚性的改性尼龙6。 实验证实该含有双键的低分子量橡胶能够成功的接枝到聚乙烯分子主链上，由于橡胶的马来酸酐化程度很高（14wt%），在同尼龙6共混过程中大大提高马酐基团和尼龙6端氨基之间反应生成的接枝共聚物的效率，可以有效减小两相间的界面张力，改善聚乙烯在尼龙6基体中的分散。通过透射电镜观察共混物内部形态结构发现，共混体系中形成了以聚乙烯为核，橡胶为壳的核－壳结构粒子。这种核－壳粒子对尼龙6有良好的增韧效果。当聚丁二烯橡胶的含量仅为1.5wt%时，尼龙6的冲击强度可以达到1100J/m，而拉伸强度还能保持在47.3MPa。 通过对核壳增韧体系冲击断面和拉伸力学曲线的分析我们发现，由于增韧体系中能够形成软壳硬核的核－壳结构粒子，在外力作用下，由橡胶相构成的壳结构能在聚乙烯核与基体之间形成纤维结构，这种纤维结构不仅能够改变体系的应力状态，引发基体屈服，而且大大增强了分散相粒子同基体之间的界面强度，提高体系的刚性。同时，由于两相间纤维结构的存在，材料内部形成一个类似“物理交联”的网络，材料表现出类橡胶的弹性拉伸性能，没有明显的屈服。 传统的S. Wu的逾渗理论不能很好预测这种核壳增韧体系的性能。Corté 和Leibler的模型不仅考虑了基体树脂的特性（ , , ）,而且还将分散相粒子尺寸（d）也考虑了进去，更好地预测了体系的脆韧转变点。同时在基体树脂相同，且都能增韧的前提下，可以通过Corté 和Leibler模型中参数C（代表分散相粒子能够引发基体发生屈服的能力）的大小预测增韧体系程度的大小，C值越大，体系增韧效果越好。 通过对从上述增韧体系中抽提出的原位生成的PE-g-PB-g-PA6接枝共聚物的热力学和形貌分析发现，PA6链段被限制在宽50-70nm条带状连续结构中，其运动能力受到限制，因此在结晶过程中PA6嵌段的扩散速度降低。导致在通常的结晶速率条件下（10oC/min）结晶不完善，其结晶度﹑结晶温度﹑熔融温度都有所降低，形成以γ晶型为主的不完善结晶。由于在PE和PA6链段之间由一个短的柔性PB链段相连接，因此PA6链段不能同PE发生共结晶，作为连续相PE的结晶行为受到接枝共聚物的影响要小很多。 关键词：低分子量马来酸酐化聚丁二烯橡胶，聚乙烯，尼龙6，核－壳结构，增韧，受限结晶。

异氰酸醋官能化乙丙共聚物的制备及其与尼龙6共混体系的研究

本工作合成了一种含异氰酸酷功能基团的不饱和单体，（3-异氰酸酯基-4-甲基）苯氨基甲酸-2-丙烯配（TAI）。以过氧化二异丙苯（OCP）为引发剂，该单体被用于乙烯丙烯共聚物（EPM）的自由基溶液接枝官能化。纯化后的接枝产物（EPM-g-TAI）的傅立叶变换红外光谱中存在2273cm-l异氰酸酷基团（-NCO），表明异氰酸醋单体已经接枝到乙丙共聚物上。接枝率采用化学滴定和红外光谱的方法确定。与EPM相比，EPM-g-TAl的分子量分布（MMO）变窄。采用旋转流变仪测定了EPM-g-TAl的流变行为。EPM-g-TAl的表观粘度高于EPM且随接枝率的增加而增加。采用接触角测定的表面分析表明，对于给定的的极性测定液体接枝产物的接触角随接枝率的增加而增大；我们同时得到接枝产物的表面自由能（75）以及表面自由能的色散分量（γs）和表面自由能的极性分量（γsρ），这些参数随接枝率提高而增大的趋势使我们可以定量估计接枝反应对改善极性的贡献。本工作研究了（3一异氰酸酯基-4-甲基）苯氨基甲酸-2-丙烯醋（TAl）官能化乙烯丙烯共聚物（EPM-g-TAI）与尼龙6（PA6）的反应共混。傅立叶变换红外光谱表明，由于EPM-g-TAl中的异氰酸醋基（-NCO）与尼龙6中的端胺基（-NH2）之间的化学反应：EPM-g-TAI／PA6谱图中3299cm-1处的阵日伸缩振动峰变窄变高，1640cm-1处阵日变形振动峰和1547cm-1处阵日弯曲振动峰变强。同时研究了共混体系的热性能、流变性能、机械性能和形态特征。OSC结果表明，在相同的共混组成下，EPM-g-TAI／PA6共混体系中尼龙6的结晶烩（△Hc）到氏于EPM／PA6共混体系中的尼龙6，这种差别随着共混物中乙烯丙烯共聚物含量的增加而增大，说明反应共混体系中尼龙6的结晶受到一定的限制；EPM-g-TAI／PA6共混体系的复数粘度和贮能模量高于相应的EPM／PA6共混体系；与相同组成的EPM／PA6相比，EPM-g-TAI／PA6中分散相的粒子尺寸更小，粒子分布更均匀，界面粘合更强；反应共混后的机械性能如拉伸强度、杨氏模量，弯曲强度和模量、缺口及非缺口冲击强度均随着接枝率的提高而增加。

Numerical Simulation of Reactive Extrusion Processes for Activated Anionic Polymerization

In order to deal with the complicated relationships among the variables of the reactive extrusion process for activated anionic polymerization, a three-dimensional equivalent model of closely intermeshing co-rotating twin screw extruders was established. Then the numerical computation expressions of the monomer concentration, the monomer conversion, the average molecular weight and the fluid viscosity were deduced, and the numerical simulation of the reactive extrusion process of Styrene was carried out. At last, our simulated results were compared with Michaeli's simulated results and experimental results. (C) 2007 Elsevier B.V. All rights reserved

Effects of SEBS-g-BTAI on the morphology, structure and mechanical properties of PA6/SEBS blends

Styrene-b-(ethylene-co-1-butene)-b-styrene (SEBS) triblock copolymer functionalized with epsilon-caprolactam blocked allyl (3-isocyanate-4-tolyl) carbamate (SEBS-g-BTAI) was used to toughen polyamide 6 (PA6) via reactive blending. Compared to the PA6/SEBS blends, mechanical properties such as tensile strength, Young's modulus, especially Izod notched strength of PA6/SEBS-g-BTAI blends were improved distinctly. Both theological and FTIR results indicated a new copolymer formed by the reaction of end groups of PA6 and isocyanate group regenerated in the backbone of SEBS-g-BTAI. Smaller dispersed particle sizes with narrower distribution were found in PA6/SEBS-g-BTAI blends, via field emitted scanning electron microscopy (FESEM). The core-shell structures with PS core and PEB shell were also observed in the PA6/SEBS-g-BTAI blends via transmission electron microscopy (TEM), which might improve the toughening ability of the rubber particles.

Numerical simulation of reactive extrusion processes of PA6

To analyze the complicated relationships among the variables during the reactive extrusion process of polyamide 6 (PA6), and then control the chemical reaction and the material structures, the process of continuous polymerization of caprolactam into PA6 in a closely intermeshing co-rotating twin screw extruder was simulated by means of the finite volume method, and the influences of three key processing parameters on the reactive extrusion process were discussed. The simulated results of an example were in good agreement with the experimental results.

Online study of the formation of PA6 droplets in PP matrix under shear flow

Breakup process of polyamide 6 (PA6) in polypropylene (PP) matrix under shear flow was online studied by using a Linkam CSS 450 stage equipped with optical microscopy. Both tip streaming and fracture breakup modes of PA6 droplets were observed in this study. It was reported that the droplet would break up by tip streaming model when the radio of the droplet phase viscosity to the matrix phase viscosity (n(r) = n(d)/n(m)) is smaller than 0.1 (Taylor, Proc R Soc London A 1934, 146, 501; Grace, Chem Eng Commun 1982, 14, 225; Bartok and Mason, J Colloid Sci 1959, 14, 13; Rumscheidt and Mason, J Colloid Sci 1961, 16, 238; de Bruijn, Chem Eng Sci 1993, 48, 277). However, the tip streaming model was observed even when the viscosity ratio was much greater than 0.1 (n(r) = 1.9). In this study for the tip streaming mode, small droplets were ruptured from the tip of the mother droplet. On the other hand, the mother droplet was broken into two or more daughter droplets with one or several satellite droplets between them for the fracture mode. It was found that PA6 droplet was much elongated at first, and then broke up via tip streaming or fracture to form daughter droplets or small satellite droplets with the shape of fiber or ellipse.

Rheology and morphology of reactively compatibilized PP/PA6 blends

This work aims to use the Palierne emulsion type model to describe the relationship between the rheological response to small amplitude oscillatory deformation and morphology of polypropylene/polyamide 6 (PP/PA6) blends compatibilized with maleic anhydride grafted polypropylene (PP-g-MAH). It was found that the Palierne emulsion type model could describe very well the linear viscoelastic responses of binary uncompatibilized PP/PA6 blends and failed to describe the ternary compatibilized PP/PP-g-MAH/PA6 blends. These features could be attributed to the fact that the morphology of the ternary blends was not of the emulsion type with the PA6 particles dispersed in the PP matrix but of an emulsion-in-emulsion type, i.e., PA6 particles dispersed in the PP matrix themselves contained PP or PP-g-MAH inclusions. By consideration of PP-in-PA6 particles as pure PA6 particles, where the volume fraction of the PA6 phase was increased accordingly, the Palierne emulsion type model could work very well for a ternary blending system. Preshear at low frequencies modified the morphology of both binary and ternary blends. The particles of the dispersed phase (PA6) became more uniform. These results suggested that the Palierne emulsion type model could be used to extract information on rheological properties and interfacial tension of polymer blends from known morphology and vice versa.

High-temperature X-ray diffraction studies on polyamide6/clay nanocomposites upon annealing

The influence of nanodispersed clay on the alpha crystalline structure of polyamide 6 (PA6) was examined in-situ with X-ray diffraction (XRD) between room temperature and melting. In pure PA6 upon annealing the alpha crystalline phase was substituted by an unstable pseudohexagonal phase at 150degreesC, then it transformed into a new stable crystalline structure - high temperature alpha' phase above the transition temperature. However, in PA6/clay nanocomposite (PA6CN), the alpha phase did not present crystalline phase transition on heating. The increase in the annealing temperature only led to continuous intensity variation. The different behaviors were caused by the confined spaces formed by silicate layers, which constrained the mobility of the polymer chains in-between.

A novel preparation method of maleic anhydride grafted syndiotactic polystyrene and its blend performance with nylon6

This work is intended to provide a method for the preparation of maleic anhydride grafted syndiotactic polystyrene (sPS-g-MA). In particular, a novel solid reaction method by a radical grafting approach is investigated. The grafting reaction is performed at a solid state, where the syndiotactic polystyrene (sPS) is swollen in solvent at relatively low temperature compared to the conventional melt modification method. The formation of sPS-g-MA is directly confirmed by Fourier transform infrared spectroscopy and by the morphology observation of sPS/polyamide-6 (Nylon6) blends, when sPS-g-MA is used as a reactive compatibilizer.