反应性聚碳酸酯/环氧树脂体系的玻璃化转变行为及力学性能

增韧;反应性聚碳酸酯/环氧树脂体系的玻璃化转变行为及力学性能     

两种碳材料混合填充聚合物复合材料的导电特性及渗流阈值的计算模型

介绍了用碳纳米管与炭黑（或石墨）混合填充的聚合物复合材料的导电特性;阐述了混合填充聚合物体系的导电机理;介绍了基于线性混合规则和已占体积理论的渗流阈值的计算模型;分析了模型计算值与实验值的差异。利用已占体积理论,重新推导了混合填充体系渗流阈值的计算公式,并与文献公式做了比较。新公式表明：混合填充聚合物复合材料的渗流阈值...     

碳纳米管改性环氧树脂的导热和阻燃性能

以双酚A二缩水甘油醚(DGEBA)环氧树脂(Epoxy Resin,EP)为基体、甲基六氢苯酐(MHHPA)为固化剂、以多壁碳纳米管(MWCNTs)为添加剂制备了环氧树脂/碳纳米管纳米复合材料。通过对微观结构、玻璃化转变温度(Tg)、热失重、热导率和锥形量热测试结果分析,研究了质量分数少于1.5%的MWCNTs对环氧树脂的导热和阻燃性能影响,结果表明,MWCNTs质量分数为1.5%时,复合材料发生团聚;纳米复合材料随着MWCNTs质量分数的增加Tg值先增加后降低;失重5%时,对应的温度先增加后降低,残炭量增加;样品的热导率呈现先升高后降低的趋势,当MWCNTs质量分数为1%时,复合材料的热导率最大;MWCNTs加入后环氧树脂的总释热量减少,释烟量增加,阻燃性得到一定程度的提高。     

多壁碳纳米管/聚乙烯复合材料的制备及其导电行为

多壁碳纳米管/聚乙烯复合材料的制备及其导电行为;碳纳米管;高密度聚乙烯;渗流阈值;导电行为;V-PTC特性     

碳纳米管及碳纤维增强环氧树脂复合材料研究进展

碳纳米管与碳纤维具有优异的力学、电学等性能,广泛用做复合材料增强体,但目前碳纳米管/碳纤维/环氧树脂复合材料的研究具有一定的局限性,只考虑了两相材料间的作用,即仅对单一相进行处理而忽略了另一相的改性。本文从碳纳米管/碳纤维协同增强环氧树脂基体复合材料的思路入手,结合自己的研究成果,综述了国内外相关研究进展。从研究结果可以看出,将三相材料之间完全有效地联系起来,发挥三者间的协同效应,复合材料的性能可以发生质的飞跃。     

The Correlation Between Particle-Size Dispersity and Percolation Threshold of Brittle-Ductile Transition in Polymer Blends

Percolation threshold of Brittle-Ductile (B-D) transition and its relation with the affecting varibles (such as particle-size dispersity, interphase adhesion)in polymer blends are studied.Percolation Threshold (Φ_(sc)) which is equivalent to that of B-D transition and critical matrix ligament thickness (T_c) are first independently calculated and the correlated equation between Φ_(sc) and σ_g is also given.In addition, a new type of master curve of S_1(G_0,toughness) with Φ_s (stress volume fraction) for polymer blends is proposed and the new parameter Φ_(so) (up-limited stress volume fraction) is also discussed. The results confirm that Φ_(sc) is not only related with σ_g,but also tightly related with the interphase adhesion.     

Epoxy matrix composites reinforced with purified carbon nanotubes for thermal management applications

The role of carbon nanotube purification treatment as a means to improve the thermal properties of polymer matrix composites was investigated. Particular emphasis was placed on clarifying the processing‐property relationship in polymer composites for thermal management applications. The results indicated that purification treatment is critical to the thermal properties of derived polymer composites. Purification treatment can yield a twofold increase in composite thermal conductivity because of improved effectiveness in interfacial interaction and increased chemical purity of the filler. However, there is a trade‐off between the benefits and disadvantages associated with purification treatment, particularly when thermal and electrical properties are both concerned. Purification treatment gives rise to a sharp decrease in composite electrical conductivity by at least two orders of magnitude because of the lack of an effective percolating network. The effect of purification treatment on composite electrical properties is more significant than on its thermal properties.     

超临界正丁醇对回收碳纤维复合材料的降解及表征

采用响应面分析方法设计超临界正丁醇降解废弃的碳纤维/环氧树脂(CF/EP)复合材料降解实验,用以回收碳纤维.通过Design-Expert V8.0建立环氧树脂降解率和工艺参数之间的数学模型,获得了最优工艺参数;通过图形优化研究了工艺参数对环氧树脂基体降解率的影响规律;通过场发射电子扫描显微镜、原子力显微镜、X射线光电子能谱仪、显微共焦激光拉曼光谱仪及单丝拉伸等分析最优工艺参数下回收的碳纤维的表面形貌、表面化学、石墨化程度及力学性能.结果表明,建立的数学模型拟合误差范围为±5.5%,实现了回收工艺参数的预估;单因素对环氧树脂基体降解率的影响程度为:反应温度保温时间添加剂浓度正丁醇含量;最优工艺参数为:反应温度330℃,保温时间60 min,添加剂浓度0.0538 mol/L,投料比0.024g/mL.回收的碳纤维表面无残留树脂,没有发生明显的石墨化,且表面平均粗糙度与原碳纤维相近;与原始碳纤维相比,回收的碳纤维的拉伸强度约为原碳纤维的93.58%,杨氏模量约为原碳纤维的94.87%.     

A Molecular‐Dynamics Study of Size and Chirality Effects on Glass‐Transition Temperature and Ordering in Carbon Nanotube‐Polymer Composites

Molecular‐dynamics simulations of single‐walled carbon nanotubes (CNTs) embedded in a coarse‐grained amorphous monodisperse polyethylene‐like model system have been carried out. The roles of nanotube diameter and chirality on the physical and structural properties of the composite are thoroughly discussed for several CNTs with different diameter and chirality. It is shown that the glass‐transition temperature of the polymer matrix increases with the diameter of the CNT while chirality effects are negligible. A denser and ordered layered region of polymer matrix is found in the vicinity of the nanotube surface. The density and ordering of this layer increases with the CNT diameter. All simulations indicate that chirality does not affect the atomic structure of the highly ordered layer surrounding the CNTs. Despite the simplicity of the polymer model, results of this study are qualitatively comparable with those obtained from experiments and numerical simulations that consider a chemically specific polymer matrix.

     

亚临界水介质回收酸酐固化环氧树脂/碳纤维复合材料

研究了不同添加剂对碳纤维增强酸酐固化环氧树脂复合材料在亚临界水中降解的影响,通过IR、GC-MS等分析,确定了环氧树脂的分解机理主要为酯键的断裂。 结果表明,KOH与苯酚对酸酐固化环氧树脂的分解没有协同效应,碱性物质更有利于酯键的断裂。 甲基四氢邻苯二甲酸酐固化的环氧树脂增强碳纤维复合材料在反应温度为250 ℃、反应时间为60 min、KOH浓度为0.2 mol/L时可完全分解,回收碳纤维的拉伸强度和表面形貌未受影响。     

In Situ Polymerized Carbon Nanotube/Polyimide Nanocomposites: Effect of Reaction Stoichiometry on the Glass Transition Properties of the Nanocomposites

A series of in situ polymerized CNT/PI nanocomposite materials synthesized at a fixed diamine‐to‐dianhydride monomer feed ratio with varying concentrations of added –COOH‐ functionalized CNT is studied. It is found that the glass transition temperature of the nanocomposite varies non‐monotonically with CNT concentration. To determine the origin of this behavior, the molecular weights of the matrix polymers are measured by the intrinsic‐viscosity method. The functional‐group density of the CNT material is determined by potentiometric titration. The results confirm that the glass transition of the CNT/PI system depends on the concentration of the CNT filler through its influence on the functional group stoichiometry and thus on the molecular weight of the polycondensation product.

     

Double‐Wall Carbon Nanotube–Porphyrin Supramolecular Hybrid: Synthesis and Photophysical Studies

Double‐wall carbon nanotubes (DWCNTs) with pyridyl units covalently attached to the external wall through isoxazolino linkers and carboxylic groups that have been esterified by pentyl chains are synthesized. The properties of these modified DWCNTs are then compared with an analogous sample based on single‐wall carbon nanotubes (SWCNTs). Raman spectroscopy shows the presence of characteristic radial breathing mode vibrations, confirming that the samples partly retain the integrity of the nanotubes in the case of DWCNTs, including the internal and external nanotubes. Quantification of the pyridyl content for both samples (DWCNT and SWCNT derivatives) is based on X‐ray photoelectron spectroscopy and thermogravimetric profiles, showing very similar substituent load. Both pyridyl‐containing nanotubes (DWCNTs and SWCNTs) form a complex with zinc porphyrin (ZnP), as evidenced by the presence of two isosbestic points in the absorption spectra of the porphyrin upon addition of the pyridyl‐functionalized nanotubes. Supramolecular complexes based on pyridyl‐substituted DWCNTs and SWCNTs quench the emission and the triplet excited state identically, through an energy‐transfer mechanism based on pre‐assembly of the ground state. Thus, the presence of the intact inner wall in DWCNTs does not influence the quenching behavior, with respect to SWCNTs, for energy‐transfer quenching with excited ZnP. These results sharply contrast with previous ones referring to electron‐transfer quenching, in which the double‐wall morphology of the nanotubes has been shown to considerably reduce the lifetime of charge separation, owing to faster electron mobility in DWCNTs compared to SWCNTs.     

碳纳米管-Mg65Cu25Gd10非晶复合材料玻璃转变的动力学性质

制备了Mg65Cu25Gd10大块非晶合金及其碳纳米管（CNTs）复合材料，对两种材料进行了不同扫描速率下的差热扫描量热分析，研究了加入CNTs对材料玻璃转变和晶化动力学效应的影响。结果表明：加入CNTs后，复合材料的玻璃转变和晶化行为仍然具有动力学效应，但加入的CNTs减小了材料晶化行为对升温速率的依赖程度；同时，加入CNTs加大了材料发生玻璃转变时需要克服的能量势垒，增大了峰值温度时的晶化反应速率常数，从而降低了材料的玻璃形成能力（GFA）；对CNTs降低GFA的原因也进行了探讨。     

Multiwalled Carbon Nanotubes Produced by a Continuous CVD Method and Their Use in Melt Mixed Composites with Polycarbonate

Summary: In this study, two samples of multiwalled carbon nanotubes (MWNT) were synthesized by CVD of acetylene over Fe₂Co catalysts supported by CaCO₃ using different temperatures. The material produced at 660 °C (MWNT600) shows slightly better performance as evidenced by lower mean tube diameter and better conductivity as compared to the sample produced at 700 °C (MWNT700). In addition, it has a higher [O]:[C] ratio. Both materials were incorporated into polycarbonate using melt mixing using a small scale compounder. The results prove that these materials are very suitable for polymer composite applications as they show low electrical percolation concentration and good mechanical enhancement. The percolation threshold is as low as <0.875 wt% for MWNT660 and <1 wt% for MWNT700. MWNT700 showed slightly better dispersability as evidenced from light microscopy, SEM, and TEM. The effects in the stress-strain curves are similar in both composites, indicating a stress increase with MWNT incorporation.     

纳米粒子填充聚合物体系中凝聚结构和渗流转变的分子动力学模拟

通过粗粒化模型,采用分子动力学模拟的方法研究了纳米粒子填充聚合物体系中粒子的凝聚过程.结果表明:纳米粒子和基体粒子间的相互作用决定了团聚体的结构,且作用力越大则团聚体的分形维数越高,当粒子的相互作用强度(εNP)为1.0时,模拟体系中团聚体的分形维数为2.05,与聚酰亚胺炭黑体系透射电镜照片结果一致.对渗流过程的模拟结果表明,相互作用力的增大会导致渗流时间的增加,渗流转变速率减慢,与动态电渗流实验的实测结果相符合.     

具有隔离结构的聚丙烯/碳纳米管复合材料的制备及电磁屏蔽性能

通过共挤出包覆-热压法制备了具有隔离结构的聚丙烯(PP)/碳纳米管(CNTs)电磁屏蔽复合材料。 其中,CNTs随机分布于PP基体中形成导电相,该导电复合物作为包覆层包敷在纯PP颗粒表面,形成包覆复合粒子,经热压后形成隔离导电网络。 结果表明,所制备的隔离结构复合材料呈现良好的导电性能,可获得较低的导电逾渗值0.28%(体积分数);在CNTs质量分数为5.6%时,该复合材料电磁屏蔽性能达到25.6 dB,同时具有良好的力学性能。 本文结果表明,共挤出包覆-热压法制备隔离结构导电复合材料方法简单可控、绿色环保,对开发高性能电磁屏蔽复合材料具有重要指导意义。     

Glass Transition Temperature and Value of the Relaxation Time at Tg in Vitreous Polymers

Summary: Many works focused on glassy polymers determine values of glass transition temperature (T_g) and an overview of the literature shows that depending on the method used, values of T_g are found different for the same material. In this paper, a review of data collected on different materials are used and interpreted in term of molecular mobility characterized by relaxation time functions. By using three independent experimental procedures (dielectric, thermally depolarized current and calorimetric), we show that the value of the glass transition and the value of the relaxation time at T_g can be correctly determined. It is also shown that the assumption: τ _(Tg) = 100 s is constant, is not correct. The protocol proposed also allows the determination of the value of the fragility index “m” of the glass forming liquid with a great accuracy.     

邻甲酚醛环氧树脂/聚氨酯互穿聚合物网络的形态与性能

邻甲酚醛环氧树脂/聚氨酯互穿聚合物网络的形态与性能;互穿聚合物网络; 邻甲酚醛环氧树脂; 聚氨酯; 力学性能; 玻璃化转变温度