聚合物/层状硅酸盐纳米复合材料

目前,聚合物／层状硅酸盐纳米复合材料是重要的工程材料之一。由于层状硅酸盐的特殊结构,聚合物层状硅酸盐纳米复合材料的各项性能得到较大改善。聚合物／层状硅酸盐纳米材料的制备、表征、结构与性能的研究取得了重要进展。本文简要概述了聚合物／层状硅酸盐的结构及其有机改性机理,研究表明,插层剂和离子交换容量是插层的重要因素。最后,讨论了聚合物／层状硅酸盐纳米复合材料的制备方法和性能。     

聚合物-层状硅酸盐纳米复合材料应用研究进展

笔者论述了聚合物-层状硅酸盐插层纳米复合材料的结构和特点，综述了聚合物-层状硅酸盐纳米复合材料的应用研究进展，评述了聚合物-层状硅酸盐纳米复合材料的制备方法和表征手段，展望了这种纳米复合材料的发展方向。     

层状硅酸盐／橡胶纳米复合材料（一）：用熔融插层法提高层状硅酸盐／天然橡胶纳米复合材料的工艺和加工性能

天然橡胶纳米复合材料是通过天然橡胶与有机改性的硅酸盐熔融复合制备的。该研究亦对比使用了未有机化的原始层状硅酸盐和非层状硅酸盐（EIC）。所用的层状硅酸盐是钠皂土（BNT）；而所用的有机粘土则是以十八烷基铵类改性的蒙脱土（MMT-ODA）和以甲基牛脂基双（2-羟乙基）季铵类改性的蒙脱土（MMT-TMDA）。采用加有促进剂的硫黄硫化体系进行硫化。借助X-射线衍射和透射电子显微镜研究这些硅酸盐的分散。加入有机粘土的纳米复合材料显示出较快的硫化速度和提高了的物理机械性能。复合材料的物理机械性能提高度按如下顺序排列：MMT-ODA〉MMT-TMDA〉EIC〉BNT。这种性能的提高归因于有机硅酸盐的插层／剥离，而硅酸盐的插层／剥离行为又是因其层内间距较大所致。     

聚合物/层状硅酸盐耐烧蚀纳米复合材料的研究进展

从层状硅酸盐的微观结构及其与聚合物插层时的热力学理论两方面概述了聚合物/层状硅酸盐(PLS)纳米复合材料制备的可行性及层状硅酸盐的修饰方法.介绍了纳米硅酸盐在聚合物熔体中的分散理论及达到纳米分散的关键技术.对该复合材料的微观结构、烧蚀机理及烧蚀性能表征测试方法进行了说明,并指出其在火箭发动机内绝热材料中的应用前景.附参考文献22篇.     

聚合物／层状硅酸盐纳米复合材料的研究进展

聚合物／层状硅酸盐（PLS）纳米复合材料是近十多年迅速发展起来的新交叉科学。由于聚合物纳米复合材料具有常规聚合物复合材料所没有的结构、形态以及较常规聚合物复合材料更优异的物理力学性能、耐热性和气体液体阻隔性能等，因而显示出重要的科学意义和应用前景。综述了聚合物／层状硅酸盐纳米复合材料的制备、结构、性能和应用情况，最后展望了其应用前景。     

聚乳酸/层状硅酸盐纳米复合材料研究进展

介绍了聚乳酸/层状硅酸盐纳米复合材料研究进展,阐述了其制备方法如原位聚合插层法、溶液插层法、熔融插层法等,详述了聚乳酸添加纳米层状硅酸盐后结构与性能的变化,包括复合材料的微观结构、结晶性能、热性能、力学性能、流变性能、加工性能、阻隔性能、阻燃性能的变化。研究表明,采用不同的制备方法如原位聚合插层法、溶液插层法、熔融插层法等能制得插层型、剥离型以及插层与剥离混合型聚乳酸/层状硅酸盐纳米复合材料;添加纳米层状硅酸盐后,得到的聚乳酸/层状硅酸盐纳米复合材料结晶速率提高,结晶度增加,说明层状硅酸盐起到了成核剂的作用;热稳定性、拉伸模量和冲击强度、阻透性能和阻燃性能都有不同程度提高;流变性能也得到改善。     

蒙脱土改性纳米复合乳液的研究进展

纳米技术是一项前沿科学技术,目前,聚合物,蒙脱土纳米复合材料是重要的工程材料之一。由于蒙脱土具有层状硅酸盐的特殊结构,使得聚合物,蒙脱土纳米复合材料的各项性能均得到较大改善。介绍了蒙脱土的特性及其复合材料的结构,详细介绍了近年来国内外学者采用共混法和插层聚合法制备蒙脱土改性纳米复合乳液所做的研究工作。对蒙脱土改性不同乳液的应用研究现状进行了综述。指出了乳液法制备聚合物／蒙脱土纳米复合材料研究中存在的问题和应努力的方向。     

天然橡胶／有机粘土纳米复合材料的制备与表征

自从丰田中心率先研究出了尼龙6／有机粘土纳米复合材料之后，聚合物／层状硅酸盐纳米复合材料引起了很多高分子科学家的关注。纳米复合材料就是一些无机填料以纳米级均匀分散在高聚物基体中形成的复合材料。粘土片层被聚合物插层或剥离可形成聚合物／粘土纳米复合材料。     

尼龙6/粘土纳米复合材料的研究

综述尼龙6／粘土纳米复合材料的研究进展、各种制备方法、复合机理及其微观性能的表征。粘土足一种层状硅酸盐，以纳米尺寸分布在聚合物中能提高聚合物的各种性能，尼龙6和粘土无论是通过原位聚合法还是熔融法都能制得剥离态的尼龙6倦土纳米复合材料。     

聚合物纳米复合材料的研究进展

介绍了聚合物基纳米复合材料的种类及制备方法，详细介绍了聚合物／层状硅酸盐纳米复合材料的研究，包括聚合物／层状硅酸盐纳米复合材料的种类、性能及研究的新进展。     

Ultrasonic Preparation of Polymer/Layered Silicate Nanocomposites during Extrusion

Summary Three kinds of polymer/layered nanocomposites were prepared via ultrasonic extrusion. Experimental results showed that ultrasonic oscillations could mostly decrease the size and its distribution of clay particles in polymer matrix. Therefore, crystal size of polymer matrix decreases. For PA6-based nanocomposites with higher compatibility, the ultrasonic oscillations can also affect the microstructure of clay, causing more regions of exfoliated clay. Due to better dispersion of clay and smaller crystal size, the elongation at break of polymer/layered nanocomposites ultrasonically treated got greatly increased, meanwhile ultrasonic oscillations also improved their other mechanical properties, such as tensile and impact strength.     

Mechanical properties of layered silicate/starch polycaprolactone blend nanocomposites

The mechanical behavior of layered silicate/starch polycaprolactone blend nanocomposites was evaluated. Three different clays (Cloisite Na⁺, Cloisite 30B and Cloisite 10A) were used as reinforcement. Nanocomposites were prepared by melt intercalation followed by compression molding. These nanocomposites were characterized using X‐ray diffraction, scanning electron microscopy, dynamic mechanical analysis and tensile testing. X‐ray diffraction results showed that most of the clays were intercalated within the polymeric chains. In all cases, mechanical properties were improved with clay incorporation and the improvement was better as the clay content was increased. The best properties were achieved with Cloisite 10A due to their greatest compatibility with the matrix. A mechanical model, which takes into account the effective parameters of the clay, was used in order to estimate the dispersion of clay within the polymer. The highest dispersion was obtained for Cloisite 10A, which is in accordance with the experimental mechanical properties. Although dynamical‐mechanical properties improved with clay incorporation, the glass transition temperature was not affected. Copyright © 2006 Society of Chemical Industry     

Novel hybrid of clay,cellulose, and thermoplastics. I. Preparation and characterization of composites of ethylene–propylene copolymer

The present study is aimed to prepare hybrid materials by incorporating layered silicates and microcrystalline cellulose into thermoplastic polymer. Using ethylene–propylene (EP) copolymer as thermoplastic polymer matrix and maleated EP (MEP) copolymer as compatibilizer, three types of composites were prepared by (i) melt mixing of cellulose with thermoplastics [I], (ii) melt mixing of clay with thermoplastics [II], and (iii) melt mixing of cellulose with the thermoplastic clay nanocomposites [III]. They were characterized by X‐ray diffractometry (XRD), differential scanning calorimetry, thermogravimetric analysis, and Fourier transform infrared spectroscopy. Instron was used to measure the mechanical properties. The composites [II] and [III] that contain layered silicates were intercalated nanocomposites as confirmed by XRD and transmission electron microscopy. The improvement in tensile properties was observed in cellulose–fiber‐reinforced composites with increasing cellulose content. In nanocomposites [II] and [III], the tensile modulus was improved. The resistance of the cellulose composites [I] for water absorption decreased with increasing content of cellulose fibers. The incorporation of layered silicates reduced the water absorption of cellulose composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2672–2682, 2007     

Microstructure and rheological behavior of block copolymer/clay nanocomposites

Organic/Inorganic hybrid nanocomposites based on poly(styrene-butadiene-styrene) copolymer (SBS) and clay are fabricated by melt intercalation. The degree of intercalation is dependent on the surface properties of clay and SBS. The epoxized block in epoxized SBS acts as a strong attractive site with the clay surface, which yields the increased interlayer space in the layered silicates. It is also shown that the thermal stability of clay as well as the surface properties is very important in fabricating the polymer/clay nanocomposites. The rheological behavior of the SBS/clay nanocomposites is quite different from that of SBS itself. Both storage moduli and complex viscosity of the SBS/layered silicate nanocomposites increase and show non-terminal flow behavior.     

Polymer/layered silicate nanocomposites by combined intercalative polymerization and melt intercalation: a masterbatch process

Poly(ε-caprolactone) (PCL) and poly(vinyl chloride) (PVC) layered silicate nanocomposites were prepared by combination of intercalative polymerization and melt intercalation. In a first step, high clay content PCL nanocomposites were prepared by in situ polymerization of ε-caprolactone intercalated between selected organo-modified silicate layers. The polymerization was catalyzed with dibutyltin dimethoxide in the presence of montmorillonites, the surface of which were previously exchanged with (functionalized) long alkyl chains ammonium cations. Then, these highly filled PCL nanocomposites were added as masterbatches in commercial PCL and PVC by melt blending. The intercalation of PCL chains within the silicate layers by in situ polymerization proved to be very efficient, leading to the formation of intercalated and/or exfoliated structures depending on the organo-clay. These masterbatches were readily dispersed into the molten PCL and PVC matrices yielding intercalated/exfoliated layered silicate nanocomposites which could not be obtained by melt blending the matrix directly with the same organo-modified clays. The formation of nanocomposites was assessed both by X-ray diffraction and transmission electronic microscopy. Interestingly, this so-called ‘masterbatch’ two-step process allowed for preparing PCL nanocomposites even with non-modified natural clay, i.e. sodium montmorillonite, which showed a material stiffness much higher than the corresponding microcomposites recovered by direct melt intercalation. The thermal stability of PCL nanocomposites as a function of clay content was investigated by thermogravimetry (TGA).     

Designing polylactide/clay nanocomposites for textile applications: Effect of processing conditions,spinning, and characterization

An experimental study was carried out to design polylactide (PLA)-clay nanocomposites for developing fibers. PLA and 1–10 wt % of a selected organomodified bentonite (Bentone® 104-B104) were melt mixed to examine the effect of processing conditions (temperature, shear, residence time) on the morphology of performed polymer nanocomposites (PNC). Because of a good compatibility with PLA matrix, the dispersion of B104 occurred under different conditions without difficulty, and a similar morphology was obtained. The results obtained showed that at low temperature of mixing, the shear stress exerted on polymer has a key role on the extent of intercalation and delamination. Upscale experiments were further performed using optimized conditions and 4 wt % B104 was added to PLA matrix by melt blending to produce PNC for spinning. Then, the recovered PNC were melt spun to produce multifilaments yarns, and it was demonstrated that surprisingly, it is not necessary to use a plasticizer to spin a blend with 4 wt % B104. The properties of the yarns have been studied in terms of clay dispersion as well as thermal, mechanical, and shrinkage properties. B104 could be added up to 4 wt % into PLA without detrimentally sacrificing the tensile strength of melt-spun filaments, especially at high draw ratio. Interestingly, the PNC-based multifilaments were knitted and the flammability studied using cone calorimeter at 35 kW/m². A strong decrease, up to 46%, of the heat release rate was measured. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of water‐assisted extrusion and solid‐state polymerization on the microstructure of PET/Clay nanocomposites

An melt‐mixing process has been used to prepare Poly(ethylene terephthalate) (PET)/clay nanocomposites with high degree of clay delamination. In this method, steam was fed into a twin‐screw extruder (TSE) to reduce the PET molecular weight and to facilitate their diffusion into the gallery spacing of organoclays. Subsequently, the molecular weight (M_W) reduction of the PET matrix due to hydrolysis by water was compensated by solid‐state polymerization (SSP). The effect of the thermodynamic compatibility of PET and organoclays on the exfoliated microstructure of the nanocomposites was also examined by using three different nanoclays. The dispersion of Cloisite 30B (C30B) in PET was found to be better than that of Nanomer I.28E (I28E) and Cloisite Na⁺. The effect of feeding rate and consequently residence time on the properties of PET nanocomposites was also investigated. The results reveal more delamination of organoclay platelets in PET‐C30B nanocomposites processed at low feeding rate compared to those processed at high feeding rate. Enhanced mechanical and barrier properties were observed in PET nanocomposites after SSP compared to the nanocomposites prepared by conventional melt‐mixing. POLYM. ENG. SCI., 54:1723–1736, 2014. © 2013 Society of Plastics Engineers     

Poly(lactic acid) and layered silicate nanocomposites prepared by melt mixing: Thermomechanical and morphological properties

Poly(lactic acid) (PLA) nanocomposites were prepared by melt mixing technique in a Haake batch mixer. The clay dispersion within the PLA matrix during melt mixing was well explained through the morphological characterization. Morphological characterizations were studied by X‐ray diffraction and transmission electron microscopy. The exfoliation/intercalation of the clay particles within the polymer matrix during melt mixing depends on the mixing torque generated during the preparation of nanocomposites. The significance of processing temperature and the mixing time in melt mixing were studied for PLA/C93A and PLA/C30B nanocomposites. The structure and properties of the nanocomposites were also characterized by differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, and mechanical properties by standard tensile testing. The incorporation of nanoclays into the PLA matrix enhanced the mechanical properties and thermal stability of the PLA nanocomposites. This may be due to the reinforcing effect of nanoclays within the polymer matrix. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

熔融插层法制备聚合物/黏土纳米复合材料研究进展

对国内外熔融插层法制备聚合物／黏土纳米复合材料(PCN)的研究进展进行了介绍。介绍了影响PCN结构形态的几种因素；对熔融插层法制备PCN的热力学、动力学的研究进行了总结；介绍了熔融插层的机理和几种理论模型。并对聚合物／黏土纳米复合材料的开发及应用前景作出了展望。     

A short review on rubber/clay nanocomposites with emphasis on mechanical properties

The invention of Nylon‐6/clay nanocomposites by the Toyota Research Group of Japan heralded a new chapter in the field of polymer composites. This article highlights the work done in the field of rubber/clay nanocomposites. The preparations of rubber/clay nanocomposites by solution blending, latex compounding, and melt intercalation are covered and a thorough discussion of the mechanical properties of the various rubber/clay nanocomposite systems is presented. Other properties such as barrier, dynamic mechanical behavior, and thermal properties are also discussed. Finally, the future trends in the rubber/clay nanocomposites are mentioned. POLYM. ENG. SCI., 47:1956–1974, 2007. © 2007 Society of Plastics Engineers