Synthesis and properties of polystyrene–clay nanocomposites via in situ intercalative polymerization

Organophilic montmorillonite (MMT) was prepared by ion exchange between Na⁺ ions in the clay and twin benzyldimethyloctadecylammonium bromine cations in an aqueous medium. The organophilic MMT particles were easily dispersed and swollen in styrene monomer. Polystyrene–MMT nanocomposites were prepared by the free‐radical polymerization of styrene containing dispersed clay. The intercalation spacing in the nanocomposites and the degree of dispersion of these composites were investigated with X‐ray diffraction and transmission electron microscopy, respectively. The nanocomposites had higher weight‐average molecular weights, lower glass‐transition temperatures, and better thermal stability (the decomposition temperature was improved by ca. 70°C) than the virgin polystyrene. The rheological behavior of the polystyrene–MMT nanocomposites was also studied. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 201–207, 2005     

Preparation and characterization of polyethylene–clay nanocomposites by using chlorosilane‐modified clay

Clay was modified by trimethylchlorosilane; after modification, hydroxyl groups at the edge of layers were reacted and CEC value was drastically decreased. Polyethylene–clay composites were prepared by melt compounding. Wide angle X‐ray diffraction (WAXD) and transmission electron microscopy (TEM) showed that intercalated nanocomposites were formed using organoclay ion‐exchanged from chlorosilane‐modified clay, but conventional composites formed using organoclay directly ion‐exchanged from crude clay. Dynamic mechanical analysis (DMA) of PE and PE–clay composites was conducted; the results demonstrated that nanocomposites were more effective than conventional composites in reinforcement and addition of organoclay resulted in the increase of glass transition temperature (T_g), but crude clay had no effect on T_g of PE–clay composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 676–680, 2004     

Preparation and characterization of polystyrene–clay nanocomposites by free‐radical polymerization

The polymerizable cationic surfactant, vinylbenzyldimethylethanolammouium chloride (VBDEAC), was synthesized to functionalize montmorillonite (MMT) clay and used to prepare exfoliated polystyrene–clay nanocomposites. The organophilic MMT was prepared by Na⁺ exchanged montmorillonite and ammonium cations of the VBDEAC in an aqueous medium. Polystyrene–clay nanocomposites were prepared by free‐radical polymerization of the styrene containing intercalated organophilic MMT. Dispersion of the intercalated montmorillonite in the polystyrene matrix determined by X‐ray diffraction reveals that the basal spacing is higher than 17.6 nm. These nanocomposites were characterized by differential scanning calorimetry (DSC), transmission electron micrograph (TEM), thermal gravimetric analysis (TGA), and mechanical properties. The exfoliated nanocomposites have higher thermal stability and better mechanical properties than the pure polystyrene. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1370–1377, 2002     

Synthesize and characterization of styrene‐N‐phenyl maleimide/montmorillonite nanocomposites prepared through emulsion polymerization

Composites of organomodified (OMMT) and pristine montmorillonite (MMT) intercalated by styrene‐N‐phenyl maleimide (PMI) copolymer were prepared by emulsion intercalative polymerization. X‐ray diffraction (XRD) and transmission electron microscopy results show that the dispersability of clay in the matrix was greatly improved by the incorporation of polar moiety PMI. The dispersability of OMMT in the matrix is better than MMT. XRD patterns of the extracted nanocomposites showed that d₀₀₁ of the clay are much larger than that of the original OMMT and MMT, which indicates that the interaction of copolymer with the clay layers was greatly improved by incorporation with polar monomer PMI. The thermal property of the composites was greatly improved by the intercalation with clay. The DSC results showed that the glass transition of the composites became inconspicuous, which indicated that the movement of the polymer segment was extremely confined by the clay layer. The consistency factor of the melts of the composites increased monotonically with a decreasing flow index showing stronger shear thinning property of the composites. The rheological activity energy of the composites decreased more than that of the pure copolymer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1010–1015, 2005     

Synthesis and properties of polystyrene–montmorillonite nanocomposites by suspension polymerization

Organophilic montmorillonite was prepared using ion‐exchange method between sodium ions in clay layers and stearyltrimethyl ammonium chloride in the various solvents, including deionized water, ethanol, acetone, and toluene. The montmorillonite has the largest d₀₀₁ spacing, as determined by X‐ray diffraction in toluene, than the other solvents considered. Ethanol can completely wash out the overexchanged stearyltrimethyl ammonium chloride among layers of montmorillonite. However, deionized water is the preferred ion‐exchange solvent. The thermal stability of organophilic montmorillonite was investigated by high‐resolution thermogravimetric analysis (TGA). Polystyrene–montmorillonite nanocomposites were obtained by suspension free radical polymerization of styrene in the dispersed organophilic montmorillonite. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) revealed that montmorillonite had been exfoliated. 5.0 wt % of clay in the synthesized nanocomposite was found to be the optimum content that improved both thermal and mechanical properties over those of pure polystyrene under the experimental conditions applied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 101–109, 2004     

不饱和聚酯/粘土纳米复合材料的制备与性能

为了改善不饱和聚酯树脂的力学性能,将有机改性的蒙脱土与苯乙烯均匀混合后再掺合到不饱和聚酯(UP)中,制备了不同粘土含量的不饱和聚酯树脂/粘土(UPR/Clay)纳米复合材料。差热分析发现随着粘土含量的增加,玻璃化温度有所增加。X射线衍射数据表明,纳米复合材料中粘土原有的峰基本消失,表明粘土结构层间距增大,结合透射电镜(TEM),确定此纳米复合材料为插层和剥离结构。冲击试验发现随着粘土加入冲击强度有一最大值。     

Thermoplastic elastomeric nanocomposites from poly[styrene–(ethylene‐co‐butylene)–styrene] triblock copolymer and clay: Preparation and characterization

Thermoplastic elastomer (TPE)–clay nanocomposites based on poly[styrene–(ethylene‐co‐butylene)–styrene] triblock copolymer (SEBS) were prepared. Natural sodium montmorillonite (MMT) clay was organically modified by octadecyl amine to produce an amine‐modified hydrophobic nanoclay (OC). Commercially available Cloisite 20A (CL20) and Cloisite 10A, tallow ammine modified nanoclays, were also used. The intergallery spacing of MMT increased on amine modification as suggested by the shifting of the X‐ray diffraction (XRD) peak from 7.6 to 4.5 and 3.8° in the cases of OC and CL20, respectively. The latter demonstrated no XRD peak when it was used at 2 and 4 parts phr in the SEBS system. Transmission electron microscopy studies showed the intercalation–exfoliation morphology in SEBS containing 4 parts of CL20₄–SEBS, agglomeration in SEBS having 4 parts of MMT, and mixed morphology in SEBS with 4 parts of OC systems. Locations of the clay particles were indicated by the atomic force micrographs. Mechanical and dynamic mechanical thermal analysis studies confirmed the best properties with the CL20₄–SEBS nanocomposites. Significant improvements in mechanical properties such as tensile strength, modulus, work to break, and elongation at break were achieved with the CL20₄–SEBS in polymer‐layered silicate nanocomposites. Dynamic mechanical studies further showed the affinity of the organoclays toward both segments of the TPE and a compatibilization effect with CL20 at a 4‐phr loading. Atomic force microscopy showed distinctly different morphologies in nanocomposites prepared through solution and melt processing. Comparisons of the mechanical, dynamic mechanical, and morphological properties of the nanocomposites prepared by melt and solution intercalation processes were done. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2040–2052, 2006     

Novel fabrication of disorderly exfoliated sodium montmorillonite in a styrene–butadiene rubber matrix

Using industrial technologies, we prepared a sodium montmorillonite (Na‐MMT) slurry and an irradiated styrene–butadiene rubber (SBR) latex, and then spray dried them to produce a novel, ultrafine fully vulcanized powder SBR (UFPSBR)/Na‐MMT nanocompound powder in which the nanoscale UFPSBR particles and exfoliated Na‐MMT were isolated and stuck together. When the UFPSBR/Na‐MMT nanocompound powder was mixed with crude SBR, the exfoliated Na‐MMT was disorderly dispersed in the SBR matrix because of the carrier nature of the UFPSBR particle, which is compatible with SBR and disperses easily in the SBR matrix, and the SBR/UFPSBR/Na‐MMT ternary nanocomposite was prepared. When compared with SBR/Na‐MMT binary composites, the SBR/UFPSBR/Na‐MMT ternary nanocomposite has a shorter vulcanization time, higher strength, and better flame retardancy because of the good dispersion of exfoliated Na‐MMT in the SBR matrix with a Na‐MMT loading range of 4 phr. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2013     

Preparation and dynamic mechanical properties of poly(styrene‐b‐butadiene)‐modified clay nanocomposites

Polybutyl acrylate (PBA) was intercalated into clay by the method of multistep exchange reactions and diffusion polymerization. The clay interlayer surface is modified, and obtaining the modified clay. The structures of the clay‐PBA, clay‐GA (glutamic acid), and the clay‐DMSO (dimethyl sulfoxide) were characterized using X‐ray diffraction (XRD). The new hybrid nanocomposite thermoplastic elastomers were prepared by the clay‐PBA with poly(styrene‐b‐butadiene) block copolymer (SBS) through direct melt intercalation. The dynamic mechanical analysis (DMA) curves of the SBS/modified clay nanocomposites show that partial polystyrene segments of the SBS have intercalated into the modified clay interlayer and exhibited a new glass transition at about 157°C (T_g3). The glass transition temperature of polybutadiene segments (T_g1) and polystyrene segments out of the modified clay interlayer (T_g2) are about ?76 and 94°C, respectively, comparied with about ?79 and 100°C of the neat SBS, and they are basically unchanged. The T_g2 intensity of the SBS‐modified clay decreases with increasing the amounts of the modified clay, and the T_g3 intensity of the SBS‐modified clay decreases with increasing the amounts of the modified clay up to about 8.0 wt %. When the contents of the modified clay are less than about 8.0 wt %, the SBS‐modified clay nanocomposites are homogeneous and transparent. The T_gb and T_gs of the SBS‐clay (mass ratio = 98.0/2.0) are ?78.39 and 98.29°C, respectively. This result shows that the unmodified clay does not essentially affect the T_gb and T_gs of the SBS, and no interactions occur between the SBS and the unmodified clay. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1499–1503, 2002; DOI 10.1002/app.10353     

Styrene–butadiene–styrene/montmorillonite nanocomposites synthesized by anionic polymerization

We successfully synthesized an exfoliated styrene–butadiene–styrene triblock copolymer (SBS)/montmorillonite nanocomposite by anionic polymerization. Gel permeation chromatography showed that the introduction of organophilic montmorillonite (OMMT) resulted in a small high‐molecular‐weight fraction of SBS in the composites, leading to a slight increase in the weight‐average and number‐average molecular weights as well as the polydispersity index. The results from ¹H‐NMR revealed that the introduction of OMMT almost did not affect the microstructure of the copolymer when the OMMT concentration was lower than 4 wt %. Transmission electron microscopy and X‐ray diffraction showed a completely exfoliated nanocomposite, in which both polystyrene and polybutadiene blocks entered the OMMT galleries, leading to the dispersion of OMMT layers on a nanoscale. The exfoliated nanocomposite exhibited higher thermal stability, glass‐transition temperature, elongation at break, and storage modulus than pure SBS. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Preparation and characterization of polypropylene–montmorillonite nanocomposites generated by in situ metallocene catalyst polymerization

An ion‐exchange method was applied to replace sodium cations inside the interlamellar space of montmorillonite with positively charged stearyl trimethyl ammonium chloride. The d₀₀₁‐spacing of montmorillonite is larger in toluene than in other solvents. The overexchanged stearyl methyl ammonium chloride in the montmorillonite layers can be completely washed out by ethanol. Polypropylene–montmorillonite nanocomposites were prepared by using the supported rac‐Et(Ind)₂ZrCl₂ catalyst on the montmorillonite. The nanocomposites that were polymerized by the supported catalyst were characterized by infrared spectroscopy, nuclear magnetic resonance, X‐ray diffraction, differential scanning calorimetry, scanning electron microscopy, and transmission electron microscopy. Transmission electron microcopy shows that each silicate sheet of montmorillonite is randomly dispersed into the polypropylene matrix following polymerization by using a supported catalyst. The polypropylene nanocomposites had higher crystallinity, hardness, and thermal properties than pure polypropylene. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1228–1236, 2005     

Fiber breakage and dispersion in carbon‐fiber‐reinforced nylon 6/clay nanocomposites

In this paper, short carbon‐fiber‐reinforced nylon 6/clay nanocomposites are prepared via melt compounding, and fiber breakage and dispersion during processing are studied. The influences of clay and processing conditions on fiber breakage and dispersion are taken into consideration. It is found that the presence of organoclay can improve fiber dispersion, which is due to dispersion at the nanoscale of exfoliated clay sheets with large aspect ratio. The bimodal distribution of fiber length is observed in fiber‐reinforced nanocomposites, which is similar to that in conventional fiber‐reinforced composites. The improvement of fiber breakage at moderate organoclay loadings is also observed, which is ascribed to the rheological and lubricating effects induced by organoclay. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Influence of granulometry and organic treatment of a Brazilian montmorillonite on the properties of poly(styrene‐co‐n‐butyl acrylate)/layered silicate nanocomposites prepared by miniemulsion polymerization

The influence of granulometry and organic treatment of a Brazilian montmorillonite (MMT) clay on the synthesis and properties of poly(styrene‐co‐n‐butyl acrylate)/layered silicate nanocomposites was studied. Hybrid latexes of poly(styrene‐co‐butyl acrylate)/MMT were synthesized via miniemulsion polymerization using either sodium or organically modified MMT. Five clay granulometries ranging from clay particles smaller than 75 μm to colloidal size were selected. The size of the clay particles was evaluated by specific surface area measurements (BET). Cetyl trimethyl ammonium chloride was used as an organic modifier to enhance the clay compatibility with the monomer phase before polymerization and to improve the clay distribution and dispersion within the polymeric matrix after polymerization. The sodium and organically modified natural clays as well as the composites were characterized by X‐ray diffraction analysis. The latexes were characterized by dynamic light scattering. The mechanical, thermal, and rheological properties of the composites obtained were characterized by dynamical‐mechanical analysis, thermogravimetry, and small amplitude oscillatory shear tests, respectively. The results showed that smaller the size of the organically modified MMT, the higher the degree of exfoliation of nanoplatelets. Hybrid latexes in presence of Na‐MMT resulted in materials with intercalated structures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of polyurethane/montmorillonite nanocomposites by in situ polymerization

In this paper, a new type of organophilic montmorillonite, co‐treated with cetyltrimethyl ammonium bromide (CTAB) and 4,4′‐diphenymethylate diisocyanate (MDI), was modified and applied to prepare polyurethane/montmorillonite nanocomposites via in situ polymerization. The nanoscale montmorillonite layers were exfoliated and dispersed relatively homogeneously in the polyurethane matrix, and characterized by X‐ray diffraction and transmission electron microscopy. The thermal degradation temperature of the nanocomposites increased, as compared with pristine polyurethane. Dynamic mechanical analysis confirmed the constraining effect of exfoliated montmorillonite layers on polyurethane chains, which benefited the increased storage modulus and increased glass transition temperature. Tensile tests showed that the exfoliated nanocomposites were reinforced and toughened by the addition of nanometer‐size montmorillonite layers. Copyright © 2006 Society of Chemical Industry     

Morphology and mechanical properties of clay/styrene‐butadiene rubber nanocomposites

Based on the character of a clay that could be separated into many 1‐nm thickness monolayers, clay styrene‐butadiene rubber (SBR) nanocomposites were acquired by mixing the SBR latex with a clay/water dispersion and coagulating the mixture. The structure of the dispersion of clay in the SBR was studied through TEM. The mechanical properties of clay/SBR nanocomposites with different filling amounts of clay were studied. The results showed that the main structure of the dispersion of clay in the SBR was a layer bundle whose thickness was 4–10 nm and its aggregation formed by several or many layer bundles. Compared with the other filler, some mechanical properties of clay/SBR nanocomposites exceeded those of carbon black/SBR composites and they were higher than those of clay/SBR composites produced by directly mixing clay with SBR through regular rubber processing means. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1873–1878, 2000     

Processing of transmission electron microscope images for quantification of the layer dispersion degree in polymer‐clay nanocomposites

Quantification of the layered silicates dispersion level is necessary to more accurately evaluate the performance in polymer/clay nanocomposites. In this article, a new approach is developed to quantify the degree of exfoliation, intercalation, and immiscibility of layered silicates in polymer matrix, based on bright‐dark pixel measurement (BDPM) in transmission electron microscope (TEM) images. Several examples of exfoliated, intercalated, and immiscible composites with different polymer and clay systems were examined. The method is capable of estimating the percent contribution of all morphologies present in the image. Comparing with X‐ray diffraction (XRD) evidences, it is indicated that as a rule of thumb, the exfoliated structure is dominant whenever the exfoliation percent calculated by BDPM methodology is over 65%, no matter what kind of clay or polymer matrix is used. The intercalated structure can be ascribed to the images with exfoliation level less than 65%, but with the intercalation degree over 28%. Application of this method can facilitate the modeling or correlation of various nanocomposite properties with respect to exfoliation degree. A quantified relation is also possible between XRD and TEM using this approach. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of poly(ε‐caprolactone)/clay nanocomposites using polyhedral oligomeric silsesquioxane surfactants as organic modifier and initiator

Poly(ε‐caprolactone)/clay nanocomposites were synthesized by in situ ring‐opening polymerization of ε‐caprolactone in the presence of montmorillonite modified by hydroxyl functionalized, quaternized polyhedral oligomeric silsesquioxane (POSS) surfactants. The octa(3‐chloropropyl) polyhedral oligomeric silsesquioxane was prepared by hydrolytic condensation of 3‐chloropropyltrimethoxysilane, which was subsequently quaternized with 2‐dimethylaminoethanol. Montmorillonite was modified with the quaternized surfactants by cation exchange reaction. Bulk polymerization of ε‐caprolactone was conducted at 110°C using stannous octoate as an initiator/catalyst. Nanocomposites were analyzed by X‐ray diffraction, transmission electron microscopy, thermo gravimetric analysis, and differential scanning calorimetry. Hydroxyl functionalized POSS was employed as a surface modifier for clay which gives stable clay separation for its 3‐D structure and also facilitates the miscibility of polymer with clay in the nanocomposites due to the star architecture. An improvement in the thermal stability of PCL was observed even at 1 wt % of clay loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Stereology‐based quantitative characterization of dispersion from TEM micrographs of polymer–clay nanocomposites

Quantitative characterization of the state of dispersion and extent of exfoliation is critical in developing processing structure–property relationships in polymer–clay nanocomposites. Quantification of dispersion, exfoliation, and nanostructure in polymer–clay nanocomposites by 3D stereological parameters using image analysis of 2D transmission electron microscopy (TEM) micrographs were recently proposed. The 3D dispersion quantifying parameters are designed such that they are free of the bias associated with not sampling the true particle diameter in a 2D TEM section. In this article, the ability of the proposed 3D dispersion quantifying parameters to describe the dispersion over the entire possible range of exfoliation, and to capture independent aspects of dispersion are demonstrated by quantifying several sets of samples that were designed using a polypropylene (PP)/maleated PP/clay system. The details of the image analysis procedure, the underlying challenges, and errors involved in the segmentation process are also discussed. The 3D dispersion quantifying parameters, exfoliation number and inter‐particle distance, were critically compared against the standard 2D dispersion quantifying parameters, such as mean length, thickness, and aspect ratio. In all cases examined in this study, the sensitivity and resolution of the 3D parameters in terms of quantifying the dispersion of the nanostructure appeared comparable if not better than the standard 2D parameters. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study on flammability of montmorillonite/styrene‐butadiene rubber (SBR) nanocomposites

The flammability of montmorillonite (MMT)/SBR nanocomposites, prepared by the technique of cocoagulating rubber latex and clay aqueous suspension, was investigated. Flammability studies, performed on the cone calorimeter, showed that the maximum heat release rate (HRR) of SBR decreased from 1987 to 1442 kw/m² with the introduction of nanoclay (20 phr). This nanocomposite had the lowest mass loss rate and the largest amount of char upon combustion compared with conventional SBR composites with the same clay loading and pure SBR. The permeability properties of MMT/SBR composites were also measured. It was deduced that the lowered permeability was responsible for the reduced mass loss rate and hence the lower HRR. Unfortunately, the oxygen index (OI) of the nanocomposites was not as high as expected. Combination of Mg(OH)₂ and clay was effective for the improvement of both mechanical properties and OI. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 844–849, 2005     

Preparation of polyethylene–clay nanocomposites directly from Na+ montmorillonite by a melt intercalation method

Polyethylene (PE)/clay nanocomposites were prepared directly from Na⁺ montmorillonite by a melt intercalation technique, using hexadecyl trimethyl ammonium bromide (C16) as a reactive compatibilizer. Three other polymer–clay nanocomposites were also prepared by this new technique. Their structures were characterized by X‐ray diffraction and transmission electron microscopy. The mechanism of this new method was studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2583–2585, 2003