Effect of the grafted silane on the dispersion and orientation of clay in polyethylene nanocomposites

The CTAB ammonium intercalated montmorillonite clay, CMT, was modified by an alkylsilane, Dodecyltrimethoxylsilane, to improve the miscibility of organoclays with PE matrix, involving the grafting reaction between the silane and silanol groups on the edge of clay. The silane modified clays (DMT) exhibited improved thermal stability due to the replacement of the physically adsorbed ammonium by the covalently bonded silane. The clays were melt compounded with polyethylene. Compared with the composite of PE/CMT, the clay dispersion state was improved, and a unique orientation of the clay layered was observed in PE/DMT nanocomposites, which was confirmed by XRD and TEM studies. The dispersion state, orientation degree of clay and, as a result, the mechanical and thermal properties of the nanocomposites were enhanced with the increasing amount of the grafted silane, indicating that the edge grafting of silane played a crucial role in controlling the structure and properties of nanocomposites. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Synthesis of effective poly(4‐vinylpyridine) nanocomposites: in situ polymerization from edges/surfaces and interlayer galleries of clay

Poly(4‐vinylpyridine) (P4VP) nanocomposites have been prepared by using an in situ polymerization method in the presence of organically modified montmorillonite (MMT) clays with a quarternary salt of cocoamine containing a vinyl group, as well as trimethoxy vinyl silane. The nanocomposites were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The desired exfoliated nanocomposite structure was achieved when the MMT modification was conducted in the presence of both modifiers, whereas individual modifications all resulted in intercalated structures. This resultant exfoliated nanocomposite was found to have better thermal stability and dynamic mechanical performance when compared to the other nanocomposites, even with 2 % clay loading. Copyright © 2005 Society of Chemical Industry     

Influence of the degree of exfoliation of an organoclay on the flame‐retardant properties of cross‐linked ethylene‐co‐Propylene‐co‐diene monomer‐g‐Maleic anhydride‐based composites

Layered montmorillonite was synthesized by hydrothermal method, progressively modified by an alkylammonium and thoroughly characterized by elemental, thermal, and X‐ray diffraction (XRD) analysis. Pristine and modified clays were introduced in maleic anhydride‐modified ethylene‐co‐propylene‐co‐diene monomer matrix. XRD and transmission electron microscopy investigations showed microcomposite as well as intercalated or exfoliated nanocomposites morphologies depending on the organic content of the clay. The inhibitor character of the pristine clay on peroxides as crosslinking agent for rubbers was then demonstrated and overcome by using electron beam irradiation for specimens containing unmodified clay. Dynamic mechanical analyses and swelling measurements showed that it is possible to obtain the same degree of crosslinking of the polymer matrix by electron beam irradiation of the composites based on pristine clay specimens and conventional peroxide curing of modified‐clay‐based ones. Finally, flame‐retardant properties of different clays‐based composites showed a direct dependence on the degree of exfoliation. It was observed that the better the exfoliation, the higher is the flame retardancy. POLYM. COMPOS., 38:966–973, 2017. © 2015 Society of Plastics Engineers     

Silane Modification of Carbon Nanotubes and Preparation of Silane Cross‐Linked LLDPE/MWCNT Nanocomposites

The objective of this study is to investigate the effects of carbon nanotube (CNT) content, surface modification, and silane cross‐linking on mechanical and electrical properties of linear low‐density polyethylene/multiwall CNT nanocomposites. CNTs were functionalized by vinyltriethoxysilane to incorporate the ─O─C2H5 functional groups and were melt‐blended with polyethylene. Silane‐grafted polyethylene was then moisture cross‐linked. Silanization of CNT was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA), and EDX analysis. Hot‐set test results showed that silane cross‐linking of polyethylene and incorporation of modified CNTs into polyethylene led to an increase in cross‐linking density and the number of entanglements resulting in a decrease in elongation. It was found that the addition of pristine multiwall carbon nanotubes (MWCNTs) and functionalized MWCNTs does not affect silane cross‐linking density. Silane modification resulted in a stronger adhesion of the silane cross‐linked LLDPE to silanized MWCNTs according to scanning electron microscopy micrographs. Additionally, the electrical tests revealed that the silane modification of CNTs results in an improvement in electrical properties of nanocomposites, while silane cross‐linking will not have an effect on electrical properties. Rheological properties of MWCNT/LLDPE nanocomposites have been studied thoroughly and have been discussed in this study. Moreover, according to TGA test results, modification of the MWCNTs led to a better dispersion of them in the LLDPE matrix and consequently resulted in an improvement in thermal properties of the nanocomposites. Crystallinity and melting properties of the nanocomposites have been evaluated in detail using DSC analysis. J. VINYL ADDIT. TECHNOL., 26:113–126, 2020. © 2019 Society of Plastics Engineers     

Morphology,Thermal and Mechanical Properties of Poly (Styrene-Acrylonitrile) (SAN)/Clay Nanocomposites from Organic-Modified Montmorillonite

Poly (styrene-acrylonitrile) (SAN)/clay nanocomposites have successfully been prepared by melt intercalation method. The hexadecyl triphenyl phosphonium bromide (P16) and cetyl pyridium chloride (CPC) are used to modify the montmorillonite (MMT). The structure and thermal stability property of the organic modified MMT are, respectively characterized by Fourier transfer infrared (FT-IR) spectra, X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The results indicate that the cationic surfactants intercalate into the gallery of MMT and the organic-modified MMT by P16 and CPC has higher thermal stability than hexadecyl trimethyl ammonium bromide (C16) modified MMT. The influences of the different organic modified MMT on the structure and properties of the SAN/clay nanocomposites are investigated by XRD, transmission electronic microscopy (TEM), high-resolution electron microscopy (HREM), TGA and dynamic mechanical analysis (DMA), respectively. The results indicate that the SAN cannot intercalate into the interlayers of the pristine MMT and results in microcomposites. However, the dispersion of the organic-modified MMT in the SAN is rather facile and the SAN nanocomposites reveal an intermediate morphology, an intercalated structure with some exfoliation and the presence of small tactoids. The thermal stability and the char residue at 700°C of the SAN/clay nanocomposites have remarkably enhancements compared with pure SAN. DMA measurements show that the silicate clays improve the storage modulus and glass transition temperature (Tg) of the SAN matrix in the nanocomposites.     

Preparation of a long-alkyl-chain silane grafted organic montmorillonite and its nanocomposite with SEBS

In this study, a modified montmorillonite (W-H-OMMT) was prepared by intercalating pristine montmorillonite using a phosphorus salt and a subsequent grafting using a long-alkyl-chain silane, and the nanocomposites with poly[styrene–(ethylene-co-butylene)–styrene] (SEBS) were prepared by melt blending. The pristine and the modified MMT were characterized by XRD, FT-IR, XPS and SEM. The morphology of the SEBS nanocomposites was studied using XRD, SEM and TEM, and the results can be correlated well with transparency, color, surface contact angle, rheological behavior, thermal and mechanical properties of the nanocomposites. As compared with pristine and the modified clay, more uniform dispersion and improved compatibility are observed for the W-H-OMMT in the SEBS matrix, resulting in better transparency and more hydrophobic surface for the SEBS/W-H-OMMT nanocomposite. Better thermal stability, a synergetic effect in tensile strength and elongation at break were observed, which can be attributed to well dispersion of the W-H-OMMT, as well as perfect adhesion between the W-H-OMMT and the SEBS matrix from the enhanced molecular interaction between the long-alkyl chain and the SEBS molecules. Compared to pure SEBS, the strength and elongation of SEBS/W-H-OMMT nanocomposite increased by 8.5 and 7.6 %; meanwhile, the water contact angel and the 50 % weight loss temperature increased by 5.3 and 13.1 %, respectively. Appropriate silane grafted organic montmorillonite provided an efficient way for the overall performance improvement of SEBS.     

Effect of both silane‐grafted and ion‐exchanged organophilic clay in structural,thermal, and mechanical properties of unsaturated polyester nanocomposites

Unsaturated polyester (UPE) resin including styrene monomer was mixed with organophilic montmorillonite (MMT) clay and its crosslinking polymerization reaction was done in the presence of free‐radical initiator. MMT clay was modified with cetyl trimethly ammonium bromide and trimethoxy vinyl silane. The nanocomposites were characterized by X‐ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), thermogravimetric and dynamic mechanical analyses (TGA and DMA). The exfoliated nanocomposite structure was obtained when the MMT clay was modified in the presence of both modifiers, whereas individual modifications all resulted in intercalated structures. The exfoliated UPE nanocomposite exhibited better thermal and dynamic mechanical properties when compared with pure UPE and other composites, even with 3 wt% clay loading. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

聚对苯二甲酸丁二醇酯/聚甲基丙烯酸甲酯季铵盐修饰蒙脱土纳米复合材料的制备与性能

用聚甲基丙烯酸甲酯苄基季铵盐和聚甲基丙烯酸甲酯十八烷基季铵盐修饰蒙脱土,制备出两种有机土（MAPS-B-MMT和MAPS-O-MMT）,通过熔融共混法制备聚对苯二甲酸丁二醇酯/蒙脱土（PBT/MMT）纳米复合材料,考察了有机土含量和修饰剂结构对复合材料性能的影响。TEM结果显示,两类复合材料均为插层型纳米复合材料。热稳定性能研究表明,PBT/MAPS-B和PBT/MAPS-O两个体系热稳定性有较大的改善,材料的初始降解温度均比纯PBT提高,PBT/MAPS-O-2纳米复合材料的初始降解温度提高了20 ℃;热稳定性受到蒙脱土分散性影响,随着黏土含量增加,蒙脱土分散性变差,导致材料初始降解温度下降,质量分数2%为蒙脱土的最佳含量;加入有机土降低了材料的熔融温度,提高了材料的结晶速率和结晶度。     

The effect of clay type and of clay–masterbatch product in the preparation of polypropylene/clay nanocomposites

Clay containing polypropylene (PP) nanocomposites were prepared by direct melt mixing in a twin screw extruder using different types of organo‐modified montmorillonite (Cloisite 15 and Cloisite 20) and two masterbatch products, one based on pre‐exfoliated clays (Nanofil SE 3000) and another one based on clay–polyolefin resin (Nanomax‐PP). Maleic anhydride‐grafted polypropylene (PP‐g‐MA) was used as a coupling agent to improve the dispersability of organo‐modified clays. The effect of clay type and clay–masterbatch product on the clay exfoliation and nanocomposite properties was investigated. The effect of PP‐g‐MA concentration was also considered. Composite morphologies were characterized by X‐ray diffraction (XRD), field emission gun scanning electron microscopy (FEG‐SEM), and transmission electron microscopy (TEM). The degree of dispersion of organo‐modified clay increased with the PP‐g‐MA content. The thermal and mechanical properties were not affected by organo‐modified clay type, although the masterbatch products did have a significant influence on thermal and mechanical properties of nanocomposites. Intercalation/exfoliation was not achieved in the Nanofil SE 3000 composite. This masterbatch product has intercalants, whose initial decomposition temperature is lower than the processing temperature (T ～ 180°C), indicating that their stability decreased during the process. The Nanomax‐PP composite showed higher thermal and flexural properties than pure PP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A Comparative Study of Polystyrene/Layered Silicate Nanocomposites,Synthesized by Emulsion and Bulk Polymerization Methods

Polystyrene/clay (PS/clay) nanocomposites were synthesized by insitu emulsion and bulk polymerization methods. Sodium montmorillonite (Na-MMT) and two organically modified clays (Cloisite 30B and Cloisite 15A) were employed. The effect of clay swelling method and sonication on the d-spacing of silicate layers was also investigated. The surface morphology of pure PS and PS/clay nanocomposites were comparatively investigated using scanning electron microscopy (SEM). Thermogravimetric analysis (TGA) of PS and PS/clay nanocomposites revealed the improved thermal stability of PS/clay nanocomposites compared to pure PS. Results of optical transparency tests showed the better transparency of nanocomposite films compared to the pure PS film.     

The structure‐property relationship of novolac cured epoxy resin/clay nanocomposites

Intercalated or exfoliated novolac cured epoxy resin nanocomposites were prepared with two different kinds of layered silicates – montmorillonite (PK‐802) and nontronite (PK‐805). The bifunctional modifiers (PI/BEN or MI/BEN) are used to modify the clays for improvement of the properties of polymer where benzalkonium chloride (BEN) acts as a compatibilizing agent and 2‐phenylimidazole (PI) or 2‐methylimidazole (MI) as the accelerators. Both the compatibilizer and accelerator are simultaneously intercalated into the gallery space of pure clays to form the modified clay. The novolac cured epoxy nanocomposites are prepared with these modified clays by crosslinking polymerization reaction. The properties of novolac cured epoxy/clay nanocomposites were characterized by wide‐angle X‐ray diffraction (WAXD), thermo‐gravimetric analysis (TGA), dynamic mechanical analysis (DMA), and transmission electron microscopy (TEM) methods. According to the measurement, these novolac cured epoxy‐clay nanocomposites have been shown the significant improvement in the thermal, mechanical, and barrier properties that may be applied to make printed circuit board. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Polymorphic behavior of nylon 6/saponite and nylon 6/montmorillonite nanocomposites

X‐ray diffraction methods and DSC thermal analysis have been used to investigate the structural change of nylon 6/clay nanocomposites. Nylon 6/clay has prepared by the intercalation of ε‐caprolactam and then exfoliaton of the layered saponite or montmorillonite by subsequent polymerization. Both X‐ray diffraction data and DSC results indicate the presence of polymorphism in nylon 6 and in nylon 6/clay nanocomposites. This polymorphic behavior is dependent on the cooling rate of nylon 6/clay nanocomposites from melt and the content of saponite or montmorillonite in nylon 6/clay nanocomposites. The quenching from the melt induces the crystallization into the γ crystalline form. The addition of clay increases the crystallization rate of the α crystalline form at lower saponite content and promotes the heterophase nucleation of γ crystalline form at higher saponite or montmorillonite content. The effect of thermal treatment on the crystalline structure of nylon 6/clay nanocomposites in the range between Tg and Tm is also discussed.     

Aliphatic polyamidoamine hyperbranched polymers/layered silicate nanocomposites

Polyamidoamine hyperbranched polymer (Hyp)/clay nanocomposites were synthesized by using both of montmorillonite and laponite clays. Poly amidoamine hyperbranched polymer (Hyp) was prepared by one‐pot polymerization via couple monomer methodology. Afterward, the amino ends of Hyp were modified with methyl methacrylate (MMA), styrene (St) and butyl methacrylate (n‐BuMA) polymers which were previously prepared via ATRP (atom transfer radical polymerization) to form the corresponding new hyperbranched polymers Hyp₁, Hyp₂ and Hyp₃. Those formed polymers were inserted into the modified clay, such as montmorillonite and laponite to form their nanocomposites. The formed polymer/clay nanocomposites were characterized via XRD, TEM, and thermal analyses. The formed hyperbranched polymers generally showed intercalation behavior more than the exfoliation one mostly because of the bulkiness of the hyperbranched skeleton. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of some polyacrylate/montmorillonite nanocomposites by in situ emulsion polymerization using redox initiation system

Intercalated modification of Montmorillonite clay (MMT) with three different amino acids—Alanine, Leucine, and Phenylalanine—in the presence of hydrochloric acid followed by surface modification by methyl triethoxy silane coupling agent to produce double modified Montmorillonite clay which is characterized by X‐ray diffraction (XRD) and Thermogravimetric analysis (TGA). The data shows an increase in d‐spacing of modified clay as a result of cationic exchange. Double modified MMT clay was used in the preparation of Polyacrylate/clay nanocomposites by using an in situ redox emulsion polymerization of polyglycidylmethacrylate (PGMA) and polymethylmethacrylate (PMMA). The structure and properties of the prepared nanocomposites were achieved by XRD, TGA, and SEM. The results show that all weight loses temperatures for the nanocomposite samples are higher than that of pure polymer in both PGMA and PMMA. It is also obvious that the increasing in the clay content plays an effective role in the increasing of thermal stability of these materials. SEM shows that the clay is more homogenously dispersed in PMMA than in PGMA matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Mechanical properties and rheological behavior of poly(butylene terephthalate)/clay nanocomposites with different organoclays

Poly(butylene terephthalate)–clay nanocomposites with three different organically modified clays were prepared via melt blending in a twin‐screw extruder. Decyl triphenylphosphonium bromide, hexadecyl triphenylphosphonium bromide, and cetyl pyridinium chloride were used to modify the naturally occurring montmorillonite clay. The organically modified clays were characterized with X‐ray diffraction for the d₀₀₁‐spacing and with thermogravimetric analysis to determine the thermal stability. The prepared nanocomposites were injection‐molded and examined for the dispersion quality of the clay, the mechanical properties, and the rheological behavior. The tensile strength of the nanocomposites increased with a 1% addition of clay; however, more clay decreased the tensile strength. Nanocomposites with finely dispersed clay platelets and nanocomposites with poorly dispersed clay platelets showed very different rheological behaviors. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of polystyrene/clay nanocomposite by suspension and emulsion polymerization

Organophilic montmorillonite was prepared using ion‐exchange method between sodium ions in clay layers and four kind of quaternary ammonium salt. The montmorillonite has the largest d₀₀₁‐spacing, as determined by X‐ray diffraction in modified by di(hydrogenated tallowalkyl) dimethyl ammonium chloride. Polystyrene montmorillonite nanocomposites were obtained by suspension and emulsion polymerization of styrene in the dispersed organophilic montmorillonite. The d₀₀₁‐spacing of clay was determined by X‐ray diffraction (XRD). The thermal stability of organophilic montmorillonite was investigated by thermogravimetric analysis (TGA). POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

A comparative study of UV active silane-grafted and ion-exchanged organo-clay for application in photocurable urethane acrylate nano- and micro-composites

A number of urethane acrylate nano- and micro-composites have been developed using both ion exchange and silane grafting chemistry. The organically modified clays which were used contained either methacrylate or acrylate functionalities which were capable of reacting with the acrylate groups in the urethane acrylate matrix. [2-(Acryloyloxy)ethyl]trimethyl-ammonium ion (AOETMA) or [2-(methacryloyloxy)ethyl]trimethylammonium ion (MAOTMA) were exchanged onto montmorillonite (MMT) as shown by an increase in the inter-gallery spacing of the MMT. Silane grafting was undertaken using [3-(acryloxy)propyl]dimethylmethoxysilane (APDMMS) or [3-(methacryloxy)propyl]dimethylmethoxysilane (MAPDMMS) and also showed an increase in inter-gallery spacing. The structures of the resulting urethane acrylate composites were characterized using X-ray diffraction (XRD) and transmission electron microscopy (TEM) and showed predominantly intercalated structures with some exfoliation (more evident in the silane-grafted systems). Dynamical mechanical thermal analysis (DMTA) showed a more significant increase in effective crosslink density (as measured from the plateau of the rubbery modulus) in the composites containing the reactive clays as compared to the unmodified clay, supporting the concept that the acrylate and methacrylate functionalities of the modified clays had reacted with the matrix. Other thermal and mechanical properties were also evaluated.     

A flammability performance comparison between synthetic and natural clays in polystyrene nanocomposites

Polymer‐clay nanocomposites are a newer class of flame retardant materials of interest due to their balance of mechanical, thermal and flammability properties. Much more work has been done with natural clays than with synthetic clays for nanocomposite flammability applications. There are advantages and disadvantages to both natural and synthetic clay use in a nanocomposite, and some of these, both fundamental and practical, will be discussed in this paper. To compare natural and synthetic clays in regards to polymer flammability, two clays were used. The natural clay was a US mined and refined montmorillonite, while the synthetic clay was a fluorinated synthetic mica. These two clays were used as inorganic clays for control experiments in polystyrene, and then converted into an organoclay by ion exchange with an alkyl ammonium salt. The organoclays were used to synthesize polystyrene nanocomposites by melt compounding. Each of the formulations was analysed by X‐ray diffraction (XRD), thermogravimetric analysis (TGA) and transmission electron microscopy (TEM). Flammability performance was measured by cone calorimeter. The data from the experiments show that the synthetic clay does slightly better at reducing the heat release rate (HRR) than the natural clay. However, all the samples, including the inorganic clay polystyrene microcomposites, showed a decreased time to ignition, with the actual nanocomposites showing the most marked decrease. The reason for this is postulated to be related to the thermal instability of the organoclay (via the quaternary alkyl ammonium). An additional experiment using a more thermally stable organoclay showed a time to ignition identical to that of the base polymer. Finally, it was shown that while polymer‐clay nanocomposites (either synthetic or natural clay based) greatly reduce the HRR of a material, making it more fire safe, they do not provide ignition resistance by themselves, at least, at practical loadings. Specifically, the cone calorimeter HRR curve data appear to support that these nanocomposites continue to burn once ignited, rather than self‐extinguish. Copyright © 2004 John Wiley & Sons, Ltd.     

Effect of clay modifiers on the morphology and physical properties of thermoplastic polyurethane/clay nanocomposites

Thermoplastic polyurethanes (TPUs)/clay nanocomposites were prepared via melt processing using the ester type and the ether type TPUs and three differently modified organoclays (denoted as C30B, C25A and C15A) as well as pristine montmorillonite (PM). XRD and TEM results showed that the addition of C30B with hydroxyl group led to the nearly exfoliated structures in both TPUs. In the case of C25A and C15A clays, partially intercalated nanocomposites were obtained in both TPUs, where C25A showed better dispersion than C15A. Natural clay (PM) was not effectively dispersed in both TPUs. The tensile properties of nanocomposites with C30B were better than ones with the other clays. Higher tensile properties were obtained for ester type TPU than ether type TPU nanocomposites with all clays tested. Although the improvement in tensile properties decreased after the second extrusion of the nanocomposites, properties of the nanocomposite after first melt processing were still good enough for practical applications. Morphological changes induced by the addition of clays were analyzed using FTIR, DSC and rheological test results. Some clays were observed to cause demixing of hard and soft segments in the nanocomposites and location of clays in either soft segment or hard segment domains was also studied.     

Effect of clay modification on the morphological,mechanical, and thermal properties of polyamide 6/polypropylene/montmorillonite nanocomposites

Polyamide 6/polypropylene (PA6/PP = 70/30 parts) blends containing 4 phr (parts per hundred resin) of organophilic montmorillonite (OMMT) were prepared by melt compounding. The sodium montmorillonite (Na‐MMT) was modified using three different types of alkyl ammonium salts, namely dodecylamine, 12‐aminolauric acid, and stearylamine. The effect of clay modification on the morphological and mechanical properties of PA6/PP nanocomposites was investigated using x‐ray diffraction (XRD), transmission electron microscopy (TEM), tensile, flexural, and impact tests. The thermal properties of PA6/PP nanocomposites were characterized using thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and heat distortion temperature (HDT). XRD and TEM results indicated the formation of exfoliated structure for the PA6/PP nanocomposites prepared using stearylamine modified montmorillonite. On the other hand, a mixture of intercalated and exfoliated structures was found for the PA6/PP nanocomposites prepared using 12‐aminolauric acid and dodecylamine modified montmorillonite. Incorporation of OMMT increased the stiffness but decreased the ductility and toughness of PA6/PP blend. The PA6/PP nanocomposite containing stearylamine modified montmorillonite showed the highest tensile, flexural, and thermal properties among all nanocomposites. This could be attributed to better exfoliated structure in the PA6/PP nanocomposite containing stearylamine modified montmorillonite. The storage modulus and HDT of PA6/PP blend were increased significantly with the incorporation of both Na‐MMT and OMMT. The highest value in both storage modulus and HDT was found in the PA6/PP nanocomposite containing stearylamine modified montmorillonite due to its better exfoliated structure. POLYM. COMPOS., 31:1156–1167, 2010. © 2009 Society of Plastics Engineers