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     

Preparation and characterization of poly(butylene terephthalate) nanocomposites with various organoclays

Layered‐silicate‐based polymer–clay nanocomposite materials were prepared depending on the surface modification of montmorillonite (MMT). Nanocomposites consisting of poly(butylene terephthalate) (PBT) as a matrix and dispersed inorganic clay modified with cetyl pyridinium chloride (CPC), benzyl dimethyl N‐hexadecyl ammonium chloride, and hexadecyl trimethyl ammonium bromide by direct melt intercalation were studied. The organoclay loading was varied from 1 to 5 wt %. The organoclays were characterized with X‐ray diffraction (XRD) to compute the crystallographic spacing and with thermogravimetric analysis to study the thermal stability. Detailed investigations of the mechanical and thermal properties as well as a dispersion study by XRD of the PBT/clay nanocomposites were conducted. X‐ray scattering showed that the layers of organoclay were intercalated with intercalating agents. According to the results of a differential scanning calorimetry analysis, clay acted as a nucleating agent, affecting the crystallization. The PBT nanocomposites containing clay treated with CPC showed good mechanical properties because of intercalation into the polymer matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The effect of organic modifier‐12‐aminolauric acid on morphology and thermal properties of polylactide nanocomposites

A novel organically modified montmorillonite (OMMT) based on a bifunctional organic modifier‐12‐aminolauric acid (ALA) was synthesized. Polylactide (PLA) nanocomposites with this new and traditional OMMT were prepared by solution casting method. The effects of the organic modifiers on structure, morphology and thermal properties of PLA nanocomposites have been investigated using Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The results indicate that ALA has distinct effects on the dispersion of MMT platelets into the PLA matrix, where partial exfoliated as well as intercalated structures have been obtained, when compared with ordinary modifier, cetyltrimethyl ammonium bromide (CTAB). TGA data verifies that PLA nanocomposites with ALA‐MMT organoclay display enhanced thermal stability. The optimal clay loading of ALA‐MMT occurs at 3%wt, leading to the best compromise between clay dispersion and thermal properties. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

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     

Poly(methyl methacrylate)/clay nanocomposites by photoinitiated free radical polymerization using intercalated monomer

A series of poly(methyl methacrylate)/montmorillonite (PMMA/MMT) nanocomposite were prepared by successfully dispersing the inorganic nanolayers of MMT clay in an organic PMMA matrix via in situ photoinitiated free radical polymerization. Methyl methacrylate monomer was first intercalated into the interlayer regions of organophilic clay hosts by “click” chemistry followed by a typical photoinitiated free radical polymerization. The intercalated monomer was characterized by FT-IR spectroscopy, elemental analysis and thermogravimetric analysis methods. The intercalation ability of the modified monomer and exfoliated nanocomposite structure were confirmed by X-ray diffraction spectroscopy (XRD), transmission electron microscopy (TEM) and atomic force microscopy (AFM). Thermal stability of PMMA/MMT nanocomposites was also studied by both differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).     

Poly(butylene terephthalate)/Clay Nanocomposites directly Prepared from Pristine Montmorillonite (MMT)

Summary Poly(butylene terephthalate) (PBT)/clay nanocomposites have been prepared by melt intercalation method directly from pristine montmorillonite (MMT), using cetyl pyridinium chloride (CPC) as the polymer/clay reactive compatibilizer. The effect of the reactive compatibilizer (CPC) proportion relative to the clay on the structure and properties of the PBT/clay nanocomposites was studied by XRD, TEM, TGA and cone calorimeter. The results show that such appropriate proportion as 1 wt % CPC to 3 wt % MMT induces well-dispersed intercalated morphology and better thermal and flame retarded properties. At last the intercalation mechanism of the technology was discussed.     

Polypropylene nanocomposite film: A critical evaluation on the effect of nanoclay on the mechanical,thermal, and morphological behavior

Polypropylene (PP)/clay nanocomposites prepared by melt blending technique using different percentages of clay with and without maleic anhydride grafted PP (MA‐PP) were studied. The intercalated and exfoliated structure of nanocomposites was characterized by X‐Ray Diffraction (XRD) and transmission electron microscopy (TEM). Because of the typical intercalated and exfoliated structure, the tensile modulus of the nanocomposites were improved significantly as compared to virgin PP. The viscoelastic behavior of the nanocomposites was studied by dynamical mechanical analysis (DMA) and the results showed that with the addition of treated clay to PP there was substantial improvement in storage modulus increases. The thermal stability and crystallization of the PP nanocomposites as studied by differential scanning calorimeter (DSC) and thermo gravimetric analysis (TGA) were also improved significantly compared to PP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Styrene-acrylonitrile (SAN) layered silicate nanocomposites prepared by melt compounding

Poly(styrene-co-acrylonitrile) (SAN) nanocomposites were successfully made by melt compounding and exhibited improved thermal stability and reduced flammability. The organoclays used in these nanocomposites were based upon fluorinated synthetic mica (FSM) or montmorillonite (MMT). Four different organic treatments were used on the clay surface to study the effect of organic treatment on clay dispersion: dimethyl, bis(hydrogenated tallow) ammonium (DMHTA), methyl tallow bis-2-hydroxyethyl ammonium (MTBHA), triphenyl, n-hexadecyl phosphonium (TPHDP), and 1,2-dimethyl-3-n-hexadecyl imidazolium (DMHDI). Along with studying the effect of clay organic treatment on the nanocomposite formation and flammability, the effect of acrylonitrile content in the SAN on nanocomposite formation and flammability was also studied. The overall findings suggest that dispersion of clay into SAN is rather facile, but certain combinations of organic treatment and clay type resulted in microcomposites rather than nanocomposites. Flammability of these materials was measured by pulse-combustion flow calorimetry (PCFC), also known as micro-cone calorimetry.     

Synthesis and evaluation of high‐performance ethylene–propylene–diene terpolymer/organoclay nanoscale composites

The main objective of this study was to synthesize and characterize the properties of ethylene–propylene–diene terpolymer (EPDM)/clay nanocomposites. Pristine clay, sodium montmorillonite (Na⁺–MMT), was intercalated with hexadecyl ammonium ion to form modified organoclay (16Me–MMT) and the effect of intercalation toward the change in interlayer spacing of the silicate layers was studied by X‐ray diffraction, which showed that the increase in interlayer spacing in Na⁺–MMT by 0.61 nm is attributed to the intercalation of hexadecyl ammonium ion within the clay layers. In the case of EPDM/16Me–MMT nanocomposites, the basal reflection peak was shifted toward a higher angle. However, gallery height remained more or less the same for different EPDM nanocomposites with organoclay content up to 8 wt %. The nanostructure of EPDM/clay composites was characterized by transmission electron microscopy, which established the coexistence of intercalated and exfoliated clay layers with an average layer thickness in the nanometer range within the EPDM matrix. The significant improvement in thermal stability and mechanical properties reflects the high‐performance nanocomposite formation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2429–2436, 2004     

Synthesis and properties of poly(methyl methacrylate)/clay nanocomposites using natural montmorillonite and synthetic Fe‐montmorillonite by emulsion polymerization

In this article, Fe‐montmorillonite (Fe‐MMT) was synthesized by hydrothermal method. For the first time, Fe‐MMT was modified by cetyltrimethyl ammonium bromide (CTAB), and poly(methyl methacrylate)(PMMA)/Fe‐MMT nanocomposites were synthesized by emulsion polymerization. Then poly(methyl methacrylate)(PMMA)/natural montmorillonite (Na‐MMT) and PMMA/Fe‐MMT nanocomposites were compared by Fourier transform infrared (FTIR) spectra, X‐ray diffraction (XRD) patterns, transmission electron microscopy (TEM), and thermal gravimetric analysis (TGA). By XRD and TEM, it was found out that the morphology of PMMA/Fe‐MMT nanocomposites was different from that of the PMMA/Fe‐MMT nanocomposites when the content of two types of clay was same in the PMMA matrix. It was possible that the presence of iron may lead to some radical trapping, which enhances intragallery polymerization to be developed to improve layer dispersion in PMMA/Fe‐MMT systems. In TGA curves, the thermal stability and residue at 600°C of PMMA/Fe‐MMT nanocomposites were higher than those of PMMA/Na‐MMT nanocomposites. Those dissimilarities were probably caused by structural Fe ion in the lattice of Fe‐MMT. POLYM. COMPOS., 27:49–54, 2006. © 2005 Society of Plastics Engineers     

Electron beam synthesis and characterization of poly(vinyl alcohol)/montmorillonite nanocomposites

Poly(vinyl alcohol) (PVA)/montmorillonite clay (MMT) nanocomposites in the form of films were prepared under the effect of electron beam irradiation. The PVA/MMT nanocomposites gels were characterized by X‐ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and mechanical measurements. The study showed that the appropriate dose of electron beam irradiation to achieve homogeneous nanocomposites films and highest gel formation was 20 kGy. The introduction of MMT (up to 4 wt %) results in improvement in tensile strength, elongation at break, and thermal stability of the PVA matrix. In addition, the intercalation of PVA with the MMT clay leads to an impressive improved water resistance, indicating that the clay is well dispersed within the polymer matrix. Meanwhile, it was proved that the intercalation has no effect on the metal uptake capability of PVA as determined by a method based on the color measurements. XRD patterns and SEM micrographs suggest the coexistence of exfoliated intercalated MMT layers over the studied MMT contents. The DSC thermograms showed clearly that the intercalation of PVA polymer with these levels of MMT has no influence on the melting transitions; however, the glass transition temperature (T_g) for PVA was completely disappeared, even at low levels of MMT clay. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1129–1138, 2006     

Synthesis of exfoliated PP/LDH nanocomposites via melt‐intercalation: Structure,thermal properties,and photo‐oxidative behavior in comparison with PP/MMT nanocomposites

Exfoliated polypropylene (PP)/layered double hydroxide (LDH) nanocomposites have been successfully synthesized via melt‐intercalation. Their structure, thermal properties, and photo‐oxidative behavior have been characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), dynamic mechanical thermal analysis (DMA), X‐ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) spectrum. TGA and DMA data show that the PP/LDH nanocomposites have enhanced thermal stability compared with virgin PP and corresponding PP/montmorillonites (MMT) nanocomposites, especially in high temperature range during the thermal decomposition of the samples. XPS and FTIR results give positive evidence that the photo‐oxidation mechanism of PP in the PP/LDH materials is not modified compared with that of virgin PP. However, photo‐oxidation rate of PP/LDH materials is much lower than that of PP and PP/MMT samples, indicating that the PP/LDH nanocomposites have better UV‐stability. POLYM. ENG. SCI. 46:1153–1159, 2006. © 2006 Society of Plastics Engineers     

Synthesis and characterization of poly(ethylene terephthalate) nanocomposites with organoclay

Poly(ethylene terephthalate) (PET)/montmorillonite (MMT) nanocomposites were prepared by solution intercalation method. The clay was organo‐modified with the intercalation agent cetylpyridinium chloride (CPC). Wide‐angle X‐ray diffraction (XRD) showed that the layers of MMT were intercalated by CPC. Four nanocomposites with organoclay contents of 1, 5, 10, and 15 wt % were prepared by solution blending. XRD showed that the interlayer spacing of organoclay in the nanocomposites depends on the amount of organoclay present. According to the results of differential scanning calorimetry (DSC) analysis, clay behaves as a nucleating agent and enhances the crystallization rate of PET. The maximum enhancement of crystallization rate for the nanocomposites was observed in those containing about 10 wt % organoclay within the studied range of 1–15 wt %. From thermogravimetric analysis (TGA), we found that the thermal stability of the nanocomposites was enhanced by the addition of 1–15 wt % organoclay. These nanocomposites showed high levels of dispersion without agglomeration of particles at low organoclay content (5 wt %). An agglomerated structure did form in the PET matrix at 15 wt % organoclay. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 140–145, 2004     

Polyimide/montmorillonite nanocomposites based on thermally stable, rigid-rod aromatic amine modifiers

The preparation and processing of most of polymer/clay nanocomposites need high temperature. This limited the application of commonly used organic modifiers of long carbon-chain alkyl ammonium salts because of their low thermal stability. In this study, we synthesized two novel thermally stable, rigid-rod aromatic amines. Montmorillonite (MMT) treated by these amines exhibited larger layer-to-layer spacing, higher thermal stability than that treated by commonly used 1-hexadecylamine and also high ion-exchange ratio (>95%). They were applied to prepare nanocomposites with polyimide (PI) by in situ polymerization. XRD, TEM were used to obtain the information on morphological structure of PI/MMT nanocomposites. DMA, TGA, DSC, universal tester were applied to characterize the mechanical and thermal properties of the nanocomposites. When the MMT content was below 3 wt%, the PI/MMT nanocomposites were strengthened and toughened at the same time. The introduction of a small amount of MMT also led to improvement in thermal stability, slight increase in glass transition temperature, marked decrease in coefficient of thermal expansion and decrease in solvent uptake. MMT treated by these aromatic amines exhibited better dispersibility and (probably) interfacial interaction with PI matrix than that treated by 1-hexadecylamine. The nanocomposites based on these MMT resultantly exhibited better mechanical, thermal and solvent resistance properties than those based on 1-hexadecylamine treated MMT.     

Synthesis and characterization of poly(ethylene terephthalate)/attapulgite nanocomposites

A kind of clay with fibrous morphology, attapulgite (AT), was used to prepare poly (ethylene terephthalate) (PET)/AT nanocomposites via in situ polymerization. Attapulgite was modified with Hexadecyltriphenylphosphonium bromide and silane coupling agent (3‐glycidoxypropltrimethoxysilane) to increase the dispersion of clay particles in polymer matrix and the interaction between clay particles and polymer matrix. FTIR and TGA test of the organic‐AT particles investigated the thermal stability and the loading quantity of organic reagents. XRD patterns and SEM micrographs showed that the organic modification was processed on the surface of rod‐like crystals and did not shift the crystal structure of silicate. For PET/AT nanocomposites, it was revealed in TEM that the fibrous clay can be well dispersed in polymer matrix with the rod‐like crystals in the range of nanometer scale. The diameter of rod‐like crystal is about 20 nm and the length is near to 500 nm. The addition of the clay particles can enhance the thermal stability and crystallization rate of PET. With the addition of AT in PET matrix, the flexural modulus of those composites was also increased markedly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1279–1286, 2007     

二聚阳离子表面活性剂改性蒙脱土的制备和表征

合成了二聚阳离子表面活性剂GeminiC12,用核磁共振氢谱(1HNMR)表征了它的结构,并用它作为有机插层剂应用于蒙脱土的改性处理。红外光谱(FTIR)、热重分析(TGA)表明,GeminiC12已插层到蒙脱土片层间。X射线粉末衍射(XRD)表明,插层后蒙脱土层间距从1 19nm增加到3 8nm,是十六烷基三甲基溴化铵(CTAB)处理效果的两倍。沉降实验表明,改性后蒙脱土在苯乙烯和石蜡中形成凝胶体系,表现出很好的相容性和分散性,这种改性效果优于目前常用的CTAB处理效果,更有利于聚合物或其单体进入蒙脱土层间形成纳米复合材料。     

Poly(vinyl chloride)/metallic oxides/organically modified montmorillonite nanocomposites: Preparation,morphological characterization,and modeling of the mechanical properties

Poly(vinyl chloride), metallic oxides (from copper, molybdenum, and zinc), and organically modified montmorillonite (O‐MMT) nanocomposites were prepared in a melt‐blending or intercalation‐in‐the‐molten‐state process. The morphology of the nanocomposites was evaluated with X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Properties, such as the mechanical, thermal, and electrical properties, and the dynamic thermal stability against dehydrochlorination were also evaluated. Nanocomposites with a hybrid intercalated/exfoliated structure were obtained in all of the situations considered, as demonstrated by the XRD and TEM results and indirectly by the increment of Young's modulus of the formulations with increasing amount of O‐MMT incorporated. The modeling of Young's modulus by the Halpin–Tsai, Hui–Shia, and Lewis–Nielsen theories showed that the process of nanocomposite preparation allowed the aspect ratio of the clay particles to increase; these values were comparable to those nanocomposites obtained by other researchers with different polymeric matrices and methodologies. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermal aging and accelerated weathering of PVC/MMT nanocomposites: Structural and morphological studies

This work focuses on the influence of weathering factors—UV radiation, humidity, and temperature on the structure and morphology of poly(vinyl chloride)/montmorillonite (PVC/MMT) nanocomposites obtained by melt blending. It has been observed that organically modified MMT (OMMT) deteriorates the weathering resistance, the thermal behavior, as well as the long‐term stability of PVC. Decomposition of the organic modifier of MMT causes substantial color changes in the PVC nanocomposites as it facilitates the dehydrochlorination process of the polymer. However, the nonmodified MMT provides some stabilization during PVC weathering. The nanocomposites after annealing are characterized by higher glass transition temperature. The increase in heat capacity step (Δc_p) during glass transition suggests that in the PVC composites with nonmodified MMT stronger molecular interactions between the polymer and clay platelets occur than in PVC/OMMT nanocomposites. The scanning electron microscopy images on the surface and the cross section show that thermal aging and weathering proceed by different mechanisms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42090.     

Synthesis and characterization of poly(propylene)/montmorillonite nanocomposites by simultaneous grafting‐intercalation

A novel process for the preparation of poly(propylene)/montmorillonite (PP/MMT) nanocomposites was developed via simultaneous solution grafting‐intercalation in the presence of a reactive ammonium cation that can be grafted onto poly(propylene). Partially introducing this reactive cation into long alkyl ammonium modified MMT interlayers can transfer a conventional microcomposite into intercalated/exfoliated nanocomposites, which was evidenced by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The PP chains were tethered onto the clay surface through the bridge of the reactive ammonium cations, which can be characterized by FTIR. The bridged chemical bonding also results in a good interface adhesion between PP and MMT, as confirmed by SEM investigation. The enhanced thermal properties of PP/MMT nanocomposites were characterized by thermogravimetric analysis. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1018–1023, 2004     

Influence of organophilic clay and preparation methods on EVA/montmorillonite nanocomposites

Ethylene‐vinyl acetate copolymer (EVA)/montmorillonite MMT nanocomposites have been prepared by using different methods: one is from the organophilic montmorillonite (OMT) and the other is from the pristine MMT and reactive compatibilizer hexadecyl trimethyl ammonium bromide (C16). In this study, different kneaders were used (twin‐screw extruder and twin‐roll mill) to prepare nanocomposites. The nanocomposite structures are evidenced by the X‐ray diffraction (XRD) and high‐resolution electronic microscope (HREM). The thermal properties of the nanocomposites were investigated by thermogravimetric analysis (TGA). Moreover, the tensile tests were carried out with a Universal testing machine DCS‐5000. It is shown that different methods and organophilic montmorillonite have influence on EVA/MMT nanocomposites.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2416–2421, 2004