Synthesis of imidazolium salts and their application in epoxy montmorillonite nanocomposites

Considerable research has been conducted in improving the performance characteristics of nanocomposites, however, relatively few attempts have been made to address the thermal stability of nanocomposites. An attempt is being made to improve the thermal properties of nanocomposites by synthesizing imidazolium salts from 2-methyl imidazole and ion exchanging the salts with clay minerals. This study focuses on the role of the chemistry of imidazolium salt(s) used in functionalizing clay and processing conditions in the formulation of epoxy nanocomposites. The nanodispersion of clay in an epoxy matrix is evaluated qualitatively by X-ray diffraction (XRD), transmission electronic microscopy (TEM), and laser scanning confocal microscopy (LSCM). We demonstrate the use of LCSM for quantitative image analysis and to study the dispersion of clay layers, tagged with a fluorescent dye in the epoxy matrix. XRD and TEM results reveal that the hand mixed nanocomposite has tactoid morphology, while ultrasonicated organoclay (without hydroxyl group) epoxy nanocomposite exhibits a mixed morphology, and an ultrasonicated organoclay (with hydroxyl group) epoxy nanocomposite had well dispersed clay distribution in the epoxy matrix. Results from the three complimentary techniques enable the characterization of the clay platelets over several length scales ranging from the micrometer to the nanometer scale.     

Polyamide-12 layered silicate nanocomposites by melt blending

Polyamide-12/tetrasilisic fluoromica (PA12-ME100) and polyamide-12/quaternary tallow ammonium chloride modified fluoromica nanocomposites (PA12-MAE) were prepared by melt compounding. The nanocomposite morphology and clay dispersion were investigated using wide angle X-ray diffraction (XRD), scanning electron microscopy (SEM), SEM-energy dispersive X-ray analysis (SEM-EDX), transmission electron miscroscopy (TEM), high resolution transmission electron microscopy (HRTEM) and atomic force microscopy (AFM). A predominantly intercalated morphology was observed for PA12-ME100, and a very high degree of exfoliation for PA12-MAE. HRTEM showed that the polymer crystallites lie perpendicular to the clay surface. The tensile and flexural properties of the PA12-MAE nanocomposite were significantly enhanced compared to neat polyamide-12, even with the addition of only 4 wt% nanoclay. Furthermore, the elongation at break (%) increased from 180% for polyamide-12 up to >500% for the PA12-MAE nanocomposite. In situ measurement of the heat generated in the test specimens during uniaxial tensile deformation using infra-red thermal imaging showed that the temperature of the dumbbell samples increased from room temperature (23 °C) to as high as 70 °C regardless of the strain rate used. This is considerably above the glass transition temperature (T_g) of PA12-MAE (30 °C), as measured by dynamic mechanical thermal analysis (DMTA). The mechanism of deformation is partially explained in terms of microvoid formation. The shear viscosity of the PA12-MAE nanocomposite determined by dual capillary rheometry was lower than both neat polyamide-12 and PA12-ME100. The reduction in shear viscosity of the nanocomposites was shown, from gel permeation chromatography (GPC) studies, not to originate from polymer degradation during melt blending. The coefficient of thermal expansion, decomposition temperature, and melting and crystallisation temperatures and relative crystalline content of the nanocomposite materials were measured by thermo-mechanical analysis (TMA), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) respectively—properties which can be related to polymer nanoclay interactions.     

Biodegradable nanocomposites from maleated polycaprolactone/soy protein isolate blend with organoclay: Preparation,characterization, and properties

New biobased, eco-friendly nanocomposites were prepared from maleated polycaprolactone/soy protein isolate blend (50/50 wt/wt) with organo-modified clay by melt compounding. The XRD, TEM, tensile, DMTA, and rheological properties of the nanocomposites were investigated. X-ray diffraction and transmission electron microscopy analysis revealed that the intercalated nanocomposite is formed and the silicate layers of the clay are uniformly dispersed at a nanometer scale in the polymer matrix. There is a great enhancement in tensile and dynamic mechanical properties of the nanocomposites. Rheological study revealed that the nanocomposite exhibits strong shear thinning behavior and clay particles form network in the melted state of the composites. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Crystalline forms in melt‐crystallized syndiotactic polystyrene/clay nanocomposites

X‐ray diffraction methods and polarized optical microscopy have been used to investigate the structural change of syndiotactic polystyrene/clay nanocomposites. The nanocomposite has prepared by mixing an sPS polymer solution with organically modified montmorillonite. Both X‐ray diffraction and transmission electron microscopy results indicate that most of the swellable silicate layers are exfoliated and randomly dispersed into the sPS matrix. The X‐ray diffraction data also show the presence of polymorphism in sPS/clay nanocomposites, which is strongly dependent on the thermal history of the nanocomposites from the melt and on the content of clay. In this study, the effect of premelting temperatures and crystallization temperatures of sPS and sPS/clay nanocomposites on their crystalline phases is discussed.     

The effect of shear forces on the microstructure and mechanical properties of epoxy–clay nanocomposites

The objective of this work is to understand the effect of shear force on the properties of epoxy–clay nanocomposites. The shear force was controlled by changing the revolutions per minute on a mechanical mixer. Differences in the aspect ratio of clay layers and differences of clay particle distribution in the epoxy matrix were caused by shear force. Shear force mechanism on epoxy–clay nanocomposites' intercalation/exfoliation were compared with the other mechanism already suggested. X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy were utilized to investigate the degree of exfoliation and morphology. The mechanical and thermal properties were also studied to demonstrate the effect of shear force. This study revealed that appropriate shear force and mixing time on nanocomposite preparation was required to achieve the desired properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3465–3473, 2006     

Nanocomposites from Polycaprolactone (PCL)/Soy Protein Isolate (SPI) Blend with Organoclay

New biobased, ecofriendly nanocomposites were prepared from polycaprolactone (PCL)/soy protein isolate (SPI) blend (80/20 wt/wt) with organically modified clay, by melt compounding. X-ray diffraction and transmission electron microscopy analysis revealed that an intercalated nanocomposite was formed and the silicate layers of the clay were uniformly dispersed at a nanometer scale in matrix polymer. There was great enhancement of both tensile and dynamic mechanical properties in the nanocomposite. A rheological study revealed that the nanocomposite exhibits strong shear-thinning behavior in the melted state, and a percolated network of clay particles was formed in the melted state.     

Single-ion conducting polymer-silicate nanocomposite electrolytes for lithium battery applications

Solid-state polymer-silicate nanocomposite electrolytes based on an amorphous polymer poly[(oxyethylene)₈ methacrylate], POEM, and lithium montmorillonite clay were fabricated and characterized to investigate the feasibility of their use as ‘salt-free’ electrolytes in lithium polymer batteries. X-ray scattering and transmission electron microscopy studies indicate the formation of an intercalated morphology in the nanocomposites due to favorable interactions between the polymer matrix and the clay. The morphology of the nanocomposite is intricately linked to the amount of silicate in the system. At low clay contents, dynamic rheological testing verifies that silicate incorporation enhances the mechanical properties of POEM, while impedance spectroscopy shows an improvement in electrical properties. With clay content ≥15 wt.%, mechanical properties are further improved but the formation of an apparent superlattice structure correlates with a loss in the electrical properties of the nanocomposite. The use of suitably modified clays in nanocomposites with high clay contents eliminates this superstructure formation, yielding materials with enhanced performance.     

Structure and conductive properties of poly(ethylene oxide)/layered double hydroxide nanocomposite polymer electrolytes

The oligo(ethylene oxide) modified layered double hydroxide (LDH) prepared by template method was added as a nanoscale nucleating agent into poly(ethylene oxide) (PEO) to form PEO/OLDH nanocomposite electrolytes. The effects of OLDH addition on morphology and conductivities of nanocomposite electrolytes were studied using wide-angle X-ray diffractometer, polarized optical microscopy, differential scanning calorimetry and ionic conductivity measurement. The results show that the exfoliated morphology of nanocomposites is formed due to the surface modification of LDH layers with PEO matrix compatible oligo(ethylene oxide)s. The nanoscale dispersed OLDH layers inhibit the crystal growth of PEO crystallites and result in a plenty amount of intercrystalline grain boundary within PEO/OLDH nanocomposites. The ionic conductivities of nanocomposite electrolytes are enhanced by three orders of magnitude compared to the pure PEO polymer electrolytes at ambient temperature. It can be attributed to the ease transport of Li⁺ along intercrystalline amorphous phase. This novel nanocomposite electrolytes system with high conductivities will be benefited to fabricate the thin-film type of Li-polymer secondary battery.     

Morphological,rheological and thermal studies in melt processed compatibilized PA6/ABS/clay nanocomposites

Multicomponent compatibilized blends of polyamide 6 (PA6) and styrene-butadiene-acrylonitrile (ABS) with co-continuous morphology are among commercial alloys with an interesting combination of properties. To further enhance the properties different amounts of nanoclay were incorporated into these blends through a one step melt mixing process. The effect of nanoclay addition on rheological, thermal stability, crystallization and morphological properties of the nanocomposites were investigated and compared with those of the neat blends. The nanoscale dispersion of the clay layers in the blends were confirmed through X-ray diffraction and transmission electron microscopy methods. Rheological investigation indicated an increased viscosity and melt elasticity for the nanocomposite systems. The viscosity of nanocomposites followed a shear thinning flow behavior and decreased with increasing shear rates. The changes in the rheological properties were accompanied by refinement of the co-continuous morphology. For thermal degradation under N₂ atmosphere, the onset and maximum of degradation temperatures for the nanocomposites were as high as the neat blends, while significant improvement in thermal stability (about 60 °C by 3 wt% clay addition) was observed in the air environment. In addition agglomerated clay particles did not significantly affect thermal stability of the polymer matrix. Non-isothermal crystallization results indicated that the clay layers had a retarding effect on the crystal growth rate and facilitated the formation of α crystalline form. In addition no nucleation effect was observed during the crystallization process due to incorporation of nanoclay into the blends.     

Assessing organo‐clay dispersion in polymer nanocomposites

Organo‐clay polymer nanocomposites offer improved material properties at very low filler loadings making them of immediate interest for application in body panels, claddings, and instrument panels. This improvement in properties requires that the organo‐clay be well dispersed if not completely exfoliated. Conventionally, the dispersion and exfoliation of the organo‐clay is evaluated using transmission electron microscopy (TEM) and X‐ray diffraction (XRD). Although both TEM and XRD data were found to correlate with flexural modulus of thermoplastic olefin nanocomposite materials, only TEM proved successful in quantifying the dispersion of the organo‐clay in all nanocomposite materials (exfoliated, tactoid, or agglomerated tactoid). XRD was found to be capable of detecting exfoliation and intercalation but is limited because of clay dilution, preferred orientation, mixed‐layering, and other peak broadening factors. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1110–1117, 2004     

Mechanical and rheological properties of the maleated polypropylene–layered silicate nanocomposites with different morphology

Three types of maleated polypropylene–layered silicate nanocomposites with different dispersion states of layered silicate (deintercalated, intercalated, and exfoliated states) are prepared from two kinds of polypropylenes with different molecular weights, organically modified layered silicate and pristine montmorillonite to investigate the effect of the final morphology of the nanocomposite on the rheological and mechanical properties. Maleated polypropylene with high molecular weight intercalates slowly and the other with low molecular weight exfoliates fast into the organophilic layered silicates. Rheological properties such as oscillatory storage modulus, nonterminal behavior, and relative viscosity has close relationship with the dispersion state of layered silicates. The exfoliated nanocomposite shows the largest increase and the deintercalated nanocomposite shows almost no change in relative shear and complex viscosities with the clay content. The exfoliated nanocomposite shows the largest drop in complex viscosity due to shear alignment of clay layers in the shear flow. In addition, the final dispersion state of layered silicates intimately relates to the mechanical property. The dynamic storage moduli of nanocomposites show the same behavior as the relative shear and complex viscosities. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1526–1535, 2003     

Characterization of nanoclay orientation in polymer nanocomposite film by small-angle X-ray scattering

The orientation distribution of layer-shaped nanoclays (e.g. organoclays and pristine clays) dispersed in a polymer matrix is an important parameter to control the properties of polymer nanocomposites. In this study, we demonstrate that the use of multi-directional 2-D small-angle X-ray scattering (SAXS) can quantitatively describe the orientation distribution of organoclays (e.g. Cloisite C20A) in melt-pressed nanocomposite films, containing ethylene-vinyl acetate (EVA) copolymers as polymer matrices. Different weight fractions of organoclays were used to alter the orientation profile of nanocomposite films, in which the dispersion and morphology of organoclays were also characterized by complementary 2-D and 3-D transmission electron microscopy (TEM). All nanocomposites exhibited mixed intercalation/exfoliation clay morphology, where the intercalated structure possessed partial orientation parallel to the in-plane direction of the film. The higher content of the clay loading showed a higher clay orientation. A simple analytical scheme for SAXS data analysis to determine the orientation parameter (P₂) was demonstrated, the results of which are in agreement with the gas permeation properties of the nanocomposite films.     

Polyurethane/clay nanocomposites foams: processing, structure and properties

Polyurethane (PU)/montmorillonite (MMT) nanocomposites were synthesized with organically modified layered silicates (organoclays) by in situ polymerization and foams were prepared by a batch process. Clay dispersion of polyurethane nanocomposites was investigated by X-ray diffraction and transmission electron microscopy. The morphology and properties of PU nanocomposites and foams greatly depend on the functional groups of the organic modifiers, synthesis procedure, and molecular weight of polyols because of the chemical reactions and physical interactions involved. Silicate layers of organoclay can be exfoliated in the PU matrix by adding hydroxyl and organotin functional groups on the clay surface. The presence of clay results in an increase in cell density and a reduction of cell size compared to pure PU foam. In the polyurethane with high molecular weight polyol, a 6 °C increase in T_g, 650% increase in reduced compressive strength, and 780% increase in reduced modulus were observed with the addition of 5% organically treated clays. Opposite effects were observed in PU nanocomposite foams with highly crosslinked structure. The interference of the H-bond in the presence of clay is probably the reason.     

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.     

Nanoclay dispersion in a miscible blend: an assessment through rheological analysis

In this study, miscible polymer blend nanocomposite of Poly(ethylene oxide)/Poly(methyl methacrylate), (PEO/PMMA), with sodium montmorillonite (Na⁺-MMT) clay were prepared at a constant concentration of nanoparticles via different solution intercalation methods. The resultant nanocomposites possess different structure and dispersion of Na⁺-MMT clays which are assessed through a combination of transmission electron microscopy (TEM) and X-ray diffraction (XRD). The rheology of the neat blend and two different layered silicate nanocomposites were investigated using linear viscoelastic measurements with a parallel plate rheometry at small strain amplitudes. It was found that regardless of the extent of dispersion, the storage and loss modulus increased by incorporating the nanoparticles into the matrix of PEO/PMMA. Moreover, at low frequencies the rheological response of the nanocomposite in which layered silicates benefit from a better dispersion becomes relatively invariant with frequency and represents a mediocre solid-like behavior in comparison to the nanocomposite in which the nanoparticles are intercalated or agglomerated.     

Polycarbonate nanocomposites. Part 1. Effect of organoclay structure on morphology and properties

Polycarbonate nanocomposites were prepared by melt processing from a series of organoclays based on sodium montmorillonite exchanged with various amine surfactants. To explore the effects of matrix molecular weight on dispersion, an organoclay was melt-mixed with a medium molecular weight polycarbonate (MMW-PC) and a high molecular weight polycarbonate (HMW-PC) using a twin screw extruder. The effects of surfactant chemical structure on the morphology and physical properties were explored for nanocomposites formed from HMW-PC. Wide angle X-ray scattering, transmission electron microscopy, and stress-strain behavior were employed to investigate the nanocomposite morphology and physical properties. The modulus enhancement is greater for nanocomposites formed from HMW-PC than MMW-PC. This trend is attributed to the higher shear stress generated during melt processing. A surfactant having both polyoxyethylene and octadecyl tails shows the most significant improvement in modulus with some of the clay platelets fully exfoliated. However, the nanocomposites formed from a range of other organoclays contained both intercalated tactoids and collapsed clay particles with few, if any, exfoliated platelets.     

Preparation of natural rubber-montmorillonite nanocomposite in aqueous medium: evidence for polymer-platelet adhesion

Nanocomposites of natural rubber latex and layered silicates are prepared by a mild dispersion shear blending process. The results of X-ray diffraction (XRD) and transmission electron microscopy (TEM) show that clay particles are well dispersed in the dry latex and the platelets have a preferential orientation, forming translucent nanocomposites. These show tensile mechanical properties analogous to those obtained with vulcanized rubber as well as an increased solvent resistance, which is expected considering that there is significant adhesion between clay lamellae and rubber. Nanocomposite swelling is strongly anisotropic. Natural rubber properties may thus be strongly modified by nanocomposite formation producing unprecedented combinations of properties.     

Ethylene Vinyl Acetate and Polycaprolactone–Organoclay Nanocomposite: Thermal,Mechanical and Morphological Properties

Organoclay of the type Cloisite^® 20A (C-20A) with two structurally different but semicrystalline polymer matrices was studied. Polycaprolactone (PCL), a linear, biodegradable polymer, and ethylene vinyl acetate (EVA), a branched copolymer, were chosen to prepare polymer clay nanocomposites via the melt-blending method. The results show that the structure of a polymer matrix plays a significant role towards compatibilization with the silicate layers of the clay. Scanning electron microscopy and X-ray diffraction analyses revealed an exfoliated-intercalated mixed morphology for the PCL matrix. However, for the EVA matrix, silicate layers agglomerated to form tactoids and resulted primarily in an intercalated morphology. Fourier transform infrared spectroscopy was used to determine the nature of the interactions between the polymer and the filler. The thermal properties were investigated using thermogravimetric analysis and indicated that, with an increase in clay loading, the thermal stability was reduced for both matrices. Tensile tests suggested that Young’s modulus improved for the EVA matrix with an increase in clay dosage whereas for PCL the modulus was found to be highest for 8% clay loading.     

Novel LDPE/vermiculite/ciclopiroxolamine hybrid nanocomposites: Structure,surface properties,and antifungal activity

The increasing number of indwelling medical materials and devices are connected with infections caused by yeast, especially Candida albicans. This pathogen produces biofilms on synthetic materials, which facilitates adhesion of the organisms to devices and renders them relatively refractory to medical therapy. Since antimicrobial polymer nanocomposites present one of the promising possibilities, this study explores a new approach to achieving this goal by developing nanocomposite based on low density polyethylene (LDPE) with clay mineral vermiculite as an active carrier for antifungal compound. The set of LDPE/clay nanocomposite with increasing amount of antifungal nanofiller was prepared by melt compounding procedure. As antifungal agent was selected generally used active substance ciclopiroxolamine and this compound was loaded into natural vermiculite through ultrasound technique. The structure of all prepared samples was studied by X-ray diffraction analysis and Fourier transforms infrared spectroscopy. Further thermal properties of polyethylene/clay nanocomposites were investigated by thermogravimetric analysis and the surface properties were evaluated by light optical microscopy, scanning electron microscopy and atomic force microscopy. From mentioned characteristics, we conclude that presence of nanofiller in LDPE primarily causes shift of thermal degradation to higher temperatures and increasing of microhardness. All prepared LDPE nanocomposites possess an excellent and prolonged antifungal activity against Candida albicans.     

Preparation of intercalating agent-free epoxy/clay nanocomposites

A simple intercalating agent-free approach to prepare epoxy/montmorillonite (MMT) clay nanocomposite is reported. Through this new approach, no organic modifiers are needed. Thus, the cost for preparing polymer nanocomposites can be significantly reduced. The extent of dispersion and exfoliation of clay in epoxy was characterized by X-ray diffraction and transmission electron microscopy observations. It is found that the MMT clay is well-dispersed in epoxy matrix. The clay platelets in epoxy show a stacked structure with dimensions of about 1–2 μm in length and about 20 nm in thickness. At 4.5 wt% of clay loading level, the flexural modulus of the epoxy nanocomposite is increased by about 35%. No reduction in fracture toughness or glass-transition temperature is observed. The implication of the present finding for commercialization of polymer nanocomposites is discussed. POLYM. ENG. SCI., 47:1708–1714, 2007. © 2007 Society of Plastics Engineers