Flammability of polystyrene layered silicate (clay) nanocomposites: Carbonaceous char formation

Polymer layered‐silicate (clay) nanocomposites have not only the unique advantage of reduced flammability, but also improved mechanical properties. This is a key advantage over many flame retardants, which reduce flammability but also reduce the mechanical properties of the polymer. In our efforts to further understand the mechanism of flame retardancy with polymer‐clay nanocomposites, we investigated the effect of the clay, the loading level and polymer melt viscosity on the flammability of polystyrene‐clay nanocomposites. The nanoscale dispersion of the clay in the polymer was analysed by wide‐angle X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Cone calorimetry and gasification studies were used to evaluate the flammability of these nanocomposites. There were major reductions in peak heat release rates (HRRs), and increased carbonaceous char formation, for these nanocomposites. It was determined that while the viscosity of the PS nanocomposite played a role in lowering the peak HRR, the clay loading level had the largest effect on peak HRR. Finally, it was found that clay catalysed carbonaceous char formation, and the reinforcement of the char by the clay was responsible for the lowered flammability of these nanocomposites. Published in 2002 by John Wiley & Sons, Ltd.     

Rheological characterization of polystyrene-clay nanocomposites to compare the degree of exfoliation and dispersion

Polymer-clay nanocomposites are of great interest due to their improvement in certain material properties relative to virgin polymer or conventional composites. For example, compared to conventional materials, Nylon 6/montmorillonite nanocomposites demonstrated significant improvements, including high strength, high modulus and high heat distortion temperature. Because viscoelastic measurements are highly sensitive to the nanoscale and mesoscale structure of polymeric materials, when combined with X-ray scattering, electron microscopy, thermal analysis, and mechanical property measurements, they will provide fundamental understanding of the state and mechanism of exfoliation of the layered silicate (clay) in a polymer matrix. In addition, understanding rheological properties of polymer nanocomposites is crucial for application development and understanding polymer processability.The objective of this research is to develop a rheological technique to analyze the clay morphology in nanocomposite. Previous work has demonstrated the utility of the rheological technique to differentiate (qualify) the degree of exfoliation/dispersion. This report utilizes findings from the earlier work to further map out the structure-rheological response of polystyrene nanocomposites with various composition, clay types, and dispersion; and to quantify the key parameter that dominates the characteristic rheological response. This report explored a series of polystyrene (PS)-clay nanocomposites with 1,2-dimethyl-3-n-hexadecyl imidazolium (DMHDI) organically modified clays. These PS nanocomposites investigated here demonstrated a change of pattern in dynamic mechanical spectrum, as a function of the degree of exfoliation, from typical polymer response to a terminal response of [G′∼ω, G″∼ω], then to a pattern with double crossover frequencies, and finally to a solid-like response with G′>G″ in all frequency ranges. We showed that the number of particles per unit volume is a key factor determining the characteristic response of nanocomposites.In addition, the rheological response of PS-clays nanocomposite made from DMHDI modified clay combined with high-energy sonication (characterized as exfoliated by XRD and TEM) was compared with that of nanocomposites made by dimethyl, benzyl hydrogenated tallow (2MBHT) modified clay. We found that PS nanocomposites made by DMHDI-modified clay with high-energy sonication are better dispersed than the nanocomposites made previously using 2MBHT-modified clay. We also showed that the glass transition temperatures were not very sensitive to the degree of dispersion.The key finding of this research is that rheological measurements are complimentary to traditional polymer nanocomposite analysis techniques, and they may also serve as an analytical tool by itself (under appropriate conditions), now that some fundamental behavior has been identified.     

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.     

Polyethylene and polypropylene nanocomposites based on polymerically-modified clay containing alkylstyrene units

Sodium montmorillonite was modified with a new polymeric surfactant. The high molecular weight of the surfactant appears to have led to incomplete cation exchange of the clays, but did promote nanocomposite formation with polyethylene and polypropylene. X-ray diffraction combined with transmission electron microscopy revealed a mixed nanocomposite morphology. The thermal stability of the nanocomposites was evaluated by thermogravimetric analysis, while flammability of the nanocomposites was evaluated by cone calorimetry. A significant 40% reduction in peak heat release rate was observed at 10% organo-clay (3% inorganic clay) loading with an even higher 50% reduction at a loading level of 16% modified clay (5% inorganic clay). Despite possible plasticization effects by the polymers used as an organic modification for the clays, the mechanical properties such as Young's modulus and elongation were not severely impacted by the nanocomposite formation.     

Preparation and characterization of polyimide/organoclay nanocomposites

Organically modified montmorrillonite clay, containing a long chain aliphatic quarternary ammonium cation, was used to prepare polyimide/organoclay hybrids. Several approaches were examined in an attempt to achieve fully exfoliated nanocomposites. These included simple mixing of the clay in a pre-made high molecular weight poly(amide acid) solution; simple mixing followed by sonication of the organoclay/poly(amide acid) solutions; and the preparation of high molecular weight poly(amide acid)s in the presence of the organoclay dispersed in N-methyl-2-pyrrolidinone (NMP). The best results were obtained using the in-situ polymerization approach. The resulting nanocomposite films (both amide acid and imide), containing 3-8% by weight of organoclay, were characterized by differential scanning calorimetry (DSC), dynamic thermogravimetric analysis (TGA), transmission electron microscopy (TEM), X-ray diffraction (XRD) and thin film tensile properties. A significant degree of dispersion was observed in the nanocomposite films of the amide acid and the imide. After thermal treatment of amide acid films to effect imidization, in both air and nitrogen, the films were visually darker than control films without clay and the level of clay dispersion appeared to have decreased. In the latter case, the separation between the layers of the clay decreased to a spacing less than that present in the original organoclay. These observations suggest that thermal degradation of the aliphatic quarternary ammonium cation occurred likely during thermal treatment to effect imidization and solvent removal. These thermal degradation effects were less pronounced when thermal treatment was performed under nitrogen. The polyimide/organoclay hybrid films exhibited higher room temperature tensile moduli and lower strength and elongation to break than the control films.     

Influence of organic modification on mechanical properties of melt processed intercalated poly(methyl methacrylate)–organoclay nanocomposites

The influence of organic modifiers on intercalation extent, structure, thermal and mechanical properties of poly(methyl methacrylate) (PMMA)–clay nanocomposites were studied. Two different organic modifiers with varying hydrophobicity (single tallow versus ditallow) were investigated. The nanocomposites were prepared from melt processing method and characterized using wide angle X‐ray diffraction, transmission electron microscopy, thermogravimetric analysis, differential scanning calorimetry (DSC), and tensile tests. Mechanical properties such as tensile modulus (E), break stress (σ_brk), and % break strain (ε_brk) were determined for nanocomposites at various clay loadings. Extent of PMMA intercalation is sufficient and in the range 9–15 Å depending on organoclay and filler loading. Overall thermal stability of nanocomposites increases by 16–30°C. The enhancement in T_g of nanocomposite is merely by 2–4°C. With increase in clay loading, tensile modulus increases linearly while % break strain decreases. Break stress is found to increase till 4 wt % and further decreases at higher clay loadings. The overall improvement in thermal and mechanical properties was higher for the organoclay containing organic modifier with lower hydrophobicity and single tallow amine chemical structure. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Polypropylene/clay nanocomposites: Combined effects of clay treatment and compatibilizer polymers on the structure and properties

Combined effects of clay treatment and compatibilizer polymers on the structure and properties of polypropylene/clay nanocomposites were studied. Dynamic mechanical analysis was used to analyze comparatively the dynamic mechanical response of different nanocomposites prepared from polypropylene and montmorillonite‐rich bentonite, and to relate such response with the material microstructure. Two different bentonites were used: a purified Spanish natural bentonite was organophillized by means of 11‐undecyl‐ammonium ion and a commercial bentonite organophillized with dimethyl dehydrogenated tallow ammonium ion. Three different polar copolymers were employed as compatibilizer agents in some of the formulations: maleic anhydride‐grafted polypropylene, maleic anhydride‐grafted poly(styrene‐co‐ethylenebutylene‐co‐styrene), and poly(ethylene terephthalate‐co‐isophthalate) (PET). To ascertain the microstructure characteristics in the nanocomposites, wide angle X‐ray diffraction, transmission electron microscopy, and differential scanning calorimetry techniques were used. The nanocomposites containing both bentonite organophillized with 11‐undecyl‐ammonium ion and PET, and maleated PP as compatibilizer system, were found to have the highest storage modulus and the smallest loss factor values, which was mainly due to the better clay platelets dispersion. The dynamic mechanical response of nanocomposites prepared with bentonite organophillized with dimethyl dehydrogenated tallow ammonium ion and maleated SEBS was strongly affected by the presence of this compatibilizer. The temperature of PP and α, β, and γ relaxations strongly depended on the interactions between the different phases in the nanocomposites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1213–1223, 2006     

Effects of organoclay Soxhlet extraction on mechanical properties, flammability properties and organoclay dispersion of polypropylene nanocomposites

The organic treatment on a layered silicate used in nanocomposite synthesis is the interface between the hydrophilic layered silicate (clay) and hydrophobic polymer in the case of polypropylene. However, the typical synthesis of an organoclay can result in excess organic treatment which can hinder mechanical and flammability benefits. This excess organic treatment may result in plasticization of the polymer matrix, possibly removing some of the mechanical and flammability property benefits provided by the nanocomposite. In this paper, the effects of using Soxhlet Extraction on the Organoclays after synthesis was investigated. Soxhlet extraction times on organoclays were found to have an effect on the mechanical and flammability properties of the resulting polypropylene nanocomposite. The removal of excess organic treatment by Soxhlet extraction resulted in improvements in flex modulus, improved clay dispersion, delayed time to ignition, and lowered heat release rate during burning.     

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.     

Effects of Charring Agents on the Thermal and Flammability Properties of Intumescent Flame-Retardant HDPE-based Clay Nanocomposites

Intumescent flame-retardant (IFR) high-density polyethylene, poly[ethylene-co-(vinyl acetate)], and organically-modified clay nanocomposites consisting of ammonium polyphosphate (APP) and other charring agents, as well as the nanocomposites pentaerythritol (PER), polyamide-6 (PA), and PA/OMT were investigated. Their thermal and flammability properties have been characterized by thermogravimetric analyses, cone calorimetry, a limiting oxygen index, and the UL-94 test. Results show that the PER-contained sample exhibits different thermal and flammability behaviors from the samples containing polymer charring agents. The difference is postulated to be responsible for the formation of various intumescent structures and their changes in response to heightened temperatures.     

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.     

The origin of synergism between an organoclay and carbon black

Synergistic effects between a montmorillonite (Mt), modified with an organophilic ammonium as the compensating cation (OMt), and carbon black (CB) are reported in the literature. This work proposes the pronounced interaction between the organophilic ammonium cation and CB as a phenomenon at the origin of the synergism. A nanocomposite based on poly(1,4-cis-isoprene) containing both CB and OMt, formed in situ through the reaction between Mt and di(hydrogenated tallow)-dimethylammonium chloride (2HTCl), was prepared. Moreover, nanocomposites containing only CB in the presence and in the absence of 2HTCl were comparatively prepared and analysed. Synergism between OMt and CB was investigated by studying the filler networking process in the PI matrix through dynamic-mechanical tests and by assessing the nanocomposite structure by transmission electron microscopy analysis. It was found that 2HTCl promoted a pronounced enhancement of the non linear dynamic-mechanical behaviour of the nanocomposite material, with a much improved CB dispersion and a remarkable reduction of bound rubber. These effects were reduced in the presence of Mt, that involved the ammonium salt in the formation of OMt. The amount of 2HTCl required to achieve the largest non linear behaviour and the lowest bound rubber was calculated to correspond to a monolayer of the ammonium salt on the carbon black surface.     

Morphology and properties of SAN‐clay nanocomposites prepared principally by water‐assisted extrusion

An efficient extrusion process involving the injection of water while processing was used to prepare poly (styrene‐co‐acrylonitrile) (SAN)/clay nanocomposites with a high degree of nanoclay delamination. The usefulness of water‐assisted extrusion is highlighted here, in comparison with classical extrusion and roll mill processes. Cloisite® 30B (C30B), a montmorillonite clay organomodified with alkylammonium cations bearing 2‐hydroxyethyl chains, and pristine montmorillonite were melt blended with SAN (25 wt% AN) in a semi‐industrial scale extruder specially designed to allow water injection. XRD analysis, visual and TEM observations were used to evaluate the quality of clay dispersion. The relationship between the nanocomposite morphology and its mechanical and thermal properties was then investigated. The superiority of the SAN/C30B nanocomposite extruded with water has been evidenced by cone calorimetry tests and thermogravimetric measurements (TGA). These analyses showed a substantial improvement of the fire behavior and the thermal properties, while a 20% increase of the Young modulus was recorded. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Synthesis and study of mechanical and fire retardant properties of (carboxymethyl cellulose -g-polyacrylonitrile)/montmorillonite biodegradable nanocomposite

Despite abundant researches on petroleum based polymer nanocomposites over micro and macro composites, these nanocomposites suffer from deprived biodegradability, highly inherent flammability and less mechanical strength. The present work describes the preparation of a biodegradable nanocomposite based on carboxymethyl cellulose-g-polyacrylonitrile (CMC-g-PAN) and montmorillonite (MMT) nanoclay by using ammonium persulfate (APS) as an initiator, methylene bis-acrylamide (MBA) as a crosslinker via emulsifier free emulsion polymerisation. The formation of the nanocomposites was confirmed by Fourier transform infrared (FTIR), X-ray diffraction (XRD) and Transmission electron microscope (TEM) analysis. The formation of CMC-g-PAN copolymer was confirmed by means of proton nuclear magnetic resonance (¹H NMR) spectra. The improvement in thermal stability of the nanocomposites over copolymer was outstanding. More importantly, incorporating MMT enables the nanocomposite to achieve a dramatically reduced peak heat release rate of 536?±?03 kW m^?2 shown in cone calorimetry tests and higher limiting oxygen index (LOI) value indicating improved fire retardancy. In addition, the tensile strength of the nanocomposite was also increased by around 41% with 5% w/v MMT contents. This is explained on the basis of strong interfacial adhesion between CMC and MMT through PAN. Meanwhile for its better commercialization, the eco-friendly nature was studied via biodegradation.     

Intumescent flame retardant–montmorillonite synergism in polypropylene‐layered silicate nanocomposites

Polypropylene/clay nanocomposites have been prepared starting from pristine mont morillonite (MMT) and reactive compatibilizer hexadecyltrimethylammonium bromide (C16). The nanocomposite structure is evidenced by the X‐ray diffraction and high resolution electronic microscopy. Intumescent flame retardant has been added to polypropylene/clay hybrids. Their flammability behaviours have been evaluated using cone calorimetry. Synergy was observed between the nanocomposites and intumescent flame retardant. Copyright © 2003 Society of Chemical Industry     

New Role of Layered Silicates as Phase Transfer Catalyst for In Situ Polymerization of Poly(ethylenetetrasulfide) Nanocomposite

In this study, polyethylenetetrasulfide/montmorillonite nanocomposite (PETS/nanoclay) is synthesized from ethylene dichloride and sodium tetrasulfide monomers by in situ polymerization method. The effect of phase-transfer catalyst (PTC) on polymerization kinetics in addition to the structure of resulting PETS containing nanoclay is investigated. The results show that surface-modified montmorillonites by methyl tallow bis-2-hydroxyethyl quaternary ammonium chloride could properly act as PTC. Therefore, it is demonstrated that the addition of nanoclay as PTC reduces the reaction time and increases the polymerization rate during the production of final nanocomposite. The samples were characterized using Fourier transform infrared and Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), nuclear magnetic resonance spectroscopy besides energy-dispersive X-ray spectroscopy (EDS) combined with SEM (SEM–EDX). In addition, thermal behavior of nanocomposite was perused by differential scanning calorimetry and thermogravimetric analysis. XRD and AFM results show proper dispersion of clay in PETS matrix and SEM–EDX results demonstrate suitable distribution of clay in polymer matrix. PETS/nanoclay nanocomposite show a better thermal stability, and also higher glass transition and melt temperature compared to pure polysulfide polymer. The solubility of nanocomposite is also studied and results show that the solubility depends on solvent concentration in addition to reinforcement (nanoclay) deals.     

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     

Effect of montmorillonite dispersion on flammability properties of poly(styrene-co-acrylonitrile) nanocomposites

Poly(styrene-co-acrylonitrile)/Cloisite 20A (95/5) nanocomposites, having various spatial dispersion levels of the clay, were prepared with controlling clay concentrations in a solvent by the coagulation method. X-ray diffraction, transmission electron microscopy and laser scanning confocal microscopy were used to characterize the structure and morphology of the nanocomposites on a nano-scale and on a micro-scale. Quantitative analysis of clay spatial dispersion in the nanocomposites based on the laser scanning confocal microscopy images was conducted from three different perspectives: 1) clay spatial distribution; 2) the non-clay-occupied domain size; and 3) the relationship between the frequency and intensity of pixels in the images. The results from these quantitative methods indicate that nanocomposites with different spatial dispersion levels of clay in the poly(styrene-co-acrylonitrile) matrix were obtained. Evidently, the ?d₀₀₁ data from the X-ray diffraction was found to be not useful in measuring the clay dispersion in the nanocomposites. The effect of clay dispersion on the flammability properties of the nanocomposites and relevant mechanism of the clay dispersion having influence on flammability were also investigated. In radiant gasification experiments at 50 kW/m², the best clay dispersion yielded a 32% reduction in peak mass loss rate, as compared to the nanocomposites with the worst dispersion.     

Structure,permeability, and rheology of supercritical CO2 dispersed polystyrene-clay nanocomposites

Improvement in clay dispersion and clay-polymer interfacial interactions are keys to producing superior nanocomposites. A supercritical CO₂ (scCO₂) processing method was utilized to pre-disperse commercial organic clays, for further solvent mixing with polystyrene (PS) to form nanocomposites with significant dispersion and interfacial enhancement. The effect of scCO₂ processing on clay pre-dispersion, and clay dispersion and interfacial interaction in nanocomposites were investigated. SEM and WAXD of the clays indicated that after scCO₂ processing the clays lose their long region ordered layer structure appreciably, associated with reduction in particle size. WAXD and TEM of the PS/clay nanocomposites showed that the polymer penetrated into the pre-dispersed clay, leading to a disordered intercalated/exfoliated structure with improved interfacial interaction rather than a disordered intercalated structure as seen with as-received clays. Relationships between those structures, rheological and barrier properties were investigated. The scCO₂-processed nanocomposites showed a plateau in the low-frequency storage modules and increased complex viscosity, each associated with significant clay dispersion in the nanocomposite. With only 1.09% volume fraction of clay, significant reduction (∼49%) of oxygen permeation was achieved.     

The critical organic modifier aliphatic tail length for the formation of poly(methyl methacrylate)-montmorillonite nanocomposites

In this article, we report the influence of organic modifier structure (alkyl chain length C8-C20, single vs ditallow) and thereby, the effect of hydrophobicity on the structure, thermal and mechanical properties of poly(methyl methacrylate) (PMMA)-clay hybrids. Melt processed PMMA-clay hybrids were characterized using wide-angle X-ray diffraction, transmission electron microscopy, and differential scanning calorimetry. The organoclays having an alkyl chain length of more than 12 CH₂ groups resulted in the formation of nanocomposites. The glass transition temperature (T_g) of PMMA increased in the presence of clay. The mean-field lattice model was used to predict the free energy for nanocomposite formation, which showed a reasonable match with the experimental results and provided a general guideline for the proper selection of polymer and organoclay (ie, organic modifier) to obtain nanocomposite. Tensile modulus showed maximum improvement of 58% for the nanocomposites compared to 9% improvement for the composites. Tensile modulus increased with increases in the alkyl chain length of the organic modifier and clay loading. The level of improvement for the tensile properties of nanocomposites prepared from primary and secondary ammonium-modified clay is the same as that obtained with the commercial organoclays.