Transport properties of organic vapors in nanocomposites of organophilic layered silicate and syndiotactic polypropylene

Syndiotactic polypropylene (sPP) nanocomposites were obtained by melt blending synthetic fluorohectorite modified octadecyl ammmonium ions (OLS), and maleic-anhydride-grafted isotactic polypropylene (iPP-g-MA) as compatibilizer. The composition of the inorganic material was varied between 5 and 20 w/w%. Films of the composites were obtained by hot press molding the pellets. Melt-direct polymer intercalation of sPP into the OLS gave rise to nanocomposites in which the silicate layers were delaminated at low clay contents, and ordered to intercalated structures at the highest clay content. The elastic modulus was higher than for the pure polymer in a wide temperature range and increased with the inorganic content. The transport properties were measured for dichloromethane and n-pentane. The sorption was reduced compared to pure sPP. There were not significative differences between the samples having different inorganic contents. The diffusion coefficient decreased with increasing clay content. Permeability (P) showed a strong decreasing dependence on the clay content. The improvement of the barrier properties was largely caused by the reduced diffusion.     

Hyperbranched polymer/montmorillonite clay nanocomposites

Two to four pseudo-generation aliphatic hyperbranched polymers (HBPs) with -OH end-groups have been solution processed with various types of montmorillonite (MMT) layered alumino-silicate clays, and carefully dried to produce solid HBP/MMT nanocomposites. Exfoliated nanocomposites were obtained by processing the polyester HBPs with up to 20 wt% Na⁺ MMT in water, and intercalation only became dominant at higher loadings, for which the MMT layer spacing was directly dependent on the HBP pseudo-generation number. Intercalation was observed at much lower MMT contents in HBPs processed with different organically modified MMTs in THF. In this case, the absolute MMT layer spacings in the nanocomposites showed little apparent dependence on the nature of the organic modifier and the pseudo-generation number of the HBP, although the difference between the final layer spacing and its value prior to mixing increased significantly with the polarity of the organic modifier. The various HBP/MMT nanocomposites were incorporated into polyurethane formulations by melt processing in the presence of a low molar mass polyol or solution processing in THF. Na⁺MMT contents as low as 1.2 wt% led to an increase in the rubbery plateau modulus by about 60% with respect to that of the corresponding unfilled matrix, whereas much smaller relative increases were observed with unexfoliated or partly exfoliated MMT.     

Effect of sodium montmorillonite source on nylon 6/clay nanocomposites

The effect of sodium montmorillonite source on the morphology and properties of nylon 6 nanocomposites was examined using equivalent experimental conditions. Sodium montmorillonite samples acquired from two well-known mines, Yamagata, Japan, and Wyoming, USA, were ion exchanged with the same alkyl ammonium chloride compound. The resulting organoclays were extruded with a high molecular weight grade of nylon 6 under the same processing conditions. Quantitative analysis of TEM photomicrographs of the two nanocomposites reveal a slightly larger average particle length and a slightly higher degree of platelet exfoliation for the Yamagata based nanocomposite than the Wyoming version, thus, translating into a higher particle aspect ratio. The stress-strain behavior of the nanocomposites appears to reflect the nanocomposite morphology, in that higher stiffness and strengths are attainable with the increased particle aspect ratio. Moreover, the trends in stiffness behavior between the two types of nanocomposites may be explained by conventional composite theory.     

Synthesis and interfacial properties of montmorillonite/polypyrrole nanocomposites

Montmorillonite/polypyrrole (MMT/PPy) nanocomposites were prepared by the in situ polymerization of pyrrole in the presence of MMT. The morphology of the MMT/PPy nanocomposites as examined by scanning electron microscopy differs slightly from that of the untreated MMT but markedly from that of polypyrrole. X-ray photoelectron spectroscopy (XPS) showed that the materials have MMT-rich surfaces, an indication that polypyrrole is essentially intercalated in the host clay galleries. The transmission electron microscopy showed, that the interlamellar spacing of the untreated MMT increased from 1.25 to 18.9 nm, when compared to nanocomposite MMT/10.8% PPy. Moreover, XPS highlighted the cation exchange of Na⁺ from montmorillonite by K⁺ (from the oxidant) and by the positively charged polypyrrole chains. Inverse gas chromatography indicated that the nanocomposites are high surface energy materials with a dispersive contribution to the surface energy reaching 200 mJ/m² at 150 °C, for a PPy loading of 21.4 wt%. The values of the MMT/PPy nanocomposites were correlated to the changes in the specific surface area of the MMT induced by the intercalation of polypyrrole.     

Fibre reinforced nanocomposites: Mechanical properties of PA6/clay and glass fibre/PA6/clay nanocomposites

In this paper, the effect of two different reinforcements: clay at the nanoscale and glass fibres at the micro-scale, on the mechanical properties of PA/clay and GF/PA/clay are studied. The Halpin-Tsai model is used to predict the modulus of PA/Clay and GF/PA/Clay, both of which are influenced by two factors: reinforcement shape and volume fraction. The relationships between the modulus and reinforcement shape and volume fraction are discussed. Tensile modulus, measured in tensile tests is used to fit the Halpin-Tsai models. The results demonstrate a synergy between the reinforcements at the two different scales.     

Enhanced thermal properties of PS nanocomposites formed from inorganic POSS-treated montmorillonite

We have prepared polystyrene/clay nanocomposites using an emulsion polymerization technique. The nanocomposites were exfoliated at up to a 3 wt% content of pristine clay relative to the amount of polystyrene (PS). We used two different surfactants for the montmorillonite: the aminopropylisobutyl polyhedral oligomeric silsesquioxane (POSS) and the ammonium salt of cetylpyridinium chloride (CPC). Both surfactants can intercalate into the layers of the pristine clay dispersed in water prior to polymerization. Although the d spacing of the POSS-intercalated clay is relatively smaller than that of the CPC-intercalated clay, PS more easily intercalates and exfoliates the POSS-treated clay than the CPC-treated clay. IR spectroscopic analysis further confirms the intercalation of POSS within the clay layers. We used X-ray diffraction (XRD) and transmission electron microscopy (TEM) to characterize the structures of the nanocomposites. The nanocomposite prepared from the clay treated with the POSS containing surfactant is exfoliated, while an intercalated clay was obtained from the CPC-treated surfactant. The molecular weights of polystyrene (PS) obtained from the nanocomposite is slightly lower than the virgin PS formed under similar polymerization conditions. The value of T_g of the PS component in the nanocomposite is 8 °C higher than the virgin PS and its thermal decomposition temperature (21 °C) is also higher significantly. The presence of the POSS unit in the MMT enhances the thermal stability of the polystyrene.     

Polymer/layered clay nanocomposites: 2 polyurethane nanocomposites

A kind of novel polyurethane/Na⁺-montmorillonite nanocomposites has been synthesised using modified 4,4′-di-phenymethylate diisocyanate (M-MDI), modified polyether polyol (MPP) and Na⁺-montmorillonite (layered clay). Here, MPP was used as a swelling agent to treat the layered clay. Experimental results indicated that with increasing the amount of layered clay, the strength and strain-at-break increased. The storage modulus below the glass transition temperature of the soft segments in the polyurethane was increased by more than 350%. With increased loading of layered clay, the thermal conductivity decreased slightly rather than increased. This finding will provide valuable information for polyurethane industry.     

Effect of intercalating agents on clay dispersion and thermal properties in polyethylene/montmorillonite nanocomposites

Alkyl pyridinium, 1‐vinyl alkyl imidazolium, 1,3‐dialkyl imidazolium, and tetraalkyl phosphonium bromides were successfully used as intercalants for the preparation of highly thermally stable organophilic montmorillonites. Nanocomposites of linear low density polyethylene (LLDPE) and linear low density polyethylene grafted with maleic anhydride (LLDPE/LLDPE‐g‐MAH) were prepared from those organoclays. The micro‐ and nano‐dispersions were analyzed through X‐ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM): intercalation and/or partial exfoliation were found to occur only for formulations based on organoclays having an initial basal distance higher than 20 Å, suggesting the existence of a critical interfoliar distance for the delamination of silicate layers in a noninteracting polymer matrix. The properties of the nanocomposites were analyzed through differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and oscillatory rheometry. The dynamic crystallization of LLDPE was not significantly affected by the presence of clay. TGA in oxidative atmosphere proved to be very sensitive to the dispersion state of the organoclay: the thermal stability was drastically enhanced for intercalated and partially exfoliated formulations. However, the inherent thermal stability of the organoclay did not appear to influence significantly the overall thermal stability of the composite in the range of temperatures investigated (160–230°C). POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

Polymer/clay nanocomposites as VOC barrier materials and coatings

The transport properties of select volatile organic compounds were measured in polyurethane/clay nanocomposite barrier membranes as a function of clay content. The nanocomposites were fabricated by two different processing methods involving stirring and sonication of the clay particles. The concentration of Cloisite^® 30B in the nanocomposite was varied from 0 to 50 wt%. Characterization of membrane transport properties was achieved via a gravimetric sorption method. Material-phase diffusivity coefficients (D) decreased with increasing Cloisite^® concentration, while changes in the material/VOC partition coefficients (K) depended on the molecular interactions of the VOCs with the membrane material.     

The dynamics of montmorillonite clay dispersion and morphology development in immiscible ethylene-propylene rubber/polypropylene blends

The evolution of morphology during the melt compounding of polypropylene (PP), maleated ethylene-propylene rubber (EPR-g-MAn) and onium-ion exchanged montmorillonite clay (NR₄⁺-MM) is described. Irrespective of the ratio of components, clay partitions into the EPR-g-MAn phase exclusively, with significant amounts of mineral exfoliation occurring in the very early stages of compounding. These changes in filler distribution and dispersion are accompanied by reductions in the size of the dispersed PP phase, as the rate of droplet coalescence falls in response to an elevated EPR-g-MAn matrix viscosity. However, when NR₄⁺-MM is localized in a dispersed EPR-g-MAn phase, coalescence increases as a result of hindered particle break-up.     

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.     

Supercritical CO2 dispersion of nano-clays and clay/polymer nanocomposites

Dispersed polymer/clay nanocomposites are of great interest because they can significantly improve the properties of existing polymeric materials. However, achieving a high level of clay dispersion has been a key challenge in the production of polymer/clay nanocomposites. In this paper, we explore a novel supercritical carbon dioxide (scCO₂) processing method that utilizes scCO₂ to disperse nano-clays. The structure and properties of the clays and the resultant nanocomposites are characterized using a combination of wide-angle X-ray diffraction (WAXD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and rheology. Significant dispersion was achieved with dry Cloisite 93A clay, whereas relatively poor dispersion was achieved with dry Cloisite Na⁺ (natural clay). The extent of clay dispersion appears to be dependent on the ‘CO₂-philicity’, which in turn appears to depend on the surface modifications and inter-gallery spacing. The presence of an acidic hydrogen on the surfactant in Cloisite 93A appears to play a strong role in its ‘CO₂-philicity’. The ability to delaminate dry clays is significant because it will likely increase the ability to produce dispersed clay/polymer nanocomposites via melt processing. In addition to delaminating dry clays, we demonstrate that CO₂-phobic Cloisite Na⁺ (natural clay) can be partially dispersed with scCO₂, using a CO₂-philic polymer, polydimethylsiloxane (PDMS). The dispersed clay/PDMS nanocomposite shows an order of magnitude increase in the dynamic storage modulus at low frequencies, accompanied by the emergence of a ‘solid-like’ plateau, characteristic of dispersed nanocomposites with enhanced clay/polymer interactions.     

Bacterial cellulose-laponite clay nanocomposites

A novel material comprised of bacterial cellulose (BC) and Laponite clay with different inorganic-organic ratios (m/m) was prepared by the contact of never-dried membranes of BC with a previous dispersion of clay particles in water. Field emission scanning electron microscopy (FE-SEM) data of composite materials revealed an effective adhesion of clay over the surface of BC membrane; inorganic particles also penetrate into the polymer bulk, with a significant change of the surface topography even at 5% of clay loading. As a consequence, the mechanical properties are deeply affected by the presence of clay, increasing the values of the Young modulus and the tensile strength. However the maximum strain is decreased when the clay content is increased in the composite in comparison to pristine BC. The main weight loss step of the composites is shifted towards higher temperatures compared to BC, indicating that the clay particles slightly protect the polymer from thermal and oxidative decomposition.     

Calculating barrier properties of polymer/clay nanocomposites: Effects of clay layers

We analyzed the effects of clay layers on the barrier properties of polymer/clay nanocomposites containing impermeable and oriented clay layers. Using the relative permeability theory in combination with the detour theory, we obtained new relative permeability expressions that allow us to investigate the relative permeability R_p as a function of lateral separation b, layer thickness w, gallery height H, layer length L, and layer volume fraction Φ_s. It was found that intercalated and/or incomplete exfoliated structures and dispersed tactoids with several layers can effectively enhance the barrier properties of the materials. Furthermore, we developed the chain-segment immobility factor to briefly discuss the chain confinement from clay layers. The results showed that the chain confinement enhanced the barrier properties of the intercalated nanocomposites. Our model is better consistent with the experiments when Φ_s>0.01. The findings provide guidelines for tailoring clay layer length, volume fraction and dispersion for fabricating polymer-clay nanocomposite with the unique barrier properties.     

The effect of clay dispersion on the properties of LLDPE/LLDPE‐g‐MAH/montmorillonite nanocomposites

In this work, three coupling agents presenting different grafting contents and molecular weights were used to prepare linear low density polyethylene (LLDPE)/linear low density polyethylene grafted with maleic anhydride (LLDPE‐g‐MAH)/montmorillonite nanocomposites with various morphologies. The clay dispersion was analyzed at the micrometric level by scanning electron microscopy and at the nanometric level by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). It was found that coupling agents having intermediate molecular weights led to the highest exfoliation extents, whereas the coupling agent presenting the highest molecular weight led to a poor delamination of the clay platelets. The properties of the nanocomposites produced and of their LLDPE/LLDPE‐g‐MAH reference blends were analyzed. It was shown that the best improvements in mechanical and barrier properties are not necessarily achieved for the nanocomposites, exhibiting the highest exfoliation extents. The length of the tactoids also plays a crucial role on the macroscopic properties. In addition, a high level of delamination could result in a loss of reinforcement effect, due to the inherent flexibility of the individual clay platelets. Finally, the strength of the clay/polymer interface, which was evaluated through surface tension measurements, seems to play a significant role on the properties of the nanocomposites. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

Interface-tuned epoxy/clay nanocomposites

Though interface has been known for a critical role in determining the properties of conventional composites, its role in polymer nanocomposites is still fragmented and in its infancy. This study synthesized a series of epoxy/clay nanocomposites with different interface strength by using three types of modifiers: ethanolamine (denoted ETH), Jeffamine^® M2070 (M27) and Jeffamine^® XTJ502 (XTJ). XTJ created a strong interface between clay layers and matrix because it bridged the layers with matrix by a chemical reaction as proved by Fourier transform infrared spectroscopy; M27 produced an intermediate interface strength due to the molecular entanglement between grafted M27 chains and matrix molecules; the interface made by ETH was weak because neither chemical bridging nor molecular entanglement was involved. The studies of mechanical and thermal properties and morphology at a wide range of magnification show that the strong interface promoted the highest level of exfoliation and dispersion of clay layers, and achieved the most increment in Young’s modulus, fracture toughness and glass transition temperature (T_g) of matrix. With ∼1.3 wt% clay, the critical strain energy release rate G_1c of neat epoxy improved from 179.0 to 384.7 J/m, 115% improvement and T_g enhanced from 93.7 to 99.7 °C, 6.4% improvement.     

Exfoliated and intercalated polyamide-imide nanocomposites with montmorillonite

Polyamide-imide (PAI) is a high performance condensation polymer, which has high heat resistance and high radiation resistance. Solvent suspensions of PAI are widely used in magnetic wire coatings. Montmorillonite (MMT) nanocomposites were investigated for the concentration effects on dispersion, glass transition, degradation, and mechanical properties. Samples were prepared using a controlled torque stirrer and slow solvent extraction was followed for the cast samples. Optical microscopy shows that the surface of the cast sample has increased edge-edge clay platelet attraction. Transmission electron microscopy of the through thickness sample indicated platelet edges, increased face-face coagulated states and some edge-edge flocculated states of tactoid formation. X-ray diffraction indicated that for 1% sample a highly exfoliated structure was obtained while between 1.5 and 3% intercalated and exfoliated dispersions were obtained. The glass transition was not significantly affected by clay presence but a drop in specific heat change was observed for all samples showing a 001 clay peak presence. The first heating scan showed PAI solvent and MMT organic emission but these emissions did not affect the PAI chemically. Degradation was altered by the level of matrix shielding by the clay. Hardness values were increased with clay presence but unaffected by concentration.     

Poly(butylene sucinate-co-adipate)/montmorillonite nanocomposites: effect of organic modifier miscibility on structure, properties, and viscoelasticity

Poly(butylene succinate-co-adipate) (PBSA)/layered silicate nanocomposites were prepared by melt extrusion of PBSA and three different types of commercially available organically modified montmorillonite (OMMT). Using three types of OMMT modified with three different kinds of surfactants, the effect of organic modification on nanocomposites was investigated by focusing of three major aspects: morphological study, property measurements, and melt rheological behavior under both small and large deformation flows. X-ray diffraction (XRD) patterns revealed that increasing the level of interactions (miscibility) between the organic modifier and PBSA matrix increases the tendency of the silicate layers to delaminate and distributed nicely within the PBSA matrix. Transmission electron micrographic (TEM) observations showed that the ordering of silicate layers in PBSA matrix is well matched with the XRD patterns. Thermal analysis revealed that extent of crystallinity of PBSA matrix is directly related to the extent of exfoliation of silicate layers in the nanocomposites. Dynamic mechanical analysis and tensile property measurements showed concurrent improvement in mechanical properties when compared to the neat PBSA and the extent of improvement is directly related to the extent of delamination of silicate layers in the PBSA matrix. The same tendency was also observed in melt rheological measurements.     

The effect of the solvent on the morphology of cellulose acetate/montmorillonite nanocomposites

Nanocomposites of cellulose acetate and sodium montmorillonite were prepared using the solution intercalation method with different solvents. The effects of solvent type on the morphology, thermal and mechanical properties of the nanocomposites were investigated by X-ray microtomography and diffraction, field emission scanning electron microscopy, analytical transmission electron microscopy based on electron loss spectroscopy imaging and dynamical mechanical analysis. XRD and TEM results indicated that the dispersion and delamination of the clay are achieved when the solvent presents favorable interactions with the clay. In this case, the storage modulus and the glass transition temperature are significantly higher than those of pure cellulose acetate. The results show that the solvent has a major effect in controlling the morphology of cellulose acetate and cellulose acetate nanocomposite and could be used as a process parameter to produce films with a range of properties.