Effect of the Mixture Composition on Shear and Extensional Rheology of Recycled PET and ABS Nanocomposites

Summary: Recycled PET as well as ABS - organomodified montmorillonite nanocomposites were prepared via melt compounding in a counter-rotating twin screw extruder. The topological changes in polymer matrices as dependency on clay modification have been evaluated from dynamic experiments in the shear flow using low amplitude oscillatory measurements. Flow characteristics of all studied organoclay nanocomposites showed shear-thinning behavior at low frequencies. Filling of PET with some organoclays led to degradation reactions, which were reflected by lower magnitudes of viscosity and storage modulus in the range of higher frequencies as compared to unfilled polymer matrix. On the contrary, no degradation during the processing of different organoclays with recycled ABS has been observed.     

Carboxylate clays: A model study for polypropylene/clay nanocomposites

Sodium-montmorillonite was intercalated by carboxylate salts to prepare carboxylate clays. The intercalation of sodium acetate doubles the clay basal spacing and no degradation of the carboxylate clay is noticed in the extrusion temperature range. These carboxylate clays were used to synthesize polypropylene-graft-maleic anhydride (PP-g-MA)/clay nanocomposites. Nanocomposites were also produced by a one-pot process using in situ prepared carboxylate clay. The carboxylate salts within the clay layers partially neutralize the maleic anhydride groups of the PP-g-MA matrix, in situ during the melt compounding. The ionic groups of the partially neutralized polymer offer favourable interactions with the clay, hence reinforcing the interfacial bond between the polymer and the clay and improving the composite properties. The use of carboxylate clay clearly improves the clay dispersion into the PP-g-MA matrix and improves the nanocomposite’s thermal and rheological properties.     

Effect of extrusion and photo-oxidation on polyethylene/clay nanocomposites

Polyethylene (a 1:1 blend of m-LLDPE and z-LLDPE) double layer silicate clay nanocomposites were prepared by melt extrusion using a twin screw extruder. Maleic anhydride grafted polyethylene (PEgMA) was used as a compatibiliser to enhance the dispersion of two organically modified monmorilonite clays (OMMT): Closite 15A (CL15) and nanofill SE 3000 (NF), and natural montmorillonite (NaMMT). The clay dispersion and morphology obtained in the extruded nanocomposite samples were fully characterised both after processing and during photo-oxidation by a number of complementary analytical techniques. The effects of the compatibiliser, the organoclay modifier (quartenary alkyl ammonium surfactant) and the clays on the behaviour of the nanocomposites during processing and under accelerated weathering conditions were investigated. X-ray diffraction, transmission electron microscopy (TEM), scanning electron microscopy (SEM), rheometry and attenuated reflectance spectroscopy (ATR-FTIR) showed that the nanocomposite structure obtained is dependent on the type of clay used, the presence or absence of a compatibiliser and the environment the samples are exposed to. The results revealed that during processing PE/clay nanocomposites are formed in the presence of the compatibiliser PEgMA giving a hybrid exfoliated and intercalated structures, while microcomposites were obtained in the absence of PEgMA; the unmodified NaMMT-containing samples showed encapsulated clay structures with limited extent of dispersion in the polymer matrix. The effect of processing on the thermal stability of the OMMT-containing polymer samples was determined by measuring the additional amount of vinyl-type unsaturation formed due to a Hoffman elimination reaction that takes place in the alkyl ammonium surfactant of the modified clay at elevated temperatures. The results indicate that OMMT is responsible for the higher levels of unsaturation found in OMMT-PE samples when compared to both the polymer control and the NaMMT-PE samples and confirms the instability of the alkyl ammonium surfactant during melt processing and its deleterious effects on the durability aspects of nanocomposite products. The photostability of the PE/clay nanocomposites under accelerated weathering conditions was monitored by following changes in their infrared signatures and mechanical properties. The rate of photo-oxidation of the compatibilised PE/PEgMA/OMMT nanocomposites was much higher than that of the PE/OMMT (in absence of PEgMA) counterparts, the polymer controls and the PE–NaMMT sample. Several factors have been observed that can explain the difference in the photo-oxidative stability of the PE/clay nanocomposites including the adverse role played by the thermal decomposition products of the alkyl ammonium surfactant, the photo-instability of PEgMA, unfavourable interactions between PEgMA and products formed in the polymer as a consequence of the degradation of the surfactant on the clay, as well as a contribution from a much higher extent of exfoliated structures, determined by TEM, formed with increasing UV-exposure times.     

One-step water-assisted melt-compounding of polyamide 6/pristine clay nanocomposites: An efficient way to prevent matrix degradation

Polyamide 6 (PA6)/clay nanocomposites, based on organo-modified and pristine (i.e. purified but non-modified) montmorillonite, were prepared using a water-assisted extrusion process based on the injection of water during extrusion. The formation of a single PA6/water phase during extrusion (shown by High Pressure Differential Scanning Calorimetry (HPDSC)) improves the clay dispersion, decreases the PA6 melting temperature by 66 °C (so-called cryoscopic effect), and thus prevents the polymer matrix degradation during processing. This process enables the compounding of pristine clay-based nanocomposites whose dispersion state, thermal and mechanical performances are close to what is generally reported for organo-modified montmorillonite-based nanocomposites. Advantage was taken of water-assisted extrusion to optimize the clay dispersion by increasing shear rate and of the cryoscopic effect to limit the degradation by decreasing the processing temperature. Using these conditions PA6/pristine clay nanocomposites properties are similar to those of more conventional PA6/organomodified clay nanocomposites.     

Effects of organoclays on the thermal processing of pe/clay nanocomposites

Nanocomposites containing both polyethylene and montmorillonite clay organically modified with four different types of quaternary ammonium salts were obtained via direct melt intercalation. Thus, the main purpose of this work was to evaluate the effect of the organoclay on the thermal stability of polyethylene. The organoclays were characterized by XRD, FTIR, DSC and TG. The polyethylene/organoclay nanocomposites were studied by XRD, TEM, TG, besides an evaluation of their mechanical properties. The results showed that the salts were incorporated by intercalation between the layers of the organoclay and, apparently that the nanocomposites were more thermally stable than pure polyethylene.     

Effect of the type of alkylammonium ion clay modifier on the structure and thermal/mechanical properties of glassy and rubbery epoxy-clay nanocomposites

Glassy and rubbery epoxy-clay nanocomposites were synthesized by using various montmorillonite organoclays in order to investigate and compare the effect of the type of alkylammonium ion clay modifier on the structure and properties of the nanocomposites. The organoclays studied were the Nanomer I.28E and I.30E and the Cloisite C10A, C15A and C20A. The functionality (acidity), size and shape of backbone chain, hydrophobicity and polarity were the varying parameters of the organic modifiers that were correlated to the ability of the organoclays to form highly intercalated or exfoliated nanocomposites and to the changes observed in the mechanical (tensile measurements), thermo-mechanical (DMA) and thermal (TGA) properties of the epoxy nanocomposites. The primary alkylammonium ion modifiers with reactive/acidic hydrogen atoms, compared to the quaternary octadecyl, dihydrogenated tallow and benzyl-substituted hydrogenated tallow ammonium ions, were the most effective for the formation of exfoliated clay glassy and rubbery epoxy nanocomposites which exhibited improved properties compared to the pristine epoxy polymers.     

Organo-modified montmorillonite/poly(?-caprolactone) nanocomposites prepared by melt intercalation in a twin-screw extruder

Nanocomposites based on biodegradable poly(?-caprolactone) organo-modified clay have been prepared by melt intercalation using a twin-screw extruder. The screw configuration developed allowed us to obtain an intercalated/exfoliated nanocomposite structure using a modified montmorillonite containing no polar groups, in contrast to previous work using mainly alkyl ammonium containing hydroxyl polar groups in poly(?-caprolactone). Montmorillonite nanocomposites were prepared using a specific extrusion profile from a 30 wt% masterbatch of organo-modified clay, which was then diluted at 1, 3 and 5%. Intercalated and/or exfoliated nanocomposites structures were assessed using rheological procedures and confirmed by transmission electron microscopy analysis. Mechanical and thermal properties were found to be strongly dependent on morphology and clay percentage. Crystallinity was only slightly affected by the clay addition. Effect of exfoliation on Young's modulus and thermal stability was investigated. Young's modulus increased significantly and onset degradation temperature measured by TGA was significantly reduced for an exfoliated nanocomposite composition containing 5 wt% organoclay.     

A novel method for preparation of exfoliated UV-curable polymer/clay nanocomposites

The half adduct of isophorone diisocyanate and 2-hydroxyethyl acrylate (IPDI-HEA), as a reactive organic modifier, was used to functionalize Na-montmorillonite (Na-MMT) clay. Unlike the electronic interaction in the conventional cation-exchange method, the driving force for the organic modification came from the chemical reaction between IPDI-HEA and framework hydroxyl groups on the surface of clay. With high degree of organic modification (48%), the d-spacing of clay layer was greatly enlarged to 3.32 nm, and the clay became more organophilic. After in situ photopolymerization among the IPDI-HEA grafted MMT clay, monomers and oligomers, the exfoliated polymer/clay nanocomposites were obtained. X-ray diffraction and transmission electron microscopy were used to detect the structure and morphology of the clay dispersed in the polymer matrix. Compared with the pure polymer materials, the exfoliated polymer/clay nanocomposites exhibited enhancements in mechanical and thermal properties.     

Effect of a silicate filler on the crystal morphology of poly(trimethylene terephthalate)/clay nanocomposites

A series of intercalated poly(trimethylene terephthalate) (PTT)/clay nanocomposites were prepared in a twin‐screw extruder by the melt mixing of PTT with either quaternary or ternary ammonium salt‐modified clays. The morphology and structure, along with the crystallization and melting behavior, and the dynamic mechanical behavior of the composites were characterized by X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry, and dynamic mechanical thermal analysis. The results showed that the PTT chains could undergo center‐mass transport from the polymer melt into the silicate galleries successfully during the blending and extrusion process. More coherent stacking of the silicate layers was reserved at higher clay concentrations and shorter blend times. Compared with conventionally compounded composites, the nanoscale‐dispersed organophilic clays were more effective as crystal nucleation agents. The influence of the nanosilicates on the crystallization and melting behavior of PTT became distinct when the concentration of clay was around 3 wt %. The changes in the crystallization behavior of the polymer/clay nanocomposites depended not only on the size of the silicates but also on the intrinsic crystallization characteristics of the polymers. The resulting nanocomposites showed an increase in the dynamic modulus of PTT and a decrease in the relaxation intensity (both in loss modulus and loss tangent magnitude). © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2275–2289, 2003     

Effect of process variables on mechanical properties of polyurethane/clay nanocomposites

This paper addresses the effects of operating variables on mechanical properties of polyurethane/clay nanocomposites including tensile strength, abrasion resistance, and hardness. The variables were prepolymer type, clay cation, clay content, and prepolymer–clay mixing time. The experiments were carried out based on the design of experiments using Taguchi methods. The nanocomposites were synthesized via in situ polymerization starting from two different types of prepolymers (polyether‐ and polyester‐types of polyol reacted with toluene diisocyanate), and methylene‐bis‐ortho‐chloroanilline (MOCA) as a chain extender/hardener. Montmorillonite with three types of cation (Na⁺, alkyl ammonium ion, and MOCA) were examined. Among the parameters studied, prepolymer type and clay cation have the most significant effects on mechanical properties. Polyester nanocomposites showed larger improvements in mechanical properties compared to polyether materials due to higher shear forces exerted by polymer matrix on clay aggregates during polymer–clay mixing. The original MMT with Na⁺ cation results in weak improvements in mechanical properties compared to organoclays. It is observed that the stress and elongation at break, and abrasion resistance of the nanocomposite samples can be optimized with 1.5% of clay loading. The morphology and chemical structure of the optimum sample were examined by X‐ray diffraction and FT‐IR spectroscopy, respectively. Copyright © 2009 John Wiley & Sons, Ltd.     

Zero‐order kinetics of the thermal degradation of polypropylene/clay nanocomposites

The thermal degradation kinetics of polypropylene/clay microcomposites and nanocomposites were studied by thermogravimetric analysis. In comparison with pure polypropylene, the reaction order of the degradation of the composites became zero‐order, and the activation energy increased dramatically. The zero‐order kinetics were associated with the acidic sites (H⁺) created on the clay layers, whereas the increase in the activation energy was coupled with the shielding effect of clay. The kinetic analysis could provide additional mechanistic clues concerning the thermal stability and flammability of polymer/clay nanocomposites. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3713–3719, 2005     

Thermal decomposition of various alkyl onium organoclays: Effect on polyethylene terephthalate nanocomposites' properties

The thermal stability of organically modified layered silicates is determinant for processing polymer nanocomposites and is believed to play a key role on their properties. In this work, alkyl phosphonium, alkyl pyridinium and dialkyl imidazolium surfactants were used as intercalating agents for the preparation of highly thermally stable organophilic montmorillonites. The thermal decomposition of the surfactants and of their organoclays was studied by combined thermogravimetric analysis (TGA) and mass spectroscopy (MS), which allowed the identification of specific volatile compounds issued from the degradation. In order to investigate the influence of the thermal decomposition of the intercalating agent during processing, the various organoclays were incorporated in a polyethylene terephthalate (PET) matrix. The color of the nanocomposites was significantly affected by the thermal decomposition of the intercalating agent. In the case of the alkyl pyridinium modified clay, the degradation of the intercalating agent during processing was found to alter the clay dispersion. Finally, the crystallization was analyzed by differential scanning calorimetric (DSC) analysis and polarized optical microscopy (POM): it was demonstrated that the kinetics of nucleation and growth is not only affected by the dispersion state of the clay, but also depends on the clay/polymer interface properties, and therefore on the nature of the intercalating agent.     

Transesterification catalysts to improve clay exfoliation in synthetic biodegradable polyester nanocomposites

We report here on the melt intercalation preparation of polymer/clay nanocomposites based on three commercial synthetic biodegradable polyesters: EastarBio Ultra, Ecoflex, and Bionolle, respectively. The montmorillonite clay addition is performed either by direct dispersion of Cloisite 30B in the polyester matrix or by dispersing a “PCL-grafted Cloisite 30B” masterbatch in the biodegradable polyesters. All obtained nanocomposites display an intercalated morphology as attested by X-ray diffraction measurements. The various analyses clearly show that the Bionolle (BIO) matrix gives the best results. Morphological characterization and mechanical properties of these nanocomposites also show that the “masterbatch route” leads to poor results as a consequence of the very low compatibility between the poly(ε-caprolactone) (PCL) of the masterbatch and the three other polyester matrices. In a second part, nanocomposites based on the BIO matrix are prepared by direct dispersion of the organo-clay in the presence of three different metal-based catalysts with the aim to promote transesterification reactions between the nanocomposite constituents. The mechanical properties and morphological characterization of these nanocomposites show that the tin-based catalyst (Sn) is the more efficient. Indeed, the effectiveness of transesterification reactions taking place between the ester functions of the BIO matrix and the hydroxyl groups of the organo-clay and the resulting “grafting” of BIO chains on the organo-clay surface are confirmed by thermogravimetric analyses performed after the extraction procedure. TEM observations show that this catalyst enhances the clay platelets exfoliation within the BIO matrix as a consequence of the transesterification reactions. Nanocomposites prepared in presence of Sn show better clay dispersion and enhanced stiffness with a 60% increase in Young’s modulus.     

Effect of matrix viscosity on the extent of exfoliation in EVA/organoclay nanocomposites

The influence of matrix viscosity and polarity on ethylene‐vinyl acetate copolymer (EVA) nanocomposites was studied. Five different EVA grades, with different melt flow indexes (MFIs) and/or vinyl acetate (VA) contents, were mixed with two montmorillonite (MMT) nanoclays: pristine and modified with a polar surfactant, producing 75/25 w/w% masterbatches which were subsequently diluted in the EVA matrix to obtain 5 wt% MMT nanocomposites. Although the same VA content, WAXS results, rheological measurements and TEM analysis showed that the lower the EVA viscosity, the greater the tendency to obtain exfoliated and well dispersed nanocomposites with the organically modified clay. On the other hand, the high viscosity EVA nanocomposites showed that the (001) organoclay diffraction peak was shifted to higher values of 2θ, suggesting lamellae collapsing. TGA and FTIR measurements were used to probe the thermal degradation of organoclay; furthermore, it was not possible to identify, by the techniques used, any reaction between the VA groups and hydroxyl surfactant groups. Thus, it was inferred that the organic surfactant was removed (or ejected) from the clay galleries as a consequence of huge shear tensions developed during processing of the masterbatches/nanocomposites with high viscosity EVA matrices. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of polymerically‐modified clay structure on the morphology and properties of UV‐cured polyurethane acrylate/clay nanocomposites

Polyurethane acrylate (PUA)/clay nanocomposites were prepared by UV‐curing from a series of styrene‐based polymerically‐modified clays and PUA resin. Effect of the chemical structure of the polymeric surfactants on the morphology and tensile properties of nanocomposites has been explored. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) experimental results indicated that surfactants having hydroxyl or amino groups show better dispersion and some of the clay platelets were fully exfoliated. However, the composites formed from pristine clay and other polymerically‐modified clays without hydroxyl or amino groups typically contained both tactoids and intercalated structure. The mechanical properties of PUA composites were greatly improved where the organoclays dispersed well. Thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC) were carried out to examine the thermal properties of the composites. The results showed that the loading of polymerically‐modified clays do not effect the thermal stability, but increased the Tgs of PUA/clay composites. Copyright © 2010 John Wiley & Sons, Ltd.     

Chlorinated polyethylene nanocomposites using PCL/clay nanohybrid masterbatches

Exfoliated nanocomposites were prepared by dispersion of poly(ε-caprolactone) (PCL) grafted montmorillonite nanohybrids used as masterbatches in chlorinated polyethylene (CPE). The PCL-grafted clay nanohybrids with high inorganic content were synthesized by in situ intercalative polymerization of ε-caprolactone between silicate layers organo-modified by alkylammonium cations bearing two hydroxyl functions. The polymerization was initiated by tin alcoholate species derived from the exchange reaction of tin(II) bis(2-ethylhexanoate) with the hydroxyl groups borne by the ammonium cations that organomodified the clay. These highly filled PCL nanocomposites (25 wt% in inorganics) were dispersed as masterbatches in commercial chlorinated polyethylene by melt blending. CPE-based nanocomposites containing 3-5 wt% of inorganics have been prepared. The formation of exfoliated nanocomposites was assessed both by wide-angle X-ray diffraction and transmission electron microscopy. The thermal and thermo-mechanical properties were studied as a function of the filler content, by differential scanning calorimetry and dynamic mechanical analysis, respectively. The mechanical properties were also assessed by tensile tests. The Young’s modulus of CPE is increased by a decade when a PCL-grafted clay masterbatch is exfoliated to reach 5 wt% of clay in the resulting nanocomposite. The influence of PCL-grafting on the properties of these nanocomposites was investigated by comparison with materials obtained with ungrafted-PCL.     

Photo‐stabilization of EPDM–clay nanocomposites: effect of antioxidant on the preparation and durability

The present study is to examine the photo‐stabilization effect of an antioxidant on the photo‐oxidation of ethylene‐propylene‐diene monomer (EPDM)–clay nanocomposites. During the preparation of EPDM–clay nanocomposites via melt processing antioxidants are usually incorporated along with clay, which allows phenolic antioxidant molecules to get adsorbed onto acidic clay platelets and their interaction with metallic impurities reduces the stabilizing efficiency of the antioxidant. The nanocomposites were obtained by solution dispersion followed by melt compounding of EPDM and organophilic montmorillonite (OMMT). The samples were characterized by conventional tools such as X‐ray diffraction (XRD), Fourier Transform Infra Red (FT‐IR) spectroscopy, and thermo‐gravimetric analysis (TGA). It was found, upon photo‐irradiation (λ > 290 nm) studies by following the changes in functional groups and surface morphology, that photo‐degradation was lowered by the antioxidant and the efficiency of the antioxidant could be improved by initial incorporation of antioxidant in the EPDM matrix. In EPDM–clay nanocomposites, a stabilizing activity of the antioxidant was observed above some threshold concentration of the antioxidant. The relationship between the nanoclay reinforcement and stabilizing efficiency in terms of photo‐oxidation and surface morphology for their applicability are discussed. The methodology adopted for this study is also justified through our observation. Copyright © 2007 John Wiley & Sons, Ltd.     

Polymorphic behavior in syndiotactic polystyrene/clay nanocomposites

X‐ray diffraction methods were used in an investigation of the structural changes in syndiotactic polystyrene (sPS)/clay nanocomposites. sPS/clay was prepared by the intercalation of sPS polymer into layered montmorillonite. Both X‐ray diffraction data and transmission electron microscopy micrographs of sPS/clay nanocomposites indicated that most of the swellable silicate layers were exfoliated and randomly dispersed in the sPS matrix. The X‐ray diffraction data also showed the presence of polymorphism in the sPS/clay nanocomposites. This polymorphic behavior was strongly dependent on the thermal history of the sPS/clay nanocomposites from the melt and on the content of clay in the sPS/clay nanocomposites. Quenching from the melt induced crystallization into the α‐crystalline form, and the addition of montmorillonite probably increased heterophase nucleation of the α‐crystalline form. The effect of the melt crystallization of sPS and sPS/clay nanocomposites at different temperatures on the crystalline phases was also examined. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 736–746, 2002     

Effects of organoclay modifiers on the flammability, thermal and mechanical properties of polycarbonate nanocomposites filled with a phosphate and organoclays

Polycarbonate was melt blended with solid bisphenol A bis(diphenyl phosphate), and a series of organoclays. Effects of the organoclay modifiers on the flammability, thermal and mechanical properties of the nanocomposites were studied by limiting oxygen index, UL-94 burning test, thermogravimetric analysis, differential scanning calorimetry, tensile test and dynamic mechanical analysis. Although all the nanocomposites exhibit an intercalated-exfoliated morphology, they vary in the magnitude of intercalation revealed by X-ray diffraction and transmission electron microscopy. Flammability of the nanocomposites is strongly related to the thermal stability rather than the morphology. Glass transition temperature (T_g) and mechanical properties are controlled by both the morphology and the affinity of the organoclays with the matrix. The modifier containing hydroxyl moiety has stronger interactions with the matrix but it can promote its degradation, thus the corresponding nanocomposite exhibits a better intercalated morphology, higher T_g, superior strength and modulus however a worse thermal stability and flame retardancy. An additional silane within the organoclays would make the organoclays more compatible with the matrix but be a steric obstacle to the intercalation of the matrix chains; however, flame retardancy of the corresponding nanocomposite is enhanced due to the flame retardant nature of the silane. Similarly, the modifier bearing two long alkyl tails shows stronger affinity with the matrix than the one bearing a single tail, but it would hinder the intercalation due to the steric effect. These establishments between organoclay modifiers and the properties of nanocomposites might be guidance for developing materials with practical applications.     

Surface modification of clay and its effect on the intercalation behavior of the polymer/clay nanocomposites

Melt intercalation of the methylsilylated organoclays with polar polymers such as SAN was examined to verify the adhesive role of guest polymeric chains between hydrophilic clay layers, so-called “glue effect” on intercalation behavior. Once methylsilylated organoclay was melt-blended with SAN, it was found that the mixture presented significant retardation of increase of interlayer spacing, d₀₀₁ with heating time, and a noticeable decrease of d₀₀₁ after the methylsilylation of organoclay, implying that the diffusion of SAN was highly suppressed by the decrease of polar interaction force caused by conversion of OH to methylsiloxyl groups. However, when applying shear force for the methylsilylated organoclay/SAN nanocomposites during melt intercalation, a noticeable increase of d₀₀₁ was observed, expressing that intercalation of clay by SAN occurred much more effectively because of the reduction of gluing force between host clay and guest polymers, which was well supported by dramatic improvements of mechanical properties after methylsilylation of organoclays. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2367–2372, 2004