Experimental investigation of the linear viscoelastic response of EVA‐based nanocomposites

Linear viscoelastic behaviors of ethylene‐vinyl acetate (EVA)‐layered silicate nanocomposites were investigated. EVA with vinyl acetate (VA) content of 18 and 28% by weight and commercially modified montmorillonite clay (Cloisite® 30B) were melt blended in a twin‐screw extruder. Nanocomposites of 2.5, 5 and 7.5% by weight were produced. Wide angle X‐ray scattering was used to ascertain the degree of layer swelling that could be attributed to the intercalation of polymer chains into the interlayer of the silicates. Transmission electron microscopy was used to analyze the dispersion and extent of exfoliation of the layered silicates in the polymer matrix. All nanocomposites were found to have mixed intercalated/exfoliated morphologies. Both storage and loss moduli and complex viscosity showed improvement at all frequencies tested with increase in silicate loading. Terminal zone behavior was also shown to disappear gradually with silicate content. Increase in silicate loading had caused the divergence of viscosity profile from low‐frequency Newtonian plateau to non‐Newtonian slope corresponding to a possible finite yield stress. The gradual disappearances of terminal zone and Newtonian homopolymer‐like characteristics with silicate loading were attributed to the formation of lattice spanning three‐dimensional network structures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2127–2135, 2006     

Physical and mechanical properties of nanocomposite barrier film containing encapsulated nanoclay

Waterborne poly(styrene‐co‐butyl acrylate) was prepared via miniemulsion polymerization in which nanoclay (Cloisite® 30B, modified natural MMT) in different concentrations was encapsulated. Scanning electron microscopy, X‐ray diffraction, and transmission electron microscopy confirmed the encapsulation and intercalated‐exfoliated structure of Cloisite® 30B within poly(styrene‐co‐butyl acrylate). The effect of nanoclay content on water vapor permeability, water uptake, oxygen permeability, thermal, and mechanical properties of thin films containing 1.5, 2.56, 3.5, and 5.3 wt % encapsulated Cloisite® 30B in poly(styrene‐co‐butyl acrylate) was investigated. The presence of encapsulated Cloisite® 30B within the polymer matrix improved tensile strength, Young's modulus, and toughness of the nanocomposites depending on the nanoclay content. Water vapor transmission rate, oxygen barrier properties, and thermal stability were also improved. The results indicated that the incorporation of Cloisite® 30B in the form of encapsulated platelets improved physicomechanical properties of the nanoclay‐polymer composite barrier films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of organoclays on the thermal,mechanical, and oxygen barrier properties of poly(methylmethacrylate‐co‐acrylonitrile)/clay nanocomposites

The nanostructured hybrid materials of poly(methylmethacrylate‐co‐acrylonitrile) copolymer were synthesized with incorporation of two organically modified clays, Cloisite® 30B and 93A by in situ intercalative emulsifier‐free emulsion polymerization method. The synthesized products were characterized by Fourier transform infrared spectroscopy to get evidence of copolymerization and formation of copolymer‐clay nanocomposite. X‐ray diffraction study and transmission electron microscopy analysis revealed that the clays were successfully intercalated and exfoliated into the copolymer matrix. Thermal properties of the nanocomposites were studied as a function of clay content of different clay types by thermogravimetric analysis. The results showed significant effect of both the clays in enhancing thermal resistance of the materials. Mechanical properties of the composites were also found to be improved at optimum clay loading. Oxygen barrier property of these materials was measured and it was found that the oxygen permeability was reduced almost by half due to incorporation of clays at 3% loading. Further, it was observed that Cloisite® 93A was more effective for improvement in properties when compared with Cloisite® 30B in the hybrid materials. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Effect of clay surfactant type and clay content on the rheology and morphology of uncured fluoroelastomer/clay nanocomposites prepared by melt‐mixing

Fluoroelastomer/clay composites were prepared by melt mixing in an internal mixer using Cloisite® Nanoclays: NA, 15A, 20A, 30B, and 93A at three different concentrations viz. 2.5, 5.0, and 10.0 phr. Rheology, X‐ray diffraction (XRD), and transmission electron microscopy (TEM) were used to characterize the composites prepared. Dynamic rheological measurements showed significant increase in storage moduli (G′) in the terminal frequency region for the uncured composites prepared from Cloisite® 15A and 20A. At higher frequencies, organically modified nanoclays plasticize the polymer matrix leading to lower modulus values. Using all three characterization techniques, Cloisite® 15A and 20A were shown to have intercalated structure in the fluoroelastomer matrix, whereas other nanoclays were shown to have inferior dispersion. The storage modulus increases proportionally with increase in the clay loading and no clay aggregation was observed at higher loadings. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphology and mechanical properties of heterophasic PP–EP/EVA/organoclay nanocomposites

The effect of vinyl acetat (VA) on the morphological, thermal stability, and mechanical properties of heterophasic polypropylene–(ethylene‐propylene) copolymer (PP–EP)/poly(ethylene vinyl acetate) (EVA)/organoclay nanocomposites was studied. Tailored organoclay C20A was selected to enhance the exfoliation of the clay platelets. Depending on the VA content, there were two morphological organoclay populations in the systems. Both populations were directly observed by scanning transmission electron microscopy and measured by wide‐angle X‐ray diffraction and small‐angle X‐ray scattering. The content of VA in EVA originated spherical and elongated morphologies in the resultant nanocomposites. High‐VA content led to a better intercalation of the organoclay platelets. Measurement of thermal properties suggested that higher VA decreases thermal stability in samples both with and without organoclay, although nanocomposites had higher thermal stability than samples without clay. The storage modulus increased both with nanoclay and VA content. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of clay content on the melting behavior and crystal structure of nonisothermal crystallized poly(L‐lactic acid)/nanocomposites

To study the effect of organophilic clay concentration on nonisothermal crystallization, poly(L ‐lactic acid) (PLLA)/montmorillonite (MMT) nanocomposites were prepared by mixing various amounts of commercial MMT (Cloisite^® 30B) and PLLA. The effect of MMT content on melting behavior and crystal structure of nonisothermal crystallized PLLA/MMT nanocomposites was investigated by differential scanning calorimetry (DSC), small‐angle X‐ray scattering, and wide‐angle X‐ray diffraction (XRD) analyses. The study was focused on the effect of the filler concentration on thermal and structural properties of the nonisothermally crystallized nanocomposite PLLA/MMT. The results obtained have shown that at filler loadings higher than 3 wt %, intercalation of the clay is observed. At lower clay concentrations (1–3 wt %), exfoliation predominates. DSC and XRD analysis data show that the crystallinity of PLLA/MMT composites increases drastically at high clay loadings (5–9 wt %). In these nanocomposites, PLLA crystallizes nonisothermally in an orthorhombic crystal structure, assigned to the α form of PLLA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Morphology,microhardness, and flammability of compatibilized polyethylene/clay nanocomposites

Morphology, thermal properties, and microhardness of ethylene‐glycidyl methacrylate copolymer (EGMA)/clay and ethylene‐acrylic ester‐glycidyl methacrylate terpolymer (EAGMA)/clay nanocomposites with different clay concentrations have been studied. The results have shown that EGMA and EAGMA are highly compatible with the organoclays Cloisite®20A (Cl20A) and Cloisite®30B (Cl30B). Intercalated structures are formed in the whole range of Cl20A loadings investigated, whereas partial degradation of the Cl30B organoclay was observed. The thermal characteristics and microhardness of EGMA/clay nanocomposites suggest that the filler dispersion deteriorates at high concentration. The concentrated EGMA/Cl20A nanocomposites have been used as masterbatches to prepare ternary high density polyethylene (HDPE)/Cl20A and low density polyethylene (LDPE)/Cl20A nanocomposites. Diffractometric characterization and scanning electron microscopy observations of these materials have shown that the intercalated structure of the starting EGMA/Cl20A masterbatches is preserved after dilution with the polyolefins. The results suggest that the silicate platelets remain localized within the EGMA droplets in the diluted nanocomposites. The latter display improved microhardness, whereas the mechanical properties, including elongation at break, are comparable with those of the neat polyolefins. Considerable enhancement of the flame retardant properties has been observed for the ternary nanocomposites. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Nanostructure of EVA/organoclay nanocomposites: Effects of kinds of organoclays and grafting of maleic anhydride onto EVA

Nanostructure of poly(ethylene‐co‐vinyl acetate)/organically modified montmorillonite (MMT; EVA/organoclay) nanocomposites prepared by melt intercalation process was investigated using X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Three kinds of organoclays were used to see their influences on the nanostructure of the EVA hybrids. The effects of the polar interactions between the polymer and the silicate layers of organoclays were also investigated by grafting maleic anhydride onto EVA. It was found that the strong polar interactions between the polymer and the silicate layers of organoclays are critical to the formation of polymer‐layered silicate nanocomposites. The results also showed that increasing the mixing temperature was unfavorable to improve the dispersion of organoclays in the EVA matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1901–1909, 2003     

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.     

Correlation of morphology,rheology, and performance improvement in gasoline tubes based on PA‐6 nanocomposites

PA‐6/organo‐modified layered silicate nanocompounds were prepared by the melt mixing of PA‐6 with different nanoclay loadings in a corotating twin‐screw extruder. Gasoline tubes based on these nanocompounds were produced at different silicate loadings. Thermal, mechanical, rheological, and barrier properties of the different samples were investigated and correlated to their morphology. Transmission electron microscopy, wide angle X‐ray scattering, and linear melt state viscoelastic measurements were used to characterize the different aspects of nanoclay dispersion in the nanocomposite samples. While tensile modulus, softening point, heat distortion temperature, and gasoline barrier properties of the prepared tubes were improved considerably by increasing the clay content, performance improvement with respect to clay content (after a certain value) decreased with increasing clay loading. It could be attributed to the re‐agglomeration of tactoids at higher concentrations. These findings were correlated with the rheological and morphological observations. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Effect of clay addition on the morphology and thermal behavior of polyamide 6

The nanostructure, morphology, and thermal properties of polyamide 6 (PA6)/clay nanocomposites were studied with X‐ray scattering, differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). The wide‐angle X‐ray diffraction (WAXD) and TEM results indicate that the nanoclay platelets were exfoliated throughout the PA6 matrix. The crystallization behavior of PA6 was significantly influenced by the addition of clay to the polymer matrix. A clay‐induced crystal transformation from the α phase to the γ phase for PA6 was confirmed by WAXD and DSC; that is, the formation of γ‐form crystals was strongly enhanced by the presence of clay. With various clay concentrations, the degree of crystallinity and crystalline morphology (e.g., spherulite size, lamellar thickness, and long period) of PA6 and the nanocomposites changed dramatically, as evidenced by TEM and small‐angle X‐ray scattering results. The thermal behavior of the nanocomposites was investigated with DSC and compared with that of neat PA6. The possible origins of a new clay‐induced endothermic peak at high temperature are discussed, and a model is proposed to explain the complex melting behavior of the PA6/clay nanocomposites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1191–1199, 2007     

Relationship between structure and rheological,mechanical and thermal properties of polylactide/Cloisite 30B nanocomposites

Melt‐state and solid state mechanical properties and thermal stability of polylactide layered silicate nanocomposites elaborated by melt intercalation were studied as a function of clay content. Wide angle X‐ray scattering results, transmission electron microscopy observations, and rheological measurements indicated that the clay was finely distributed in the polylactide matrix. Contrary to nonlinear mechanical properties, thermal and linear mechanical properties were shown to increase with increasing clay fraction. The nanoindentation measurements confirm the significant increase of linear mechanical properties previously observed by tensile tests. The good correlation of linear mechanical properties at the macrometric and nanometric scales is explained by the high dispersion degree of the nanofiller in the biodegradable polymer matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The Role of Organically Modified Clay Particle on Thermal,Mechanical and Gas Barrier Properties of Polyimide Nanocomposites and Toward Improvement of Gas Selectivities

ABSTRACT

Novel mixed matrix membranes with various Cloisite®15A in polyimide (PI) matrix were developed for gas separation. The synthesized membranes were characterized by the FE-SEM, XRD, DTG and TEM. According to FE-SEM results, at 3 wt% of Cloisite®15A, the fillers were dispersed homogeneously in the PI polymer matrix. The tensile properties of PI/Cloisite®15A increased gradually with clay content. It was interesting to note that the pure gas selectivity was seen to be increased with decreasing the filler loading. At 1 wt% clay loading, PI/Cloisite®15A nanocomposites showed an increase of 55% in CO₂/CH₄ ideal selectivity over pristine PI membrane.     

Ethylene propylene diene terpolymer/ethylene vinyl acetate/layered silicate ternary nanocomposite by solution method

A new ternary nanocomposite has been developed using ethylene propylene diene terpolymer (EPDM), ethylene vinyl acetate (EVA‐45) copolymer, and organically modified layered silicate (16 Me‐MMT) from sodium montmorillonite (Na⁺‐MMT). Wide angle X‐ray diffraction and transmission electron microscopic analysis confirmed the intercalation of the polymer chains in between the organosilicate layers and the nanoscale distribution of 16 Me‐MMT in polymer matrix, respectively. The measurement of mechanical properties for 2–8 wt% of 16 Me‐MMT loadings showed a significant increase in tensile strength, elongation at break, and modulus at different elongations. Such an improvement in mechanical properties has been correlated based on the fracture behavior of nanocomposite by SEM analysis. Thermal stability of EPDM/EVA/layered silicate ternary nanocomposites also showed substantial improvements compared with the neat EPDM/EVA blend, confirming thereby the formation of a high performance nanocomposite. POLYM. ENG. SCI., 46:437–843, 2006. © 2006 Society of Plastics Engineers     

Natural rubber/poly(ethylene‐co‐vinyl acetate)‐blend‐based nanocomposites

Natural rubber (NR)/poly(ethylene‐co‐vinyl acetate) (EVA) blend–clay nanocomposites were prepared and characterized. The blend nanocomposites were prepared through the melt mixing of NR/EVA in a ratio of 40/60 with various amounts of organoclay with an internal mixer followed by compression molding. X‐ray diffraction patterns revealed that the nanocomposites formed were intercalated. The formation of the intercalated nanocomposites was also indicated by transmission electron microscopy. Scanning electron microscopy, used to study the fractured surface morphology, showed that the distribution of the organoclay in the polymer matrix was homogeneous. The tensile modulus of the nanocomposites increased with an increase in the organoclay content. However, an increase in the organoclay content up to 5 phr did not affect the tensile strength, but the organoclay reduced this property when it was increased further. This study also indicated that a low silicate content dispersed in the blend matrix was capable of increasing the storage modulus of the material. The addition of the organoclay also increased the decomposition temperature of the NR/EVA blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 353–362, 2006     

Microstructure and thermal properties of ethylene‐(vinyl acetate) copolymer/rectorite nanocomposites

Ethylene‐(vinyl acetate) copolymer (EVA)/rectorite nanocomposites were prepared by direct melt extrusion of EVA and organo‐rectorite. The microstructures and thermal properties of EVA nanocomposites were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), solid‐state nuclear magnetic spectroscopy, positron annihilation spectroscopy, thermal gravimetric analysis (TGA) and dynamic mechanical analysis techniques. XRD pattern and SEM images show that the intercalated structure is formed and rectorite is finely dispersed in EVA matrix. When organoclay content of the hybrid increases to 7.5 wt%, or pristine rectorite was used instead of organoclay, the crystallization behavior of EVA nanocomposite changes greatly and the ratio of the monoclinic to orthorhombic crystal increases significantly. The relative fractional free volume of the nanocomposite decreases with the increasing organo‐rectorite content, and the values of damping factor (tan δ) for all nanocomposites are lower than that of pure EVA. These facts illuminate that intercalated structure restricts the segment motion and mobilization of polymer chain. TGA results of EVA nanocomposites in air indicate that deacylation of EVA is accelerated because of the catalytic effect and the thermal degradation of the main chain is delayed owing to the barrier effect of silicate layers. Copyright © 2005 Society of Chemical Industry     

Characterization of polymer‐layered silicate (clay) nanocomposites by transmission electron microscopy and X‐ray diffraction: A comparative study

Several polymer‐layered silicate (clay) nanocomposites (PLSNs) were analyzed by transmission electron microscopy (TEM) and wide‐angle X‐ray diffraction (XRD) in an effort to characterize the nanoscale dispersion of the layered silicate. The PLSNs investigated included thermoset (cyanate esters) and thermoplastic polymers (polystyrene, nylon 6, and polypropylene‐g‐maleic anhydride). The results of this study reveal that the overall nanoscale dispersion of the clay in the polymer is best described by TEM, especially when mixed morphologies are present. XRD is useful for the measurement of d‐spacings in intercalated systems but cannot always observe low clay loadings (<5%) or be used as a method to identify an exfoliated nanocomposite where no XRD peaks are present (constituting a negative result). Most importantly, the study showed that XRD is not a stand‐alone technique, and it should be used in conjunction with TEM. Our studies suggest that new definitions, or a clarification of existing definitions, are needed to properly describe the diversity of PLSN nanostructures seen in various materials. Published 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1329–1338, 2003     

Transport properties of natural rubber latex layered clay nanocomposites

Natural rubber latex layered clay nanocomposites were prepared with low loadings of nanoclay using conventional compounding technique. A higher loading of clay resulted in processing difficulties due to viscosity build up. X‐ray analysis showed that nanocomposites in which layered silicate layers were either delaminated or ordered as in an intercalated structure was obtained. Partially exfoliated structure was observed from TEM photographs of nanocomposites with 3 phr nanoclay. The transport properties, sorption, diffusion, and permeation coefficients were measured using the solvent toluene at 303 K. A higher decrease for the diffusion coefficient for nanocomposites directs the presence of tortuous path for the diffusing molecules. Thermodynamic parameters show a better compatibility for the silicates with rubber resulted in the formation of an elastomeric network. Gas permeability results of the nanocomposites suggest a better barrier resistancefor oxygen molecules even in lower loading of nanoclay and different gas transport models (Nielsen, Bharadwaj, Cussler) were applied to describe the behavior of these nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Visualisation of Nanoclay Dispersion in Polymer Matrix by High‐Resolution Electron Microscopy Combined with Electron Tomography

In order to establish the structure‐property relationship in the case of clay containing polymer nanocomposites, detailed understanding of silicate layers dispersion into the polymer matrix is necessary. In this study, biodegradable poly[(butylene succinate)‐co‐adipate] (PBSA) was chosen as a model polymer and the nanocomposite of PBSA with organically modified montmorillonite (OMMT) was prepared via the melt‐mixing in a batch mixer. The degree of dispersion of silicate layers in the PBSA matrix was investigated by means of wide angle X‐ray diffraction, small angle X‐ray scattering, high‐annular‐angle‐dark‐field scanning transmission electron microscopy, and high resolution transmission electron microscopy combined with electron tomography. Results demonstrated the homogeneous dispersion of clay platelets in the PBSA matrix. However, the true exfoliation of silicate layers in the polymer matrix is quite difficult to achieve, although there are strong favourable interactions between the polymer matrix and the OMMT surface.

     

Estimation of reinforcement in compatibilized polypropylene nanocomposites by extensional rheology

Structural characterization in polymer nanocomposites is usually performed using X‐ray scattering and microscopic techniques, whereas the improvements in processing and mechanical properties are commonly investigated by rotational rheometry and tensile testing. However, all of these techniques are time consuming and require quite expensive scientific equipment. It has been shown that a fast and efficient way of estimating the level of reinforcement in polymer nanocomposites can be performed by melt extensional rheology, because it is possible to correlate the level of melt strength with mechanical properties, which reflect both the 3D network formed by the clay platelets/polymer chains as well as final molecular structure in the filled system. The physical network made of silicate filler and polymer matrix has been evaluated by X‐ray diffraction and transmission electron microscopy. Extensional rheometry and tensile testing have been used to measure efficiency of the compatibilizer amount in a polypropylene‐nanoclay system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009