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     

Polymer nanocomposites based on transition metal ion modified organoclays

A unique class of nanocomposites containing organoclays modified with catalytically active transition metal ions (TMI) and ethylene vinyl acetate (EVA) copolymers was prepared. The morphology, thermal and rheological properties of these nanocomposites were studied by thermal gravimetric analysis (TGA), transmission electron microscopy (TEM), extended X-ray absorption fine structure (EXAFS) spectroscopy, X-ray scattering/diffraction and oscillatory shear rheometry. TMI-modified organoclays were thought to possess pillaring of multivalent TMI in the interlayer silicate gallery, leading to a notable reduction of the interlayer d-spacing. The resulting nanocomposites exhibited significantly improved thermal stability and fire retardation properties, but similar morphology (i.e., an intercalated-exfoliated structure) and rheological properties comparable with EVA nanocomposites containing unmodified organoclays. It appears that the compressed organic component in the TMI-modified organoclay can still facilitate the intercalation/exfoliation processes of polymer molecules, especially under extensive shearing conditions. The improved fire retardation in nanocomposites with TMI-modified organoclays can be attributed to enhanced carbonaceous char formation during combustion, i.e., charring promoted by the presence of catalytically active TMI.     

Oxygen permeability and the mechanical and thermal properties of (low‐density polyethylene)/poly (ethylene‐co‐vinyl acetate)/organoclay blown film nanocomposites

Various (low‐density polyethylene)/poly(ethylene‐co‐vinyl acetate) (LDPE/EVA) nanocomposites containing organoclay were prepared by one‐ and two‐step procedures through melt blending. The resultant nanocomposites were then processed via the film blowing method. From the morphological point of view, X‐ray diffraction and optical microscopy studies revealed that although a prevalent intercalated morphology was evident in the absence of EVA, a remarkable increase of organoclay interlayer spacing occurred in the EVA‐containing systems. The advantages of the addition of EVA to the LDPE/organoclay nanocomposites were confirmed in terms of oxygen barrier properties. In other words, the oxygen transmission rates of the LDPE/EVA/organoclay systems were significantly lower than that of the LDPE/organoclay sample. The LDPE/EVA/organoclay films had better mechanical properties than their counterparts lacking the EVA, a result which could be attributed to the improvement of the organoclay reinforcement efficiency in the presence of EVA. Differential scanning calorimetry and thermogravimetric analysis experiments were performed to follow the effects of the EVA and/or organoclay on the thermal properties of LDPE. Finally, the films produced from the two‐step‐procedure compound showed enhanced oxygen barrier properties and mechanical behavior as compared to the properties of the films produced via the one‐step procedure. J. VINYL ADDIT. TECHNOL., 19:132–139, 2013. © 2013 Society of Plastics Engineers     

Rheological properties of poly(lactic acid) based nanocomposites: Effects of different organoclay modifiers and compatibilizers

Poly(lactic acid) (PLA) nanocomposites containing five types of organically modified, layered silicates and two elastomeric compatibilizers, namely ethylene‐glycidyl methacrylate (E‐GMA) and ethylene‐butyl acrylate‐maleic anhydride (E‐BA‐MAH), were prepared using a twin screw extruder. The morphologies of the nanocomposites were determined by X‐ray diffraction (XRD) and transmission electron microscopy (TEM), and the rheological properties of the melts were measured using small‐amplitude oscillatory shear. XRD revealed that the addition of E‐GMA to the binary nanocomposites resulted in higher compatibility between the organoclay nanoplatelets and the polymer matrix. TEM showed that all of the nanocomposites contained mixed dispersed structures, involving tactoids of various sizes, as well as intercalated and exfoliated organoclay layers. Rheological properties were found to be affected by the differences in the compatibility between the organoclays and the polymer matrix, and by the addition of the compatibilizer. Organoclay types that resulted in high level of dispersion exhibited higher values of complex viscosity compared to that of neat PLA. The addition of E‐GMA introduced a solid‐like rheological behavior at low frequencies. All of the nanocomposites had similar rheological behavior at high frequencies. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42915.     

Preparation and characterization of polypropylene/solid‐state organomodified montmorillonite nanocomposites

A novel organomodified montmorillonite prepared by solid‐state method and its nanocomposites with polypropylene were studied. The interaction between modifying agent and montmorillonite was investigated by X‐ray diffraction (XRD) analysis, contact angle determination, and Fourier‐transform infrared spectroscopy. The results showed that the modifying agent behaves as an effective intercalating agent, enlarging the interlayer spacing of montmorillonite and making montmorillonite more hydrophobic. Polypropylene/solid‐state organomodified montmorillonite composites were prepared by melt‐mixing method. The dispersion of the silicates was investigated by XRD analysis and transmission electron microscopy. It was found that the nanocomposites are formed with solid‐state organomodified montmorillonite and polypropylene. The thermogravimetric analysis and differential scanning calorimetry results showed that the organoclay could enhance the thermal stability and decrease the relative crystallinity of polypropylene. Mechanical and rheological tests indicated that the organoclay improves the mechanical properties but has no obvious effect on rheological properties of polypropylene. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

An investigation on the correlation between rheology and morphology of nanocomposite foams based on low‐density polyethylene and ethylene vinyl acetate blends

This article presents the correlation between rheology and morphology of nanocomposite foams of low‐density polyethylene (LDPE), ethylene vinyl acetate (EVA), and their blends. LDPE/EVA nanocomposites were prepared via melt mixing and then foamed using batch foaming method. To assess the rheological behavior of polymer melts, frequency sweep and creep recovery tests were done. Morphology of the samples was also studied by scanning electron microscopy and X‐ray diffraction. The results showed that with increase in clay content, storage modulus, complex and zero shear viscosities will be increased, which affect the foam morphology. In addition, elasticity plays an important role in foaming process, in a way that samples with more elasticity percentage have the highest cell density and the lowest cell size. POLYM. COMPOS., 31:1808–1816, 2010. © 2010 Society of Plastics Engineers.     

Master batch approach for developing PVDF/EVA/CNT nanocomposites with co-continuous morphology and improved electrical conductivity

Conducting polymer composites constituted by co-continuous poly (vinylidene fluoride) (PVDF)/ ethylene- vinyl acetate copolymer (EVA) blends with multiwalled carbon nanotube (CNT) were prepared by melt mixing using different procedures. The effect of the master batch approach on the conductivity, morphology, mechanical, thermal and rheological properties of PVDF/EVA/CNT nanocomposites was compared with that based on one step mixing strategy. The selective extraction experiments revealed that CNT was preferentially localized in the EVA phase in all situations, even when PVDF@CNT master batch was employed. Nanocomposites prepared with EVA@CNT master batch displayed higher conductivity, whose value reached around 10⁻¹ S m⁻¹ with the addition of 0.56 vol% of CNT. The better electrical performance was attributed to the better distribution of the filler, as indicated by transmission electron microscopy and rheological behavior. The electrical and rheological behavior were also investigated as a function of the CNT content.     

Multiwalled carbon nanotube/montmorillonite hybrid filled ethylene‐co‐vinyl acetate nanocomposites with enhanced mechanical properties,thermal stability,and dielectric response

Homogeneous multiwalled carbon nanotube/montmorillonite hybrid filler (HMM) dispersion was prepared by co‐ultrasonication and was subsequently used to prepare ethylene‐co‐vinyl acetate (EVA) nanocomposites by solution blending method. XRD and TEM analysis of HMM confirm significant interaction between the montmorillonite (MMT) layers and multiwalled carbon nanotubes (MWCNT) in line with previous reports. Analysis of the nanocomposites shows the constituent fillers to be homogeneously dispersed in EVA matrix. Mechanical properties of neat EVA are remarkably improved with HMM content up to 3 wt% followed by reversion. Maximum improvement observed in tensile strength, elongation at break, and toughness are 424%, 109%, and 1122%, respectively. Results show maximum thermal stability at 4 wt% and best dielectric response at 1 wt% HMM content. Exceptional mechanical and dielectric properties of EVA nanocomposites attained may be attributed to homogeneous dispersion of fillers and improved polymer–filler interaction. Comparison shows excellent synergy between MWCNT and MMT towards mechanical reinforcement of EVA. POLYM. ENG. SCI., 58:1155–1165, 2018. © 2017 Society of Plastics Engineers     

Morphology, rheology and dynamic mechanical properties of PP/EVA/clay nanocomposites

This paper reports on morphology, rheology and dynamic mechanical properties of polypropylene (PP)/ethylene vinyl acetate (EVA) copolymer/clay nanocomposite system prepared via a single step melt compounding process using a twin screw micro-compounder. Scanning electron microscopic (SEM) investigations revealed that the dispersed phase droplet size was reduced with incorporation of an organo-modified montmorillonite (OMMT). This reduction was more significant in presence of a maleated PP (PP-g-MAH) used as compatibilizer. Phase inversion in the compatibilized blends caused a further decrease in PP droplet size. The OMMT gallery spacing was higher in nanocomposites with EVA as matrix which could be attributed to higher tendency of OMMT nanoparticles towards EVA rather than PP. This enhanced tendency was confirmed by rheological analysis too. Transmission electron microscopy (TEM) results also showed that the majority of OMMT nanoparticles were localized on the interface and within EVA droplets. According to dynamic mechanical analysis, the compatibilized nanocomposites showed higher storage and loss moduli due to better dispersion of OMMT layers. The modulus enhancement of nanocomposites as a function of OMMT volume fraction was modeled by Halpin-Tsai’s-Nielsen expression of modulus for nanocomposites. The results of modeling suggested that the aspect ratio of the intercalated OMMT, in the form of Einstein coefficient (K _E), plays a determining role in the modulus enhancement of nanocomposites.     

Influence of organophilic clay and preparation methods on EVA/montmorillonite nanocomposites

Ethylene‐vinyl acetate copolymer (EVA)/montmorillonite MMT nanocomposites have been prepared by using different methods: one is from the organophilic montmorillonite (OMT) and the other is from the pristine MMT and reactive compatibilizer hexadecyl trimethyl ammonium bromide (C16). In this study, different kneaders were used (twin‐screw extruder and twin‐roll mill) to prepare nanocomposites. The nanocomposite structures are evidenced by the X‐ray diffraction (XRD) and high‐resolution electronic microscope (HREM). The thermal properties of the nanocomposites were investigated by thermogravimetric analysis (TGA). Moreover, the tensile tests were carried out with a Universal testing machine DCS‐5000. It is shown that different methods and organophilic montmorillonite have influence on EVA/MMT nanocomposites.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2416–2421, 2004     

Effect of polymer matrix/montmorillonite compatibility on morphology and melt rheology of polypropylene nanocomposites

In this study, Ca²⁺‐montmorillonite (Ca²⁺‐MMT) and organo‐montmorillonite (OMMT) were modified by three compatibilizers with different degrees of polarity [poly(ethylene glycol) (PEG), alkyl‐PEG, and polypropylene (PP)‐g‐PEG]. PP/MMT nanocomposites were prepared by melt blending and characterized using X‐ray diffraction and transmission electron microscopy. The results showed the degree of dispersion of OMMT in the PP/PP‐g‐PEG/OMMT (PMOM) nanocomposite was considerably higher than those in the PP/PEG/OMMT and PP/alkyl‐PEG/OMMT nanocomposites, which indicated that the dispersion was relative to the compatibility between modified OMMT and PP matrix. Linear viscoelasticity of PP/MMT nanocomposites in melt states was investigated by small amplitude dynamic rheology measurements. With the addition of the modified MMT, the shear viscosities and storage modulus of all the PP/MMT nanocomposites decreased. It can be attributed to the plasticization effect of PEG segments in the three modifiers. This rheological behavior was different from most surfactant modified MMT nanocomposites which typically showed an increase in dynamic modulus and viscosity relative to the polymer matrix. The unusual rheological observations were explained in terms of the compatibility between the polymer matrix and MMT. In addition, the mechanical properties of PP/MMT nanocomposites were improved. A simultaneous increase in the tensile strength and toughness was observed in PP/PMOM nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Poly(ethylene‐co‐vinyl acetate)/calcium phosphate nanocomposites: Mechanical,gas permeability,and molecular transport properties

Poly(ethylene‐co‐vinyl acetate) (EVA)‐based nanocomposites were prepared by melt mixing in an internal mixer with nanocalcium phosphate in different weight percentages. The nanocalcium phosphate with 10‐nm size was prepared by the polymer‐induced crystallization technique. The mechanical properties as well as the gas permeability tests were performed to analyze the effect of nanofiller incorporation in to the polymer. Molecular transport of different solvents such as water, benzene, and n‐heptane was undertaken at room temperature for EVA nanocomposites with 0, 3, and 5% filler loading. Among the three, water showed less uptake and benzene showed maximum uptake. Transport parameters such as diffusion coefficient, sorption coefficient, and permeation coefficient were calculated, and all of them showed a decrease with respect to the filler loading. First‐order kinetics model was applied to investigate the transport kinetics. Also, the sorption curves were compared to theoretical predictions and found to be in good agreement except for water. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Influence of screw speed on the mechanical and rheological properties of poly(ethylene‐co‐vinyl acetate)—organomodified montmorillonite nanocomposites

Poly(ethylene‐co‐vinyl acetate) (EVA) and organophilic montmorillonite clay nanocomposites were manufactured in a co‐rotating twin‐screw extruder using screw speeds ranging between 200 and 800 rpm. The morphology and thermal‐mechanical and rheological properties were studied to establish processing–morphology–property relationships. Particularly for samples produced under higher screw speed ranges, X‐ray diffraction and transmission electron microscopy revealed a tendency of increased exfoliated clay. Although the mechanical properties improved by the presence of clay, they were not altered by the screw speed. The rheological behavior in the solid and melt states were evaluated and showed that the storage modulus of neat EVA subjected to higher screw speed undergoes more pronounced decrease in the storage modulus than the nanocomposites, suggesting that the clay minimizes the effect of the screw speed. This minimization effect could be explained in the light of the assessment of relaxation times that showed stronger physical interactions with the nanocomposites in the molten state. POLYM. COMPOS., 36:854–860, 2015. © 2014 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     

Ethylene vinyl acetate/ethylene propylene diene terpolymer‐blend‐layered double hydroxide nanocomposites

Ethylene vinyl acetate (EVA‐45)/ethylene propylene diene terpolymer (EPDM) blend‐layered double hydroxide (LDH) nanocomposites have been prepared by solution blending of 1:1 weight ratio of EVA and EPDM with varying amounts of organo LDH (DS‐LDH). X‐ray diffraction and transmission electron microscopy analysis suggest the formation of partially exfoliated EVA/EPDM/DS‐LDH nanocomposites. Measurement of mechanical properties of the nanocomposites (3 wt% DS‐LDH content) show that the improvement in tensile strength and elongation at break are 35 and 12% higher than neat EVA/EPDM blends. Dynamic mechanical thermal analysis also shows that the storage modulus of the nanocomposites at glass transition temperature is higher compared to the pure blend. Such improvements in mechanical properties have been correlated in terms of fracture behavior of the nanocomposites using scanning electron microscopy analysis. Thermal stability of the prepared nanocomposites is substantially higher compared to neat EVA/EPDM blend, confirming the formation of high‐performance polymer nanocomposites. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Metallocene‐based functionalized polyolefins as compatibilizers in polyolefin nanocomposites

This article reports a study of some functionalized polyolefins evaluated as compatibilizers in polyethylene nanocomposites. The functionalized polymers were prepared by direct metallocene‐mediated copolymerizations of ethylene and a functional comonomer. The prepared nanocomposites were evaluated for mechanical and barrier property enhancement. A good combination of mechanical and barrier properties was obtained with the metallocene‐based functionalized polyethylene. The toughness–stiffness balance was better than or comparable to that achieved with conventional functionalized polymers such as maleic anhydride grafted polyethylene. The results also indicated that these metallocene‐based functionalized polyolefins, when used as compatibilizers, could have relatively higher molar masses and lower functionality than those of conventional post‐reactor‐modified compatibilizers, and so the drawbacks associated with the latter could be avoided. Their inherent properties could also further improve the final nanocomposite properties. This was attributed to the more homogeneous nature of metallocene‐catalyzed polymers in comparison with post‐reactor‐modified products. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1094–1100, 2004     

EVA Copolymer Based Nanocomposites

Nanocomposites are a new class of polymer material with an ultrafine phase dispersion of the order of a few nanometers that shows very interesting properties often very different from those of conventional filled polymers. In this work the mechanical and optical properties of Poly[ethylene‐co‐(vinyl acetate)] (EVA copolymer) based nanocomposites have been investigated to evaluate its possible use in several applications. For example, films for covering greenhouses made by EVA copolymer are appealing because of their interesting optical properties and for the so‐called greenhouse effect. Mechanical properties, and the rigidity in particular, are, on the contrary, quite low. Nanocomposites should avoid this shortcoming if optical properties and processability are not unfavorably effected. EVA copolymer based nanocomposites have been prepared by compounding polymer matrix and two different functionalized silicates (0–10 wt.‐%) in molten state. X‐Ray diffractograms show that the in the adopted experimental conditions no exfoliation of the filler is obtained, but an intercalated morphology is observed. Rheological behavior both in shear and in non‐isothermal elongational flow is only slightly influenced by the presence of the filler. As for the mechanical properties, the elastic modulus strongly increases without any worsening of the elongation at break. The permeability in the UV region is not influenced by adding even relatively high contents of the silicates. The improved mechanical and optical properties and the unmodified processability suggest then the use of these new polymeric systems in many applications and in particular as films for covering greenhouses.

UV spectra of the EVA/Nanofil system.     

Rheological and mechanical characteristics of low density polyethylene/ethylene‐vinyl acetate/organoclay nanocomposites

Attempts were made to trace the effect of organoclay (OC) on the rheological and mechanical behaviors of the low density polyethylene (LDPE)/ethylene‐vinyl acetate (EVA) blends. To do this effectively, in addition to LDPE/EVA/OC system, pure LDPE and LDPE/EVA blends were also examined as model systems. The rheological behavior was determined by the capillary rheometer. Morphological characterization was also carried out using X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and theoretical approach based on interfacial energies. Shear viscosity, tensile strength and elastic modulus of LDPE/EVA were found to decrease by increasing the EVA content, while for LDPE/EVA/OC ternary nanocomposites, such properties showed an increase by increasing the content of EVA. Such behavior was explained by the morphological characteristic of the system in which OC was mainly intercalated/exfoliated in the EVA phase. This morphological characteristic was corroborated by the XRD, TEM and interfacial energies data. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Characteristics of polystyrene/polyethylene/clay nanocomposites prepared by ultrasound‐assisted mixing process

In this study, polymer‐clay nanocomposites of various concentrations were prepared by ultrasonically assisted polymerization and melt‐mixing processes. A sonication process using power ultrasonic waves was employed to enhance nano‐scale dispersion during melt‐mixing of polymer blends and organically modified clay. We expected enhanced breakup of layered silicate bundles and further reduction in the size of the dispersed phase, with better homogeneity compared to the different immiscible blend pairs. X‐ray diffraction (XRD) and Transmission Electron Microscopy (TEM) were used to characterize the structures of the nanocomposites. The rheological behaviors of the obtained nanocomposites were measured with parallel plate rheometry. It was found that the ultrasound‐assisted process successfully generated exfoliated nanocomposites and promoted in‐situ compatibilization of the matrix comprising an immiscible pair of polymers in a blend. The resulting nanocomposite exhibited superior thermal stability and elastic modulus compared to the base polymer. Polym. Eng. Sci. 44:1198–1204, 2004. © 2004 Society of Plastics Engineers.     

Dynamic mechanical properties,magnetic and electrical behavior of iron oxide/ethylene vinyl acetate nanocomposites

Nanocomposites of ethylene vinyl acetate (EVA) containing iron oxide nanoparticles (IONPs) were prepared by open mill‐mixing technique. The effect of loading of IONPs in EVA was characterized by Fourier transform infrared (FTIR), X‐ray diffraction (XRD), transmission electron micrograph (TEM), and dynamic mechanical analysis (DMA). The FTIR spectra ascertain the intermolecular interaction between the polymer and IONPs. TEM and XRD studies revealed the structurally ordered arrangement of nanoparticles within the polymer matrix. DMA showed an increase in storage modulus and lesser damping characteristics of composite with the increase in loading of nanoparticles, whereas these properties decreased significantly with increase in temperature. The glass transition temperature shifted toward higher temperature with the increase in content of IONPs. Magnetic properties of the nanocomposites were investigated using vibrating sample magnetometer at room temperature. The saturation of magnetization was progressively increased with the increase in content of nanoparticles. The electrical conductivity, dielectric constant, and dielectric loss of the composite were found to be increased with the increase in volume fraction of nanoparticles. The polymer–filler interaction was also determined from the swelling studies. POLYM. COMPOS., 35:1989–1996, 2014. © 2014 Society of Plastics Engineers