Preparation and characterization of EVA/clay Nanocomposites with improved barrier performance

Poly (ethylene‐co‐vinyl acetate) (EVA)/clay nanocomposites containing two different organoclays with different clay loadings were prepared. The transport of gases (oxygen and nitrogen) through the composite membranes was investigated and the results were compared. These studies revealed that the incorporation of nanoclays in the polymer increased the efficiency of the membranes toward barrier properties. It was also found that the barrier properties of the membranes decreased with clay loadings. This is mainly due to the aggregation of clay at higher loadings. The morphology of the nanocomposites was studied by scanning electron microscopy, transmission electron microscopy and X‐ray scattering. Small angle X‐ray scattering results showed significant intercalation of the polymer chains between the organo‐modified silicate layers in all cases. Better dispersed silicate layer stacking and more homogeneous membranes were obtained for Cloisite® 25A based nanocomposites compared with Cloisite® 20A samples. Microscopic observations (SEM and TEM) were coherent with those results. The dispersion of clay platelets seemed to be maximized for 3 wt % of clay and agglomeration increased with higher clay loading. Wide angle X‐ray scattering results showed no significant modifications in the crystalline structure of the EVA matrix because of the presence of the clays. The effect of free volume on the transport behavior was studied using positron annihilation spectroscopy. The permeability results have been correlated with various permeation models. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and morphological evolution of heterophasic PP‐EP/EVA/organoclay nanocomposites: Effect of the nanoclay organic modifier

A study is presented on the morphological effects caused by the nanoclay organic modifier and the nanoclay concentration. This was made under previously determined compatibility conditions of heterophasic polypropylene copolymers (PP‐EP)/poly(ethylene vinyl acetate) (EVA)/organoclay nanocomposites. The nanocomposites were prepared using the fluidity of the EVA phase to disperse the nanoclay platelets. Therefore, no additional compatibilizer was used to achieve the clay dispersion. Two organoclays were used with different characteristics and polarity of the substituent groups. Transmission electron microscopy and X‐ray diffraction results first indicated that two hydrogenated tallow modifiers are more effective than one to enhance nanoclay exfoliation. Thermogravimetric studies indicated a low probability of thermal degradation of the nanoclay modifiers and as a consequence of their effect on the layer–layer exfoliation. Molecular simulations were made with the purpose to study additional factors affecting exfoliation. The introduction of nanoclay, within the compatibility conditions of the PP‐EP/EVA system, was also studied. It was determined that the system preserved its original morphology and that the silicate layers were hosted by the EVA domains. The crystallization characteristics of the PP‐EP/EVA mixtures indicated a gradual evolution of the overall crystalline structures depending on the EVA content. In the case of the ternary nanocomposites PP‐EP/EVA/nanoclay, the β crystalline structure was partially formed, although it decreased with increasing nanoclay content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of blending sequence on the microstructure and properties of PBT/EVA‐g‐MAH/organoclay ternary nanocomposites

Ternary nanocomposites based on poly(butylene terephthalate) (PBT), maleic anhydride grafted poly(ethylene‐co‐vinyl acetate) (EVA‐g‐MAH), and organically modified montmorllonite (organoclays) were prepared through four different blending sequences in a Haake rheocord mixer: (1) To blend PBT, EVA‐g‐MAH and organoclays in one step; (2) First to prepare EVA‐g‐MAH/organoclay nanocomposite, then mix it with PBT to get the final nanocomposite; (3) To mix PBT with organoclays first, then the PBT/organoclay nanocomposite with EVA‐g‐MAH. (4) To mix organoclays with the PBT/EVA‐g‐MAH blend. The microstructure of the PBT/EVA‐g‐MAH/organoclay ternary hybrids was characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). It was found that the blending sequence significantly influences the microstructure of PBT/EVA‐g‐MAH/organoclay ternary hybrids and the dispersion behavior of the organoclays in the polymer matrix. Tensile and impact properties of the hybrids were also studied. The results showed that the mixing sequence (2) gives the best tensile and impact strength due to its fine “sea‐island” morphology of PBT/EVA‐g‐MAH blend and good dispersion of the organoclays in the continuous PBT matrix.     

Effect of layered silicate on EPDM/EVA blend nanocomposite: Dynamic mechanical,thermal, and swelling properties

Polymer blend nanocomposites have been developed by solution method using ethylene propylene diene terpolymer (EPDM), ethylene vinyl acetate (EVA‐45) copolymer, and organically modified layered silicate. Morphological investigation made by wide‐angle X‐ray diffraction and transmission electron microscopic analysis indicates intercalated structure of EPDM/EVA nanocomposites with partial disorder. Scanning electron microscopic studies exhibit the phase behavior of EPDM/EVA blend nanocomposites. Dynamic mechanical thermal analysis shows a significant increase in storage modulus in the rubbery plateau. The decrease in damping (tan δ) value and enhanced glass‐transition temperature (T_g) demonstrate the reinforcing effect of layered silicate in the EPDM/EVA blend matrix. The tensile modulus of these nanocomposites also showed a significant improvement with the filler content. The main chain scission of EPDM/EVA blend nanocomposites compared with the neat EPDM/EVA blend showed substantial improvement in thermal stability in nitrogen, whereas a sizeable increase is observed in air. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

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.     

Exertion of Inhibiting Effect by Aluminosilicate Layers on Swelling of Solution Blended EVA/Clay Nanocomposite

Summary: Ethylene vinyl acetate (EVA) copolymer/dodecyl ammonium ion intercalated montmorillonite (12Me‐MMT) nanocomposites were swelled in xylene under atmospheric condition. Swelling index of these nanocomposites decreased with filler loading indicating that the solvent uptake of these nanocomposites was inversely related to the filler contents. The volume fractions of nanocomposites showed an increasing trend with filler concentration because of unswelling effect exerted by aluminosilicate layers. The cross‐link density was determined using the Flory‐Rehner equation and it was observed that the cross‐link density of these nanocomposites also showed an increasing trend with increasing filler loading. Free energy change (ΔG_mix) and the change in entropy (ΔS_mix) on swelling of EVA/12Me‐MMT nanocomposites in xylene were calculated and these values reaffirmed that the interaction between polymer chains and silicate layers was very strong which induced remarkable inhibiting ability on EVA matrix when swelled in xylene.

TEM photograph of EVA/12Me‐MMT nanocomposite containing 8 wt.‐% 12Me‐MMT.     

Effects of epoxy treatment of organoclay on structure, thermo-mechanical and transport properties of poly(ethylene terephthalate-co-ethylene naphthalate)/organoclay nanocomposites

Poly(ethylene terephthalate-co-ethylene naphthalate) (PETN) nanocomposites containing two different organoclays, Cloisite 20A and 30B, were prepared by melt intercalation using an extruder. The organoclays was treated with epoxy monomer to further improve the polar interactions with PETN matrix. The morphological, thermal-mechanical, mechanical and gas barrier characteristics of the nanocomposites were evaluated using several characterization tools. It is found that the Cloisite 30B had better interactions with PETN and was more uniformly dispersed within PETN than Cloisite 20A. Epoxy treatment of Cloisite 30B organoclay resulted in improvements in d-spacing between silicate layers, thermo-mechanical and tensile properties, as well as thermal stability, processing and gas barrier characteristics of the PETN/30B nanocomposites. These results suggest that the epoxy acted as the compatibilizer as well as the chain extender, improving the chemical interactions between PETN and organoclay, while discouraging the macromolecular mobility of polymer chains in the vicinity clay particles. The implications and the mechanisms behind these observations are discussed.     

Preparation and interaction characteristics of exfoliated ABS/organoclay nanocomposite

A series of poly(acrylonitrile‐co‐butadiene‐co‐styrene) (ABS)/organoclays (Cloisite10A, Cloisite25A, and Cloisite30B) nanocomposites are prepared via two different methods: one is a solution blending and the other is a two‐step process where the solution blended mixture is subsequently compounded in the melt state using a torque rheometer (SOAM method). The effect of surfactants on the surface of three different organoclays that are modified with alkylammonium salts in polymer/organoclay nanocomposites is investigated by focusing on two major aspects; Flory‐Huggins interaction parameters and physical (thermal and mechanical) properties. The d‐spacing of both neat organoclays and intercalated/exfoliated organoclays is examined by X‐ray diffraction analysis, and the microstructure of these nanocomposites is examined by FE‐TEM. Solubility parameters of both polymer and organoclays of interest are calculated according to the group contribution method. Viscoelastic behavior of the nanocomposites is also investigated by measuring rheological properties under an oscillatory shear. The increase in the onset temperature of the thermal degradation indicates the enhancement of thermal stability of ABS due to intercalation or partial exfoliation. Mechanical properties, such as, tensile strength, tensile modulus, and elongation at break of the nanocomposites are measured. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

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     

Synthesis and properties of poly(methyl methacrylate)/montmorillonite (PMMA/MMT) nanocomposites

PMMA/MMT nanocomposites were successfully synthesized via in situ intercalative polymerization, and characterized by means of wide‐angle X‐ray diffractometry, transmission electron microscopy, thermal gravimetric analysis, dynamic mechanical analysis and Fourier‐transform infrared analysis. The nanocomposites possess partially exfoliated and partially intercalated structure, in which the silicate layers are exfoliated into nanometre secondary particles with thickness of less than 20 nm and uniformly dispersed in the polymer matrix. In comparison with pure PMMA, the thermal stability, glass transition temperature, and mechanical properties of the polymer are notably improved by the presence of the nanometric silicate layers. It was found that part of the PMMA chains in the nanocomposites are well immobilized inside and/or onto the layered silicates and, therefore, the unique properties of the nanocomposites result from the strong interactions between the nanometric silicate layers and the polymer chains. Copyright © 2003 Society of Chemical Industry     

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     

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 copolymer/multiwalled carbon nanotube/organoclay nanocomposites

Ethylene‐vinyl acetate copolymer (EVA) was melt‐mixed with multiwalled carbon nanotubes (MWCNTs) and organoclays, and the effects of simultaneous use of organoclays and MWCNTs on the surface resistivity and tensile properties of EVA nanocomposites were investigated. The surface resistivity of EVA/MWCNT nanocomposite with 1 phr of MWCNT is out of our measurement range (above 10¹² Ω/square). With increasing content of organoclay from 0 to 3 phr, the surface resistivity of the EVA/MWCNT/organoclay nanocomposites with 1 phr MWCNT remains out of our measurement range. However, the surface resistivity of the nanocomposite decreases to 10⁶ Ω/square with addition of 5 phr organoclay. The tensile properties of EVA/MWCNT/organoclay nanocomposites with 1 phr MWCNT and 5 phr organocaly are similar to those of EVA/MWCNT nanocomposites with 5 phr MWCNT except tensile modulus. POLYM. COMPOS. 2012. © 2012 Society of Plastics Engineers     

Manipulating the microstructure and rheology in polymer‐organoclay composites

A series of nanocomposites prepared by melt‐blending of cloisite‐based organoclays with poly(ethylene‐vinylacetate) (EVA) and neutralized poly (ethylene‐methacrylic acid) (EMA) copolymers were investigated via DSC, small‐angle X‐ray scattering (SAXS), and rheological techniques. SAXS results indicated partial clay exfoliation in all samples. In both EMA and EVA systems, the nominal melting temperature T_m and bulk crystallinity are not significantly affected by the presence of organoclays, suggesting that clay particles are predominantly confined in the amorphous phase. In rheological measurements (above T_m), the EVA‐clay system demonstrated a solid‐like rheological behavior under the small‐strain oscillatory shear, yet it was able to yield and flow under a steady shear, which is the characteristic of physical crosslinking. In contrast, the EMA‐clay system exhibited a melt‐like rheological behavior, where the influence of organoclay on the thermorheological behavior of the EMA composite was quite minimal. We propose that the carbonyl groups of vinylacetate in EVA interact with the clay surface, resulting in a strong physically crosslinking like interaction in the melt. On the other hand, the interaction between EMA and clay is weak because of repulsion between carboxyl anions and negatively charged clay surface.     

Nanocomposites of ethylene-vinyl acetate copolymer (EVA) and organoclay prepared by twin-screw melt extrusion

Preparation of nanocomposites based on ethylene-vinyl acetate copolymer (EVA) and organoclay by melt intercalation is described in this paper. Effects of VA content, melt flow index (MFI) and maleation of EVA on melt intercalation were investigated by X-ray diffraction. The level of intercalation into the organoclay increases greatly as VA content increases from 6 to 12 wt%, but shows minimal change from 12 to 28 wt%. For 28 wt% VA content polymers with MFI from 3 to 150, interlayer expansion exhibited a maximum at MFI = 6. Exfoliated nanocomposites were not obtained for a range of unfunctionalized EVA's of different VA content and MFI. Use of maleated EVA (MEVA) had an obvious improvement on exfoliation of the silicate layers probably due to chemical interaction between the MEVA matrix and silicate layers. FTIR results showed that the MA functionality reacts during processing. Lower clay content favored formation of an exfoliated nanocomposite structure. Exfoliated nanocomposites from MEVA exhibited higher Young's modulus and tensile strength than either pure EVA or intercalated nanocomposites from non-maleated EVA. Polym. Compos. 25:535–542, 2004. © 2004 Society of Plastics Engineers.     

Morphology of EVA based nanocomposites under shear and extensional flow

Shear and extensional rheological measurements were conducted in conjunction with laser light scattering (LLS) on ethylene‐vinyl acetate copolymer (EVA) nanocomposites. The materials were prepared by melt‐mixing EVA and commercially acquired layered silicates. Wide Angle X‐Ray Scattering (WAXS) was used to ascertain the degree of layer swelling. This could be attributed to the intercalation of polymer chains into the interlayer of the silicates. The nanocomposites prepared were determined to be predominantly intercalated in nature. In shear rheological tests, the nanocomposites exhibited an increase in viscoelastic properties compared to the pure EVA. The extent of this property enhancement was not as pronounced as had been reported in many instances with respect to other polymer nanocomposites. This could be attributed to the absence of a network structure normally observed in an exfoliated system. The extensional rheological tests showed an increase in extensional flow properties. This was confirmed by the LLS, which indicated that the filled systems had higher deformability than the unfilled one. Polym. Eng. Sci. 44:1220–1230, 2004. © 2004 Society of Plastics Engineers.     

Effects of different kinds of clay and different vinyl acetate content on the morphology and properties of EVA/clay nanocomposites

A series of EVA/clay nanocomposites and microcomposites have been prepared via melt-blending. Using four kinds of EVA with different vinyl acetate (VA) contents: 28, 40, 50 and 80 wt%, and four kinds of clay: three are organophilic clay (OMMT) and one unfunctionalized clay (Na-MMT), the effects of different VA content of EVA and the kinds of the clay on the morphology and properties of EVA/clay nanocomposites were systematically investigated. In previous studies, there are only two distinct nanostructures to distinguish polymer/clay nanocomposites: the intercalated and the exfoliated. But in this paper, we proposed a new nanostructure—‘the wedged’ to describe the dispersion degree of clay in nanocomposites, it means the sheets of clay were partly wedged by the chains of polymer. The wedged, the intercalated and the partially exfoliated structures of EVA/clay nanocomposites were characterized by X-ray diffraction (XRD) and by high-resolution transmission electron microscopy (HRTEM). The enhanced storage modulus of EVA/clay nanocomposites was characterized by dynamic mechanical thermal analysis (DMTA). The enhanced degree in the storage modulus of the OMMT on EVA/clay nanocomposites with the partially exfoliated and intercalated structure is much higher than that with wedged structure, and that with the higher VA content is higher than that with the lower. The thermal stabilities of EVA/clay nanocomposites were also studied by thermal gravimetric analysis (TGA).     

Effect of processing conditions on the structural morphology of PP–EP/EVA/organoclay ternary nanocomposites

The effect of processing conditions on the morphology of heterophasic PP–EP/EVA/organoclay ternary nanocomposites was examined. The nanocomposites were prepared in a co-rotating twin screw extruder with different screw configurations and incorporation methods. Three different sizes of EVA granules were used. The results obtained by X-ray scattering (WAXD) and electronic microscopy (TEM) showed an increase in d spacing value of the clay associated with the polar interactions between the vinyl acetate of EVA and the surface of the nanoclays. In addition, some chains of the non-polar copolymer PP–EP may have become intercalated into the clay galleries as a result of polymer diffusion induced by shear stress during melt mixing. An increase in surface area of EVA granules resulted in a more homogenous clay dispersion and intercalation. The morphologic changes resulted in an increase in heat distortion temperature (HDT) and flexural modulus of the ternary nanocomposites.     

EVA／Al（OH）3纳米复合材料性能的研究

采用熔融共混挤出法制备了EVA／Al(OH)3纳米复合材料。用TEM、SEM分析了Al(OH)3粉体改性前后在EVA树脂中的分散性与相容性。研究了表面处理对复合材料阻燃与力学性能的影响，并对Al(OH)3阻燃机理进行了探讨。结果表明：采用钛酸酯偶联剂对粉体进行表面改性可有效改善其在树脂中的分散与结合情况，复合材料阻燃级别提高到UL94 V-1级，拉伸性能得到改善。     

Short communication: Carbon nanotubes as flame retardants for polymers

Flame retardant nanocomposites were synthesized by melt‐blending ethylene‐vinyl acetate copolymer (EVA) with multi wall carbon nanotubes. Fire property measurements by cone calorimeter revealed that the incorporation of multi wall carbon nanotubes into EVA significantly reduced the peak heat release rates compared with the virgin EVA. Peak heat release rates of EVA with multi‐wall carbon nanotubes were slightly improved compared with EVA nanocomposites based on modified layered silicates. Char formation is the main important factor for these improvements. There was also a synergistic effect by the combination of carbon nanotubes and organoclays resulting in an overall more perfect closed surface with improved heat release values. Copyright © 2002 John Wiley & Sons, Ltd.