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     

Multiple melting and partial miscibility of ethylene‐vinyl acetate copolymer/low density polyethylene blends

Multiple melting behaviors and partial miscibility of ethylene‐vinyl acetate (EVA) copolymer/low density polyethylene (LDPE) binary blend via isothermal crystallization are investigated by differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD). Crystallization temperature T (°C) is designed as 30, 50, 70, 80°C with different crystallization times t (min) of 10, 30, 60, 300, 600 min. The increase of crystallization temperature and time can facilitate the growth in lateral crystal size, and also the shift of melting peak, which means the completion of defective secondary crystallization. For blends of various fractions, sequence distribution of ethylene segments results in complex multiple melting behaviors during isothermal crystallization process. Overlapping endothermic peaks and drops of equilibrium melting points of LDPE component extrapolated from Hoffman–Weeks plots clarify the existence of partial miscibility in crystalline region between EVA and LDPE. WAXD results show that variables have no perceptible influence on the predominant existence of orthorhombic crystalline phase structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of organoclay content on the mechanical properties of ethylene‐vinyl acetate copolymer/ multi‐walled carbon nanotube/organoclay foams

The main objective of this study is to obtain ethylene‐vinyl acetate copolymer (EVA)/multi‐walled carbon nanotube (MWCNT)/organoclay foams with improved mechanical properties without increase of their density, compared with EVA/MWCNT foams. MWCNT content was fixed at 5 phr in this study. To achieve the objective, EVA was melt‐mixed with MWCNTs and organoclays in a bench kneader. And the obtained EVA/MWCNT/organoclay mixtures were mixed with chemical blowing agent and cross‐linking agent in a two roll‐mill. After being mixed in a two roll‐mill, the mixtures were put in a mold and the foams were obtained by compression‐molding. The effect of organoclay content on the mechanical properties and surface resistivity of EVA/MWCNT (5 phr)/organoclay foams was investigated. The addition of 1 phr organoclays to the EVA/MWCNT (5 phr) foams resulted in the improvement of tensile strength, 100% tensile modulus, tear strength, and compression set without increase of the density. However, further increase in content of organoclay (3 phr) leaded to a deterioration of mechanical properties. Therefore, determining the optimal content of organoclay was very important in order to achieve the main objective of this study. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Rheological study on high‐density polyethylene/organoclay composites

Maleic anhydride‐grafted polyethylene (MAPE) is investigated as a compatibilizer of polyethylene/organoclay nanocomposite. With MAPE help, partial exfoliation of the organoclay occurs in the nanocomposites with the melt compounding method for organoclay loading up to 8.0 wt%. Investigation of the rheological behaviors shows that at high frequencies or shear rates, the viscosity is essentially unaffected by the presence of organoclay; however, at low frequencies or shear rates, viscoelastic behavior alters dramatically, and this is attributed to the presence of anisotropic stacks of randomly oriented organoclay sheets and the formation of network structures. The important observations are firstly the initial stress overshooting observed in steady shear. At low shear rates, stress is much greater at the initial stage than the stress at the steady state; however, it can be eliminated by preshear at low shear rates, which means that preshearing can effectively break down the network structures and align the organoclay. Second, the normalized stress at the overshoot point is a function of the critical strain unit. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

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     

Morphological influence on mechanical characterization of ethylene‐vinyl acetate copolymer–clay nanocomposites

Ethylene‐vinyl acetate copolymer (EVA)/montmorillonite (MMT) clay nanocomposites with varying degree of intercalation and exfoliation have been prepared using direct melt blending techniques with various degrees of polarity (9, 18, and 28 wt% vinyl acetate [VA]) and two different types of clay modification. Morphological characterization using wide‐angle X‐ray scattering (WAXS) and transmission electron microscopy (TEM) have indicated/confirmed the presence of intercalation and/or a combination of intercalation and exfoliation existing in the nanocomposites. The effects of these (simple intercalation or mixed intercalation/exfoliation) states and the effect of changing matrix polarity (by changing VA wt% content) on the nanocomposite mechanical behavior were studied. There is sufficient evidence from the mechanical studies that 1) the presence of nanoclay can simultaneously improve modulus and strength of the nanocomposites, and 2) the mechanical properties are a combined function of the clay concentration and the nanocomposite morphology (due to the VA wt% and presence of clay). It is shown here that interrelation between the VA wt% content and the clay exfoliation affects the mechanical properties in a way that has a positive and increasing slope with increasing loading of clay. It is shown that a clear understanding of the nanocomposite mechanical properties can be obtained from its morphological analysis. POLYM. ENG. SCI., 45:889–897, 2005. © 2005 Society of Plastics Engineers     

Rheological and dynamic mechanical characteristics of rotationally moldable linear low‐density polyethylene fumed silica nanocomposites

In rotational molding process, polymer powders undergo a cycle of heating, melting, cooling, and subsequent solidification in the mold. Resins, like linear low‐density polyethylene (LLDPE), are used in this process on a large scale mainly because of its good mechanical properties and excellent thermal stability. Yet, incorporation of additives is necessary to further improve the visco‐elastic, thermal as well as melt flow properties of the resin. This study investigates the effects of nanocomposites of fumed silica (FS) with rotationally moldable LLDPE. Thermal transitions in the LLDPE‐FS nanocomposites were investigated and correlated with their melt flow characteristics. The effect on melt processing during rotational molding and compounding, were analyzed by melt flow index and torque rheometry studies. A suitable blend of FS in LLDPE has been recommended for rotational molding based on rheological studies and dynamic mechanical analysis. POLYM. COMPOS., 37:2995–3002, 2016. © 2015 Society of Plastics Engineers     

Influence of crosslinking on crystallization,rheological, and mechanical behaviors of high density polyethylene/ethylene‐vinyl acetate copolymer blends

High density polyethylene (HDPE)/ethylene‐vinyl acetate copolymer (EVA) blends with selective crosslinking the EVA phase were prepared and the crystallization, rheological, and mechanical behaviors were studied. Selective crosslinking of EVA component could greatly improve both tensile and impact strengths of the HDPE‐rich blends and influence melting enthalpy at different annealing temperature in successive self‐nucleation and annealing procedure. Dynamic mechanical analysis reveals that glass transition temperatures of both the HDPE and EVA components are lowered upon blending and are raised upon crosslinking. The uncrosslinked HDPE/EVA blends are unstable in the melt and show increment in storage modulus (G′) and decay in loss tangent (tanδ) with annealing time associated with phase coarsening. However, morphology of selectively crosslinked blends in the melt state is highly unstable, characterized by a fast migration of uncrosslinked HDPE component out of the crosslinked EVA phase to the surface resulting in a rapid decay in G′ and an increment in tanδ at the early stage of annealing. POLYM. ENG. SCI., 54:2848–2858, 2014. © 2014 Society of Plastics Engineers     

Effect of electron beam irradiation on the properties of ethylene‐(vinyl acetate) copolymer/natural rubber/organoclay nanocomposites

The effects of electron beam (EB) irradiation on the morphology, crosslink density, and tensile properties of EVA/SMR L (Standard Malaysian Rubber)/organoclay nanocomposites prepared by a melt‐blending technique were investigated. All the samples were irradiated by using a 3.0‐MeV EB apparatus with doses ranging from 50 to 200 kGy. Organoclay loading was varied from 0 to 10 phr (parts by weight per hundred parts of resin). X‐ray diffraction results and transmission electron microscopy images proved that the dispersion of organoclay in the nanocomposites was slightly improved by EB irradiation. The gel fraction yield for the nanocomposites increased with irradiation dose but decreased with organoclay loading. However, at 200 kGy, the gel fraction yield was almost the same at all organoclay loadings. Tensile strength and stress at 100% elongation increased proportionally with the irradiation dose. Elongation at break of the nanocomposites increased up to 100 kGy but then decreased at higher irradiation doses. The intercalation and exfoliation of the organoclay, the barrier effect, and the Hofmann degradation of the modification agent are the three major factors leading to the improvement of the properties of the irradiated nanocomposites. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Effect of dispersion state of organoclay on cellular foam structure and mechanical properties of ethylene vinyl acetate copolymer/ethylene‐1‐butenecopolymer/organoclay nanocomposite foams

In this study, our goal is to obtain lower density of ethylene‐vinyl acetate copolymer (EVA)/ethylene‐1‐butene copolymer (EtBC) foams without sacrificing mechanical properties. For this purpose EVA/EtBC/organoclay (Cloisite 15A, Closite 30B) nanocomposite foams were prepared. To investigate the effect of compatibilizer on the dispersion state of organoclay in cellular foam structure and mechanical properties of the EVA/EtBC/organoclay foams composites were prepared with and without maleic anhydride grafted EtBC (EtBC‐g‐MAH). The dispersion of organoclay in EVA/EtBC/organocaly foams was investigated by X‐ray diffraction and transmission electron microscopy. The EVA/EtBC nanocomposite foamswith the compatibilzer, especially EVA/EtBC/Cloisite 15A/EtBC‐g‐MAH foams displayed more uniform dispersion of organoclay than EVA/EtBC nanocomposite foams without the compatibilzer. As a result, EVA/EtBC/Cloisite 15A/EtBC‐g‐MAH foams have the smallest average cell size and highest 100% tensile modulus followed by EVA/EtBC/Cloisite 30B/EtBC‐g‐MAH foams. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3879–3885, 2007     

Migration of antifog additives in agricultural films of low‐density polyethylene and ethylene‐vinyl acetate copolymers

In this work, polymer films of low density polyethylene and ethylene‐vinyl acetate copolymers containing two types of antifog additives (nonionic surfactants) were exposed to two simulated horticultural greenhouse environments, reproducing hot and cold climate conditions. The evolution of the antifog effect was visually observed and that of the additive concentration measured using Fourier transform infrared spectroscopy (FTIR). All the films studied showed good antifog properties, but in all cases, the duration of the antifog effect was longer in the hot‐climate test. From the FTIR, we can conclude that the additives studied showed a low migration rate and, therefore, when the antifog effect is lost, important quantities of the additive remain in the bulk. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Enhancement of radiation‐resistant effect in ethylene–vinyl acetate copolymers by the formation of ethylene–vinyl acetate copolymers/clay nanocomposites

Ethylene–vinyl acetate (EVA) copolymers/clay nanocomposites, prepared by using nonreactive organophilic clay and reactive organophilic clay, were characterized by X‐ray diffraction and by high‐resolution transmission electron microscopy. The influence of gamma irradiation on the structure and properties of the pure EVA and EVA/clay nanocomposites was systematically investigated. In the presence of gamma radiation, the clay can effectively restrain the increase of the storage modulus of EVA/clay nanocomposites, which was supported by dynamical mechanical analysis. Gamma irradiation had almost no effect on the thermal properties of EVA/clay nanocomposites by using nonreactive organophilic clay, but it obviously improved the thermal stability of EVA/clay nanocomposites by using reactive organophilic clay. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2532–2538, 2005     

Double‐yielding behavior in injection‐molded polycarbonate/high‐density polyethylene/ethylene–vinyl acetate copolymer blends

A uniaxial tensile test was performed for polycarbonate (PC)/high‐density polyethylene (HDPE)/ethylene–vinyl acetate copolymer (EVA) blends with a fixed EVA content but various PC contents. The double‐yielding phenomenon and its composition dependence, as observed in the PC/HDPE blend, were again detected. EVA did not serve as a successful compatibilizer of PC and HDPE in the PC/HDPE/EVA blend. The incorporation of EVA resulted in a larger size and a more irregular shape of the PC fibers, as indicated in the scanning electron microscope observations; this, consequently, produced a higher serious stress concentration in the blend. This more complicated and instable morphology produced different double‐yielding behaviors in the PC/HDPE/EVA blends compared with the binary one. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal characteristics of ethylene‐co‐vinyl acetate/cellulose microfibers composites

Cellulose microfibers were obtained from Hibiscus sabadariffa by steam explosion technique. Structural and surface analysis of the microfibers showed a reduction in diameter and changes in surface morphology from that of raw fibers. The chemical composition of fibers showed increase in α‐cellulose content and decrease in lignin and hemicelluloses for the microfibers. These factors were further confirmed by XRD, SEM, and FTIR results. The CMF were introduced to EVA at different loading by melt extrusion. The composites were analyzed for their thermal stability and phase transition using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). TGA analysis of the composites showed increased onset temperatures for composites compared with pure EVA indicating the superior thermal stability of the composites with fiber loading. DSC analysis shows increase in melting enthalpy and percentage crystallinity with fiber loading increases. Kinetic parameter for the degradation of the composites was obtained using Broido, Coats–Redfern, and Horowitz‐Metzger methods. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

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     

Morphology and mechanical properties of ethylene‐vinyl acetate rubber/polyamide thermoplastic elastomers

High performance thermoplastic elastomers based on ethylene‐vinyl acetate rubber (EVM) and ternary polyamide copolymer (tPA) were prepared through a dynamic vulcanization process in the presence of dicumyl peroxide (DCP). The morphology, crystallization, and mechanical properties of the EVM/tPA blends were studied. A phase transition of EVM/tPA blend was observed at a weight ratio of 60/40. The presence of EVM increased the melting enthalpy at the high temperature of tPA, ascribing to the heterogeneous nucleating effect of EVM. The tensile strength of EVM/tPA (70/30) blends was increased up to 20.5 MPa as the DCP concentration increased to 3.5 phr, whereas the elongation at break of the blends kept decreasing as the DCP concentration increased. The addition of ethylene‐acrylic acid copolymer (EAA) or maleic anhydride‐grafted EVM (EVM‐g‐MAH) to the EVM/tPA blends both induced finer dispersion of the EVM particles in the tPA phase and improvement in the tensile strength and elongation at break of the blends, which were ascribed to the compatibilization of EAA or EVM‐g‐MAH. Finally, a high performance EVM/tPA (70/30) thermoplastic elastomer with Shore A hardness of 75, tensile strength of 24 MPa, elongation at break of 361%, and set at break of 20% was obtained by adding 5 wt % of EVM‐g‐MAH and 3.5 phr DCP. It has great potential in automotive and oil pipeline applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and characterization of ethylene‐vinyl acetate nanocomposites: enhanced flame retardant

Ethylene‐vinyl acetate (EVA) nanocomposites with enhanced flame retardance were prepared by the sol–gel process in the melt. Two EVAs with different vinyl acetate (VA) contents and aluminium isopropoxide were used as organic and inorganic phases. The nanocomposites were prepared in a batch mixer under constant processing conditions and were analysed by several characterization techniques. Aluminium isopropoxide presented low activation energy, which allows the synthesis of the nanoparticles without a post step treatment. The reaction mechanism is proposed. Nanocomposites with smaller and well dispersed metal nanoparticles were produced with an EVA with higher VA content. EVA nanocomposites achieve the requirements for 94 V‐0 classification. © 2013 Society of Chemical Industry     

Poly(ethylene‐co‐vinyl acetate)/calcium phosphate nanocomposites: Thermo mechanical and gas permeability measurements

Poly(ethylene‐co‐vinyl acetate) (EVA)/Calcium phosphate nanocomposites were prepared by melt mixing in a Brabender plasticoder. Nanoparticles of calcium phosphate were synthesized by the polymer‐mediated synthesis and characterized by X‐ray diffractometry and transmission electron microscopy. Mechanical properties such as tensile strength, tensile modulus, tear strength, etc., were measured with respect to the filler loading. Thermal stability of the composites under nitrogen atmosphere was also measured. The composites showed better thermal stability due to the nanoreinforcement. Oxygen gas permeability of the composites showed considerable decrease due to tortuous path created by the nanofillers. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Compatibility of low‐density polyethylene/poly(ethylene‐co‐vinyl acetate) binary blends prepared by melt mixing

The compatibility of low‐density polyethylene and poly(ethylene‐co‐vinyl acetate) containing 18 wt % vinyl acetate units (EVA‐18) was studied. For this purpose, a series of different blends containing 25, 50, or 75 wt % EVA‐18 were prepared by melt mixing with a single‐screw extruder. For each composition, three different sets of blends were prepared, which corresponded to the three different temperatures used in the metering section and the die of the extruder (140, 160, and 180°C), at a screw rotation speed of 42 rpm. Blends that contained 25 wt % EVA‐18 were also prepared through mixing at 140, 160, or 180°C but at a screw speed of 69 rpm. A study of the blends by differential scanning calorimetry showed that all the prepared blends were heterogeneous, except that containing 75 wt % EVA‐18 and prepared at 180°C. However, because of the high interfacial adhesion, a fine dispersion of the minor component in the polymer matrix was observed for all the studied blends with scanning electron microscopy. The tensile strengths and elongations at break of the blends lay between the corresponding values of the two polymers. The absence of any minimum in the mechanical properties was strong evidence that the two polymers were compatible over the whole range of composition. The thermal shrinkage of the blends at various temperatures depended mainly on the temperature and EVA‐18 content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 841–852, 2003     

High‐performance antistatic ethylene–vinyl acetate copolymer/high‐density polyethylene composites with graphene nanoplatelets coated by polyaniline

Graphene nanoplatelets coated by polyaniline (GNP@PANI) and ethylene–vinyl acetate (EVA) copolymer–high‐density polyethylene (HDPE) were used for the first time to prepare high‐performance antistatic composites through an effective method that combined solution mixing and melt blending. GNP@PANI nanocomposites were fabricated by in situ polymerization to improve the dispersion of graphene nanoplatelets (GNPs) in the EVA–HDPE matrix and the compatibility between the GNPs and the EVA–HDPE matrix. The GNP@PANI nanocomposites and EVA were first prepared as a premix through solution mixing, and then, the premix and HDPE were prepared as highly antistatic composites through melt blending. The dispersion of the GNPs in the EVA–HDPE matrix and the compatibility between the GNPs and the EVA–HDPE matrix were confirmed by field emission scanning electron microscopy and transmission electron microscopy observations. The GNP@PANI–EVA–HDPE composites met the requirements for antistatic materials when the content of the GNP@PANI nanocomposites was 5 wt % with only about 1 wt % GNPs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45303.