Viscoelasticity and morphology of poly(ethylene‐co‐vinyl acetate)/polyisobutylene blends

Blends of an ethylene/vinyl acetate copolymer (EVA) and polyisobutylene of various compositions were prepared by mechanical mixing at a temperature above the melting point of EVA (T_m^EVA) but below the upper critical solution temperature of 170°C for given blends. The rheological properties of the components and blends were studied in the region of small‐amplitude oscillating deformation at temperatures above and below T_m^EVA in the frequency range of 0.01–100 rad/s. At temperatures lower than T_m^EVA, the rheological properties were determined by the existence of the yield stress. With diminishing frequency, the viscosity increased, and the plateau in the relaxation spectrum at low frequencies broadened. The morphology of the blends depended on the conditions of sample heating. The introduction of a finely dispersed filler into the blends led to an anomalous drop in the viscosity. The morphology of the systems that arose by mechanical blending of the molten components was the important factor in the rheological behavior. The observed effects were examined in the framework of the concept of structural networks formed in melts by nonmelted crystallites of EVA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2700–2707, 2006     

Solid‐state NMR and morphological studies of poly(ethylene‐co‐vinyl acetate)/poly(vinyl acetate) blends

To obtain a correlation among structure–morphology–mobility–compatibility properties of poly(ethylene‐co‐vinyl acetate) (EVA)/poly(vinyl acetate) (PVAc) blends, we have used scanning electron microscopy and solid‐state nuclear magnetic resonance in our investigations. The results are discussed in terms of blends, component dispersion, plasticization effect, and domain mobilities to acquire a response of the correlation between structural properties. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2990–2996, 1999     

Evaluation of mechanical properties and physical interactions of a ternary blend of poly(ethylene‐co‐octene)/poly(ethylene‐co‐vinyl acetate)/poly(vinyl chloride) in the molten state

In this work, ethylene‐co‐vinyl acetate (EVA), poly(ethylene‐co‐octene) (POE), and poly(vinyl chloride) (PVC) blends were processed in a molten state process using a corotating twin‐screw extruder to assess both the balance of mechanical properties and physical interactions in the melt state. Tensile measurements, scanning electron microscopy, and oscillatory rheometry were performed. By means of flow curves, the parameters of the power law as well as the distribution of relaxation times were assessed with the aid of a nonlinear regularization method. The mechanical properties for the EVA‐POE blend approximated the values for POE, while inclusion of PVC shifted the modulus values to those of neat EVA. The rise in modulus was corroborated by the PVC phase dispersion as solid particles that act as a reinforcement for the ternary blend. The rheological properties in the molten state show that the POE does not present molecular entanglement effects and so tends both to diminish the EVA mechanical properties and increase the fluidity of the blend. However, the addition of PVC both restored the EVA typical pseudoplastic feature and promoted the increase in the viscosity and the mechanical properties of the ternary blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Fabrication,characterization, and properties of poly(ethylene‐co‐vinyl acetate)/magnetite nanocomposites

Poly(ethylene‐co‐vinyl acetate) (EVA)/magnetite (Fe₃O₄) nanocomposite was prepared with different loading of Fe₃O₄ nanoparticles. The mixing and compounding were carried out on a two‐roll mixing mill and the sheets were prepared in a compression‐molding machine. The effect of loading of nanoparticles in EVA was investigated thoroughly by different characterization technique such as transmission electron microscopy (TEM), X‐ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), limiting oxygen index (LOI), and technological properties. TEM analysis showed the uniform dispersion of filler in the polymer matrix and the dispersion of filler decreased with increase in filler content. XRD of the nanocomposite revealed the more ordered structure of the polymer chain. An appreciable increase in glass transition temperature was observed owing to the restricted mobility of Fe₃O₄‐filled EVA nanocomposite. TGA and flame resistance studies indicated that the composites attain better thermal and flame resistance than EVA owing to the interaction of filler and polymer segments. Mechanical properties such as tensile strength, tear resistance, and modulus were increased for composites up to 7 phr of filler, which is presumably owing to aggregation of Fe₃O₄ nanoparticle at higher loading. The presence of Fe₃O₄ nanoparticles in the polymer matrix reduced the elongation at break and impact strength while improved hardness of the composite than unfilled EVA. The change in technological properties had been correlated with the variation of polymer–filler interaction estimated from the swelling behavior. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40116.     

Dynamic–mechanical properties of modified poly(ethylene‐co‐vinyl acetate)

To study the relationship among relaxation peaks observed in dynamic mechanical experiments and the structure of poly(ethylene‐co‐vinyl acetate) (EVA), EVA copolymers with different substitution in the carbonyl group were synthesized. EVA was hydrolyzed to obtain poly (ethylene‐co‐vinyl alcohol) and was subsequently reacted with formic, hexanoic, and octanoic acids. The copolymers synthesized were characterized by infrared spectroscopy. Analysis of the DMA spectra of the copolymers showed that their relaxation behavior depends on the vinyl acetate concentration. The α‐ and β‐transitions were observed in EVA copolymers with 8 and 18 wt % of functional groups, and the relationship among relaxation process with the structure of polymer was investigated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1371–1376, 2005     

Production of polymeric membranes made of polypropylene,poly(ethylene‐co‐vinyl acetate), and poly(vinyl alcohol)

In this study, we prepared and characterized membranes containing polypropylene, poly(ethylene‐co‐vinyl acetate) (EVA), and poly(vinyl alcohol) (PVA). The production process involved blend extrusion and calendering followed by solvent extraction by toluene and water of the EVA and PVA phases. Morphology studies involving scanning electron microscopy determined the pore size distribution at the surface and in the internal regions of the membrane. The resulting membrane properties were related to the processing variables (extension rate, process temperature, and solvent extraction methods) and blend composition. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3275–3286, 2004     

Organic vapor permeation through natural rubber/poly(ethylene‐co‐vinyl acetate) blend membranes

Natural rubber/poly(ethylene‐co‐vinyl acetate) (NR/EVA) blend membranes, crosslinked with dicumyl peroxide, have been prepared and tested for vapor permeation characteristics. The effects of structure and morphology of the blend membranes on the permeability were investigated. The permeability was found to decrease with increase in EVA content which has been attributed to the semicrystalline nature of EVA. The permeation process has been observed to be controlled mainly by the molecular mass of the penetrants. In the case of benzene/acetone mixtures, it has been found that when acetone concentration increases the vapor permeation rate decreases. This clearly indicates less interaction of acetone towards NR/EVA membranes. For supporting all the observations, the parameters such as swelling coefficient and permeability coefficient have been calculated. POLYM. ENG. SCI., 48:198–202, 2008.© 2007 Society of Plastics Engineers     

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     

Effects of peroxide crosslinking on the mechanical and morphological properties of poly(ethylene‐co‐vinyl acetate)/zeolite composites

Uncrosslinked and chemically crosslinked ethylene‐vinyl acetate copolymers (EVAs) with 5–25 volume percentages of zeolite were prepared in a melt‐mixing process and then compression‐molded on a hot‐press machine according to standard test specifications. The mechanical properties measured by tensile test showed a reduction in tensile strength and elongation at break with increasing zeolite content. However, an increasing trend was observed for tensile modulus with addition of zeolite. Experimental results for ultimate stress were compared with those from Pukanszky equation. The experimental data showed a good fit to the Pukanszky model. The improvement in the interfacial interaction for crosslinked composites was also confirmed by this model. Morphological changes of EVA/zeolite composites were analyzed by scanning electron microscopy (SEM). The fractured surface of the composites indicated more complex morphology at higher zeolite loading. The influence of crosslinking induced by 2 wt% of dicumyl peroxide on the properties of EVA/zeolite composites was also investigated. The crosslinked composites showed better tensile properties than the uncrosslinked ones, a result which might be an indication of enhanced interaction between the EVA and zeolite. Density measurements, gel content determinations, and Fourier transform infrared analyses were also performed to evaluate the crosslink content of the composites. The changes in the properties of chemically crosslinked EVA/zeolite composites were observed. Meanwhile, SEM micrographs of the crosslinked EVA/zeolite composites showed better interfacial strength between zeolite and the EVA matrix as compared to that of the uncrosslinked composites. J. VINYL ADDIT. TECHNOL., 2012. © 2012 Society of Plastics Engineers     

Foaming of poly(ethylene‐co‐vinyl acetate) and poly(ethylene‐co‐vinyl acetate‐co‐carbon monoxide) and their blends with carbon dioxide

Poly(ethylene‐co‐vinyl acetate) (EVA‐25) and poly(ethylene‐co‐vinyl acetate‐co‐carbon monoxide) (EVACO‐2410) and their blends with EVACO:EVA ratios of 80:20, 60:40, 40:60, and 20:80 were foamed using CO₂. These foams are of interest for applications ranging from footwear to medical devices. Foaming experiments were carried out using 1 mm thick melt‐extruded films in CO₂ at a range of pressures (100, 200, and 300 bar) and temperatures (30, 40, 50, and 60 °C). Foamability of the polymers was explored both under isothermal and gradient temperature conditions. Foams of EVACO‐2410 displayed high initial expansions followed by postfoaming relaxation and shrinkage while foams generated from EVA‐25 showed more dimensional stability. Blending EVACO‐2410 with EVA‐25 was explored as an approach to reduce postfoaming relaxation and shrinkage. The surfaces of the foamed samples displayed blistering that was linked to CO₂ bubble entrapment and coalescence at the surface. Scanning electron micrographs of the foams generated from blends displayed distinct morphologies reflecting whether the sections were representing the machine‐ or cross‐machine direction of extruded films. In going from EVACO‐2410 to EVA‐25, the cell densities ranged from about 10⁶ to 10¹⁰ cells/cm³. Foams with low bulk densities of about 0.11 g/cm³ could be generated. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45841.     

High‐resolution solid‐state NMR and SEM study of the interaction behavior of poly(ethylene‐co‐vinyl acetate)/poly(vinyl acetate) blends

Binary blends formed by two types of ethylene‐co‐vinyl acetate (EVA), which have different vinyl acetate contents, and poly(vinyl acetate) (PVAc) were prepared in a Haake Rheocord 9000 plastograph. A series of samples were obtained varying the PVAc amount up to 50%. The studies were carried out employing solid‐state nuclear magnetic resonance spectroscopy (NMR) and scanning electronic microscopy (SEM). The xenon‐129 (¹²⁹Xe) and carbon‐13 (¹³C) NMR response together with the microscopy results showed that the systems are heterogeneous. Therefore, EVA with a higher vinyl acetate content presented some interaction between the polymer blend components. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 116–124, 2002     

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     

The effectiveness of magnesium carbonate‐based flame retardants for poly(ethylene‐co‐vinyl acetate) and poly(ethylene‐co‐ethyl acrylate)

In this report we outline recent work on the evaluation of magnesium carbonate‐based flame retardants for polymers commonly used in halogen‐free flame retardant wire and cable applications: poly(ethylene‐co‐vinyl acetate) (EVA) and poly(ethylene‐co‐ethyl acrylate) (EEA). Natural magnesium carbonate (magnesite), synthetic magnesium carbonate (hydromagnesite), and hydromagnesite/huntite blends were combined with EVA or EEA and tested for flame retardancy effectiveness with the cone calorimeter. The flammability results showed that the effectiveness of these carbonates was polymer dependent, suggesting that polymer degradation chemistry played a role in the flammability reduction mechanism. Hydromagnesites were, in general, more effective in reducing flammability, being comparable in performance to magnesium hydroxide. Finally, we report some polymer–clay (organically treated montmorillonite and magadiite) + magnesium carbonate flame retardant results which showed that the nanocomposite yielded mixed results. Specifically, the polymer–clay nanocomposite samples did not always yield the greatest reductions in peak heat release rate. Copyright © 2007 John Wiley & Sons, Ltd.     

Use of pyrolyzed oil shale as filler in poly(ethylene‐co‐vinyl acetate) with different vinyl acetate contents

Pyrolyzed oil shale (POS) obtained from the pyrolysis of bituminous rock was used as filler in poly(ethylene‐co‐vinyl acetate) (EVA). The effects of the VA content of EVA and the particle size of POS on the mechanical properties were investigated. The composites were prepared in a rotor mixer at 180°C with a concentration of POS of up to 30 wt %. The stress–strain plots of the compression‐molded composites are similar to the EVA (18% VA content) behavior for low concentrations (1–5 wt %) of POS with a particle size lower than 270 mesh. It was observed that decreasing the POS particle size and increasing the VA content of EVA produced better compatibility between the polymer and filler. The mechanical properties, differential scanning calorimetry, and dynamic mechanical analysis also demonstrated the compatibility between EVA and POS under the increase of the VA content in the EVA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1544–1555, 2002; DOI 10.1002/app.10494     

Influence of chemical treatments on cellulose fibers for use as reinforcements in poly(ethylene‐co‐vinyl acetate) composites

This work evaluates different chemical treatments on cellulose fibers as reinforcement agents in poly(ethylene‐vinyl acetate) (EVA) composites. The cellulose fibers were prepared with three chemical modifications using triethoxyvinylsilane, acetic anhydride (AA), and glycidyl methacrylate (GMA). Composites were prepared with 10 phr of cellulose fibers by means of extrusion and hot press conformation. The fiber treatment levels were successfully demonstrated through Fourier transform infrared spectroscopy with the appearance of characteristic bands in each chemical group, and scanning electron micrographs showed altered textures on the surfaces, polymerized material and fiber agglomerations after the chemical treatments that were most evident in the AA and GMA treatments. The composites reinforced with treated fibers showed improvement in their mechanical properties at the yield points and were reduced in deformation. When activated with dicumyl peroxide, the mechanical properties were even more improved and the interface regions exhibited better interactions between the cellulose fibers and the EVA matrix. POLYM. COMPOS., 37:1991–2000, 2016. © 2015 Society of Plastics Engineers     

Poly(ethylene‐vinyl co‐vinyl acetate)/clay nanocomposites: Mechanical,morphology, and thermal behavior

Nanocomposites of ethylene‐vinyl acetate copolymer (EVAL) with Dellite organoclay were prepared in a laboratory extruder. The extent of intercalation of the nanocomposites was studied by field emission scanning electron microscopy and X‐ray diffraction. It was established that the organoclay is well dispersed and preferentially embedded in the EVAL phase. Further, the intercalation degree of the organoclay decreased with increasing organoclay content. The mechanical properties of the nanocomposites were studied as a function of clay loading and EVAL type. The nanocomposites exhibited enhanced thermal stability as seen in thermogravimetric studies. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Poly(ethylene‐co‐vinyl acetate) blends with phenoxy

EVA was blended with phenoxy over the whole range of composition using a twin‐screw Brabender. Two‐phase separation caused by EVA crystallization was observed in the EVA‐rich blends and the dispersed domain of EVA was not clearly shown in the phenoxy‐rich blends. Differential scanning calorimetry (DSC) showed that the glass transition temperature (T_g) of EVA was increased by 5–10°C in the EVA‐rich blends but the T_g of phenoxy was superposed over the melting behavior of EVA. X‐ray diffraction measurement indicated that EVA crystallization was restricted in the phenoxy‐rich blends and the EVA crystal structure was influenced by incorporation of phenoxy into the EVA‐rich blends. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 227–236, 1999     

Effects of different preparation methods on the properties of poly[ethylene‐co‐(vinyl acetate)]/(Standard Malaysian natural rubber)/organoclay nanocomposites

Poly[ethylene‐co‐(vinyl acetate)] (EVA)/(Standard Malaysian natural rubber) (SMR L)/organoclay nanocomposites were prepared by using melt intercalation and solution blending methods. In both preparation methods, the EVA: (SMR L) ratio was prefixed at 50:50, while the organoclay loading was varied from 0 to 10 phr. The effects of two different processing routes and organoclay loading on the morphology, tensile, properties thermal properties, and flammability of the nanocomposites were studied. X‐ray diffraction results and transmission electron microscopy images proved that solution blending promotes better dispersion of organoclay than melt intercalation. Thus, the nanocomposites prepared by the solution‐blending method exhibited higher values of tensile strength, stress at 100% elongation (M100), and thermal stability. The M100 value and thermal stability improved proportionally with the increase of organoclay content, owing to the demobilizing effect and the barrier properties of the organoclay. The optimum tensile strength value was achieved at a 2‐phr organoclay loading. Further increases in loading decreased the strength of the nanocomposites. Tensile fracture surfaces of the nanocomposites prepared by both methods showed different fracture behavior, as evidenced by scanning electron microscopy images. Flammability decreased when the organoclay loading increased for the nanocomposites prepared by both methods. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Preparation and flame retardancy of a novel flame‐retardant poly(ethylene‐co‐vinyl acetate)/aluminum hydroxide composites containing phosphorus

A novel flame‐retardant (SPDH) containing phosphorus was synthesized through the reaction of 10‐(2,5‐dihydroxyphenyl)‐9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide and synthesized intermediate product 3,9‐dichloro‐2,4,8,10‐tetraoxa‐3,9‐diphosphaspiro[5.5] undecane‐3,9‐dioxide, which was used for optimizing the flame retardancy of ethylene‐vinyl acetate copolymer (EVM) rubber/aluminum hydroxide (ATH) composites. The microstructure of SPDH was characterized and determined by Fourier transform infrared and nuclear magnetic resonance spectroscopy. Thermogravimetric analysis (TGA) showed that SPDH had good charring effect at high temperature (600°C). The flame retardancy of the optimized EVM/ATH composites by SPDH was investigated by limiting oxygen index (LOI), cone calorimeter, and UL‐94 vertical burning tests. A higher LOI value (29.8%) and better UL‐94 rating (V‐0) can be achieved for the optimized EVM/ATH composite (EVM‐7) than EVM/ATH composite without SPDH (EVM‐3) with the total loading of additives. The heat release rate decreased and residual mass increased gradually as the loading of SPDH increased for the optimized EVM/ATH composites. There existed distinct synergistic flame‐retardant effect between SPDH and ATH in EVM matrix. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Effect of nanocellulose fibers and acetylated nanocellulose fibers on properties of poly(ethylene‐co‐vinyl acetate) foams

Cellulose nanofibers are promising materials in the development of polymeric foams, because they act as heterogeneous nucleation sites for the growth of cells during foaming. In this research, we studied the incorporation of cellulose nanoparticles in poly(ethylene‐co‐vinyl acetate)‐EVA foams. The foams were produced with different fiber contents. We observed the effect of a chemical treatment by acetylation on the cellulose fibber, that is, we evaluated the use of hydrophilic and hydrophobic cellulose nanofibers in EVA foams. The main results indicate that with the addition of only 1% of cellulose nanofibers, cell density significantly reduces when compared with the pure EVA foams. On the other hand, by increasing the cellulose content, the agglomeration of nanofibers also increases, which results in heterogeneous cell sizes. The same phenomenon was observed in the foams produced with acetylated cellulose nanofibers, regardless of the fiber content used. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44760.