Ethylene/vinyl acetate copolymer/clay nanocomposites

This article highlights the history, synthetic routes, material properties, and scope of ethylene/vinyl acetate copolymer (EVA)/clay nanocomposites. These nanocomposites of EVAs are achieved with either unmodified or organomodified layered silicates with different methods. The structures of the resulting polymer/inorganic nanocomposites have been characterized with X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. The addition of a small amount of clay, typically less than 8 wt %, to the polymer matrix unusually promotes the material properties, such as the mechanical, thermal, and swelling properties, and increases the flame retardancy of these hybrids. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 471–480, 2006     

Flammability characteristics and synergistic effect of hydrotalcite with microencapsulated red phosphorus in halogen-free flame retardant EVA composite

The flammability characteristics and synergistic effect of hydrotalcite with microencapsulated red phosphorus (MRP) in halogen-free flame retardant ethylene vinyl acetate (EVA) composite have been studied by cone calorimeter test (CCT), thermogravimetric analysis (TGA), limiting oxygen index (LOI) and UL-94 test. The results obtained by comparing the flame retardancy of hydrotalcite with magnesium hydroxide (MH) and aluminium hydroxide (AH) for their EVA composites showed that hydrotalcite has higher flame retardant effect than MH and AH at the same loading level. The CCT tests indicated that the heat release rate (HRR) and mass loss rate (MLR) of EVA composite blended with hydrotalcite greatly decreased compared with those blended with MH and AH. The LOI values of EVA/hydrotalcite composites are 3-4% higher than those of the corresponding MH composites at 40-60 wt% loading levels, and 6% higher than that of the corresponding AH composite at 40 wt% loading level. Moreover, the addition of a given amount of MRP apparently resulted in the increase of LOI value and decrease of the HRR and MLR as well the loading of hydrotalcite in EVA blend while keeping the V-0 rating in UL-94 test. However, the smoke release increased during the combustion of EVA/hydrotalcite blend containing MRP.     

Selective distribution,reinforcement, and toughening roles of MWCNTs in immiscible polypropylene/ethylene‐co‐vinyl acetate blends

Polypropylene/ethylene‐co‐vinyl acetate (PP/EVA) nanocomposites with functionalized multiwalled carbon nanotubes (FMWCNTs) have been prepared. The dissolution experiment, transmission electronic microscope, and scanning electronic microscope characterizations prove that, in the nanocomposites with sea–island morphology, although some FMWCNTs are observed in both PP and EVA phases, most of FMWCNTs distribute at the interface; however, in the nanocomposites with cocontinuous morphology, FMWCNTs mainly distribute in EVA phase. Further results based on (differential scanning calorimetry) measurements show that the different dispersion states of FMWCNTs, which are resulted by the different melt blending sequences, result in the different crystallization behaviors of PP matrix. The mechanical measurements show that FMWCNTs exhibit apparent reinforcement and toughening effects for immiscible PP/EVA blends, and such effects are greatly dependent upon the blending sequences. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1882–1892, 2010     

Thermal stability and flame retardancy of LDPE/EVA blends filled with synthetic hydromagnesite/aluminium hydroxide/montmorillonite and magnesium hydroxide/aluminium hydroxide/montmorillonite mixtures

The combination of organophillised montmorillonite (MMT), synthetic hydromagnesite and aluminium hydroxide (ATH) as flame retardant system for polyethylene-based materials was studied and compared with a similar system with magnesium hydroxide, ATH and MMT. The thermal stability and the flame retardant properties were evaluated by thermogravimetric analysis (TGA), differential thermal analysis (DTA), limiting oxygen index (LOI) and cone calorimeter tests. The results indicated that the addition of montmorillonite makes it possible to reduce the total filler content to achieve the flame retardant requirements. The thermal stability of filled LDPE/EVA blends increases to a higher extent for the samples containing MMT. In the cone calorimeter tests we observed a reduction of the peak heat release rate for the sample containing montmorillonite in comparison with a sample with higher filler loading without this nanoclay. An increase of the stability of the char formed could be responsible for this favourable behaviour when montmorillonite is added.In addition, mechanical properties significantly improved for the composites containing montmorillonite both for the filler loading reduction and the reinforcement effect of the nanoclay.     

Carbon nanotubes induced microstructure and mechanical properties changes in cocontinuous poly( L‐lactide)/ethylene‐co‐vinyl acetate blends

Toughening of poly( L ‐lactide) (PLLA) by elastomer attracts much attention in recent years; however, it is usually associated with the deterioration of modulus and/or strength, resulting in limitation in many applications of the material. In this work, functionalized multiwalled carbon nanotubes (FMWCNTs) were introduced into ethylene‐co‐vinyl acetate toughened PLLA blends. The effects of FMWCNTs content on crystalline structure of PLLA matrix and the morphology of the blends, as well as the selective distribution of FMWCNTs in the ternary nanocomposites were investigated using differential scanning calorimetry (DSC), wide angle X‐ray diffraction, scanning electron microscope, and transmission electron microscope. The results show that FMWCNTs exhibit excellent nucleation role in improving the cold crystallization behaviors of PLLA during the annealing and/or DSC heating processes. The results of mechanical property measurements demonstrate that the modulus, strength, and ductility of the blends can be further improved simultaneously through introducing FMWCNTs. Copyright © 2011 John Wiley & Sons, Ltd.     

High-temperature two-dimensional liquid chromatography of ethylene-vinylacetate copolymers

Temperature rising elution fractionation hyphenated to size exclusion chromatography (TREF × SEC) is a routine technique to determine the chemical heterogeneity of semicrystalline olefin copolymers. Its applicability is limited to well crystallizing samples. High-temperature two-dimensional liquid chromatography, HT 2D-LC, where the chromatographic separation by HPLC is hyphenated to SEC (HPLC × SEC) holds the promise to separate such materials irrespective of their crystallizability. A model blend consisting of ethylene-vinyl acetate (EVA) copolymers covering a broad range of chemical composition distribution including amorphous and semicrystalline copolymers and a polyethylene standard was separated by HT 2D-LC at 140 °C. Both axes of the contour plot, i.e. the compositional axis from the HPLC and the molar mass axis from the SEC separation were calibrated for the first time. Therefore, a new approach to determine the void and dwell volume of the developed HT 2D-LC instrument was applied. The results from the HT 2D-LC separation are compared to those from a cross-fractionation (TREF × SEC) experiment.     

Flame retardancy properties of α-zirconium phosphate based composites

α-Zr phosphate (hereafter referred to as ZrP) based composites were prepared by melt blending in order to improve the flame retardancy properties of polyamide 6 (PA6), polyethylene terephthalate (PET), polypropylene (PP) and ethylene vinyl acetate copolymer (EVA). Different morphologies are distinguishable by electron microscopy: PA6-ZrP seems to be a nanocomposite by Transmission Electron Microscopy (TEM) whereas PET-, PP- and EVA-ZrP blends appear micro-composites by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) analyses. ZrP acts as flame retardant in PA6 reducing the total heat evolved and consequently the heat release rate during the combustion measured by cone calorimetry. Moreover, ZrP reduces the flammability of PET and EVA acting in synergistic effect with phosphorous based flame retardants. Indeed, it is showed that it is possible to reduce the amount of phosphorous flame retardant adding ZrP to reach UL94 classification V0 for both polymers.     

Relationship between electrical resistivity and particle dispersion state for carbon black filled poly (ethylene-<Emphasis Type="Italic">co</Emphasis>-vinyl acetate)/poly (<Emphasis Type="SmallCaps">L</Emphasis>-lactic acid) blend

It is known that the electrical volume resistivity of insulating polymers filled with conductive fillers suddenly decreases at a certain content of filler. This phenomenon is called percolation. Therefore, it is known that controlling resistivity in the semi-conductive region for carbon black (CB) filled composites is very difficult. When poly (ethylene-co-vinyl acetate) (EVA) is used as a matrix, the percolation curve becomes gradual because CB particles disperse well in EVA. In this study, the relationship between the dispersion state of CB particles and electrical resistivity for EVA/poly (L-lactic acid) (PLLA) filled with CB composite was investigated. The apparent phase separation was seen in the SEM photograph. It was predicted that the CB particles located into the EVA phase in the light of thermodynamical consideration, which was estimated from the wetting coefficient between polymer matrix and CB particles. The total surface area per unit mass of dispersed CB particles in the polymer blend matrix was estimated from small-angle X-ray scattering and the volume resistivity decreased with increasing CB content. The values of the surface area of CB particles in CB filled EVA/PLLA (25/75 wt%) and EVA/PLLA (50/50 wt%) polymer blends showed a value similar to that of the CB filled EVA single polymer matrix. In electrical volume resistivity measurement, moreover, the slopes of percolation curves of EVA/PLLA (25/75 wt%) and EVA/PLLA (50/50 wt%) filled with CB composite are similar to that of EVA single polymer filled with CB composite. As a result, it was found that CB particles selectively locate in the EVA phase, and then the particle forms conductive networks similar to the networks in the case of EVA single polymer used as a matrix.     

Gas permeation properties of ethylene vinyl acetate–silica nanocomposite membranes

The effect of silica nanoparticles on the gas separation properties of ethylene vinyl acetate (EVA) copolymer containing 28% vinyl acetate has been investigated. The EVA and hybrid EVA–silica membranes were prepared via thermal phase inversion method. Silica nanoparticles prepared by hydrolysis of tetraethylorthosilicate (TEOS), through the sol–gel mechanism. The prepared membranes were characterized using FT-IR, SEM, DSC and XRD methods. FT-IR and SEM results indicated the nanoscale dispersion of silica particles in polymer matrix. As confirmed by XRD and DSC analyses, increasing the silica content enhances the amorphous regions significantly. Gas permeation of EVA–silica nanocomposite membranes with silica contents of 5, 6 and 10 wt.% was studied for N₂, O₂, CO₂ and CH₄ single gases at pressures of 4, 6 and 8 bar. The obtained results suggest a significant increase in permeability of all gases and an increase in CO₂/N₂ and CO₂/CH₄ gases selectivities upon increasing the silica content. The possible reasons for such behavior were stated and discussed. The pressure dependence of the gas permeabilities of the membranes was also investigated.     

Thermal stability and flammability characteristics of ethylene vinyl acetate (EVA) composites blended with a phenyl phosphonate-intercalated layered double hydroxide (LDH), melamine polyphosphate and/or boric acid

A phenyl phosphonate-intercalated MgAl-LDH (MgAl-PPh), melamine polyphosphate (MP), and boric acid (BA) were independently and concomitantly added to neat ethylene vinyl acetate (EVA) copolymer at loading fractions of 10% (w/w). The structural morphology of MgAl-PPh was established via powder X-ray diffraction (PXRD) and scanning electron microscopy (SEM) while the presence of phenyl phosphonate in the galleries was confirmed by Fourier transform infrared (FTIR). Thermogravimetric analysis (TGA) and cone calorimetry were used to evaluate the thermal stability and flammability behavior of EVA and its composites. While time-to-ignition is greatly reduced for EVA composites compared to the virgin polymer, there are remarkable reductions in the peak heat release rate (PHRR) which relates to a reduction in flame intensity. Synergistic effects were observed in cone calorimetry for the formulation containing MgAl-PPh, MP, and BA.