Effect of vinyl acetate content and electron beam irradiation on the flame retardancy, mechanical and thermal properties of intumescent flame retardant ethylene-vinyl acetate copolymer

Ethylene vinyl acetate copolymer (EVA) flame retarded by ammonium polyphosphate (APP) and pentaerythritol (PER) was cross-linked by electron beam irradiation. The effects of vinyl acetate content and electron beam irradiation on the flame retardancy, mechanical and thermal properties of EVA composites were investigated. The volatilized products of EVA/APP/PER composites were characterized by thermogravimetric analysis/infrared spectrometry. As VA content increased, the volatilized products increased in the second decomposition step, but decreased in the third decomposition step. For all samples, the increase of irradiation dose could improve both the gel content and the Limit Oxygen Index (LOI, the minimum oxygen concentration by volume for maintaining the burning of a material) values of irradiated composites. The mechanical and thermal properties of the irradiated EVA composites were also evidently improved at appropriate irradiation dose as compared with those of unirradiated EVA composites, whereas these properties decrease at higher irradiation dose because of the electron beam irradiation-induced oxidative degradation or chain scission.     

Irradiation crosslinking and halogen-free flame retardation of EVA using hydrotalcite and red phosphorus

Halogen-free flame retarded ethylene vinyl acetate copolymer (EVA) composites using Mg-Al-CO₃ hydrotalcite (MALDH) and microcapsulated red phosphorus (MRP) have been prepared in a melt process. The flame retardation of the composites has been studied by the limited oxygen index (LOI) and UL-94 methods, and the thermal decomposition by the thermogravimetric analysis (TGA). The changes of their properties of the composites before and after the Gamma irradiation are compared. The synergistic effect in the flame retardation between MALDH and MRP in EVA has been found. The EVA/MALDH/MRP composites after the irradiation crosslinking result in a great increase in the Vicat softening point. The LOI value, the mechanical properties and thermal stability are also improved for the composites irradiated by a suitable irradiation dose.     

Mechanical and fire retardant properties of EVA/clay/ATH nanocomposites - Effect of particle size and surface treatment of ATH filler

Mechanical and flame retardant properties of ethylene vinyl acetate (EVA) copolymer/organoclay/alumina trihydrate (ATH) nanocomposites have been studied. ATH with different particle sizes, ATH1 (2.2-5.2 μm) and ATH2 (1.5-3.5 μm), and three different surface treatments, uncoated, fatty acid coated and silane coated, have been used. A synergistic effect was observed in EVA/organoclay/ATH nanocomposites with the total heat evolved (THE) and the heat release rate (HRR) lower than that of EVA/ATH composite. It was also found that mechanical and flame retardant properties are affected in different ways by the particle size and the surface treatment of ATH fillers. Improvements in tensile and flame retardant properties were observed in nanocomposites when uncoated ATH fillers and fatty acid coated ATH2 filler were used. On the other hand, silane coating on ATH1 and ATH2 improves limiting oxygen index (LOI) and leads to higher t_ignition and the best char stability after cone calorimeter test.     

The effect of gamma irradiation on mechanical, and thermal properties of recycling polyethylene terephthalate and low density polyethylene (R-PET/LDPE) blend compatibilized by ethylene vinyl acetate (EVA)

A study has been made on the compatibility of recycled polyethylene terephthalate (R-PET) and low density polyethylene (LDPE) blend in the presence of ethylene vinyl acetate (EVA) as a compatibilizing agent prepared by extrusion hot stretching process. EVA content in the blend as a compatibilizing agent was an enhancement effect on radiation crosslinking of R-PET/EVA/LDPE blends and the highest radiation crosslinking was obtained when the EVA content was reached at 10 % EVA when irradiated by gamma irradiation. Blends containing different (EVA) ratios were irradiated to different doses of gamma irradiation 25, 50 and 100 kGy. The effect of the compatibilizer and radiation on mechanical, thermal properties of R-PET together with LDPE and morphology has been investigated. It was found that gamma irradiation together with the presence of compatibilizing agent (EVA) has positive effect on the mechanical and thermal properties of R-PET/LDPE blend. The structural properties of R-PET/LDPE modified by gamma irradiation and EVA as compatibilizing agent was examined by SEM. Also, it was found that the optimum concentration of EVA and gamma irradiation dose was found to be 10 % EVA and 100 kGy, respectively.     

Characterization of irradiation-induced crosslink of epoxidised natural rubber/ethylene vinyl acetate (ENR-50/EVA) blend

The effect of irradiation on tensile, dynamic mechanical properties, thermal properties and morphology of ENR-50, EVA and ENR-50/EVA blend was investigated. All the samples were irradiated using a 3.0 MeV electron beam (EB) machine with doses ranging from 20 to 100 kGy. Results indicate that the gel fraction of ENR-50, EVA and ENR-50/EVA blend increases with irradiation dose. Concerning tensile properties, it can be seen that EB radiation increases the tensile strength of all the samples, increases the elongation at break of ENR-50 and ENR-50/EVA blend, reduces the elongation at break of EVA, increases M200 (modulus at 200% strain) of ENR-50 and EVA, while decreases M200 of the ENR-50/EVA blend. For dynamic mechanical studies, it was found that EB radiation increases the T_g of all the samples due to the effect of irradiation-induced crosslinking. The compatibility of ENR-50/EVA blend also found to be improving upon irradiation. In the case of thermal properties, it was detected that T_m, T_c and the degree of crystallinity of ENR-50/EVA blend increase with an increase in irradiation dose. This was due to the perfection in the crystal growth occurring upon radiation. Morphology changes play a major role in the changes of the properties of ENR-50/EVA blend. Finally, it can be concluded that ENR-50/EVA blend can be vulcanized by EB radiation.     

X-ray investigation of polypropylene and poly(ethylene-co-vinyl acetate) blends irradiated with fast electronsWAXS investigation of irradiated i-PP/EVA blends

Blends consisting of poly(propylene-ethylene) (PP) and poly(ethylene-co-vinyl acetate) (EVA) copolymers were investigated. Specimens were irradiated with fast electrons at different doses. Some of the samples show thermo-shrinkable properties. The interplanar spacing, paracrystalline factor, degree of crystallinity and crystallite sizes were determined by WAXS measurements. Results have been reported in respect to PP content and irradiation dose. A decrease of the crystallite’s imperfections with the rise of the irradiation dose was observed. An interface built up of partially interpenetrated amorphous molecular chains of incompatible polymers and separate PP and EVA small crystallites is suggested.     

Effect of organoclay loading and electron beam irradiation on the physico‐mechanical properties of low‐density polyethylene/ethylene‐vinyl acetate blend

The influence of electron beam (EB) irradiation and organoclay (OC) loading on the properties of low‐density polyethylene (LDPE)/ethylene‐vinyl acetate (EVA) blends was investigated. The samples were subjected to the EB irradiation with the dose values of 50 and 250 kGy. X‐ray diffraction (XRD), gel content, mechanical, thermal, and electrical properties were utilized to analyze the characteristics of the LDPE/EVA blends with and without OC at different irradiation dosages. Gel content analysis showed that the OC promotes considerably the insoluble part so that the LDPE/EVA blends filled with OC become fully crosslinked at 250 kGy; possibly through the formation of further crosslinks between OC and polymer chains. The samples irradiated by EB showed enhanced mechanical properties due to the formation of three‐dimensional networks. In addition, thermogravimetric analysis indicated that combined OC loading and radiation‐induced crosslinking improved thermal stability of LDPE/EVA blends considerably. Copyright © 2011 John Wiley & Sons, Ltd.     

Electron beam crosslinking of poly(ethylene-co-vinyl acetate)/clay nanocomposites

Effect of electron beam irradiation on the thermal and mechanical properties of poly(ethylene-co-vinyl acetate) (EVA)/clay nanocomposites prepared by melt blending method has been investigated. The hot set test results show that elongation at high temperature under static load decreased with the increase of irradiation dose. The tensile modulus increased continuously with increasing dose. While the tensile strength increased up to 100 kGy, it decreased with further increase in dose. The elongation at break decreased continuously with increasing dose. Thermogravimetric analysis showed that thermal stability of the EVA/clay nanocomposites improved with increasing dose. The improvement in the mechanical and thermal properties is attributed to the formation of radiation-induced crosslinking as evidenced by the gel content results.     

Photocrosslinking of EVA/inorganic filler blends and characteristics of related properties

The blends of EVA filled with talc, calcium carbonate, and glass ball (GB) have been photocrosslinked by UV irradiation in the presence of benzophenone (BP) as a photoinitiator and triallyl isocyanurate (TAIC) as a crosslinker. The various factors affecting the crosslinking process and the related properties have been studied by gel determination, heat extension test, mechanical and thermal aging test, UV spectroscopy, and scanning electron microscopy. The results show that the EVA/talc, EVA/CaCO₃, and EVA/GB samples of 1 mm thickness filled with 25 phr inorganic filler can be photocrosslinked to gel content of above 70 wt% by 5 sec UV‐irradiation under optimum conditions, which is sufficient for some applications of EVA blend materials. The crosslinking rate and final gel content level are in the order of EVA/GB > EVA/talc > EVA/CaCO₃. The data from mechanical and thermal aging tests give evidence that the photocrosslinked EVA/talc, EVA/CaCO₃, and EVA/GB samples are of much better tensile strength and thermal aging properties than those of the unphotocrosslinked ones. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of Electron Beam Irradiation and Ethylene Vinyl Acetate Copolymer on the Properties of NBR/HDPE Blends

The mechanical and physical properties of blends based essentially on nitrile butadiene rubber (NBR) and different ratios of high density polyethylene (HDPE) up to 25 parts per hundred part of rubber (phr) before and after electron beam irradiation were investigated. The values of tensile strength (TS), tensile modulus at 50% elongation (M₅₀), hardness and gel fraction % (GF%) of NBR/HDPE blends were increased with both irradiation dose and by increasing the content of HDPE in the blends. On the other hand, the values of elongation at break (E _b ) were decreased with both irradiation dose and the content of HDPE in the blends. By loading NBR/HDPE (100/25) blend with ethylene vinyl acetate (EVA) copolymer the mechanical and physico-chemical properties were improved. Moreover, the degree of improvement is proportional to the loading content of EVA.     

Role of temperature during ageing under gamma irradiation of filled EPDM: consequences on mechanical properties

Filled EPDM materials have been processed and aged by gamma radiation at ambient temperature and at 80 °C to study the influence of the fillers presence in the material degradation. The acceleration of the polymer degradation by the ATH fillers, evidenced when irradiation is performed at 25 °C, is also effective at 80 °C. In addition, in the case of silica‐filled EPDM, the creation of strong filler‐matrix bonds, already reported for irradiation at 25 °C, is also thermally activated; this enables to this material to keep its integrity at high irradiation dose, whereas the irradiated ATH‐filled EPDM is so degraded that it flows. Thus, the introduction of fillers in the polymer has an impact on its resistance to irradiation, whatever the temperature at which the irradiation is performed. Moreover, the consequences of the degradation on the evolution of the mechanical properties of the composite are very dependent on the filler nature. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1319–1328, 2010     

Influence of gamma irradiation on high density polyethylene/ethylene‐vinyl acetate/clay nanocomposites

The study of high density polyethylene (HDPE)/ethylene‐vinyl acetate (EVA)/and organically‐modified montmorillonite (OMT) nanocomposites prepared by melt intercalation followed by exposure to gamma‐rays have been carried out. The morphology and properties of the nanocomposites were studied using X‐ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and cone calorimetry. The purpose of the study focuses on the influence of gamma irradiation on the morphology, thermal stability and flammability properties of the nanocomposites. XRD studies and TEM images verified that the ordered intercalated nanomorphology of the nanocomposites was not disturbed by gamma irradiation. TGA data showed that the nano‐dispersion of clay throughout the polymer inhibited the irradiation degradation of HDPE/EVA blend, which led to the nanocomposites exhibiting superior irradiation‐resistant properties than that of the pure blend. Cone calorimetry results indicated that the improvement in heat release rate (HRR) for irradiated HDPE/EVA blend was suppressed efficiently when clay was present. Increasing clay loading from 2 to 10% was beneficial by improving the flammability properties of the nanocomposites, but promoted a rapid increase in the sub‐peak HRR at high irradiation dose level. Copyright © 2004 John Wiley & Sons, Ltd.     

Layered double hydroxides intercalated with borate anions: Fire and thermal properties in ethylene vinyl acetate copolymer

Fire and thermal properties of ethylene vinyl acetate (EVA) composites prepared by melt blending with layered double hydroxides (LDH) have been studied. Two types of LDHs intercalated with borate anion were prepared using the coprecipitation method and the metals Mg²⁺, Zn²⁺ and Al³⁺. Characterization of the LDHs and the EVA composites was performed using X-ray diffraction, thermogravimetric analysis, and cone calorimetry. Thermal analyses show that the addition of LDHs improves the thermal stability of EVA. Fire properties evaluated using the cone calorimeter were significantly improved in the EVA/LDH composites. The peak heat release rate was reduced by about 40% when only 3% by weight of the LDH was added to the copolymer. Comparison of the fire properties of the LDHs with those of aluminum trihydrate (ATH), magnesium hydroxides (MDH), zinc hydroxide (ZH) and their combinations at 40% loading, reveal that the LDHs were more effective than when MDH and ZH are used alone.     

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.     

Improvements of physical and mechanical properties of electron beam irradiation—crosslinked EVA foams

In this work, ethylene–vinyl acetate (EVA) copolymer foams were prepared and crosslinked by using high‐energy electron beam (e‐beam) radiation (10 MeV). The effect of parameters such as irradiation dose, the contents of foaming agent, radiation activator, and radiation sensitizer on improvement of physical and mechanical properties of the EVA foamed samples were investigated. The foams were obtained through a four‐step process of melt mixing, forming, crosslinking, and foaming. During the melt mixing process EVA was compounded with different amounts of azodicarbonamide (ADCA) as a blowing agent, zinc oxide (ZnO) as a radiation activator, and trimethylol propane‐trimethacrylate (TMPTMA) as a radiation sensitizer. The samples were compression molded into flat sheets at low temperature (110°C) and were then radiation‐crosslinked by 20–80 kGy e‐beam. Finally, the crosslinked samples were converted to foams by a high temperature (210°C) compression molding process. The foamed samples were analyzed in terms of gel content, density, compression molding set, tensile properties, and micro‐structural features. It was found that an increase in absorbed radiation dosage increases crosslink density, elasticity, percentage recovery, tensile strength, and compression properties of the EVA foams. Due to the increased recovery the percentage of compression set was reduced. Similarly increasing the TMPTMA content in the formulation increased the crosslink density and the resulting mechanical properties. Contrary to these findings, addition of ADCA led to the formation of extra gases which in turn reduced the crosslink density, and resulted in the deterioration of the mechanical properties and hence an increase in the compression set. However, addition of ZnO and TMPTMA led to the formation of smaller and more uniform cell size with improved mechanical properties. Copyright © 2008 John Wiley & Sons, Ltd.     

Co γ-ray irradiation effect and degradation behaviors of a carbon nanotube and poly(ethylene-co-vinyl acetate) nanocomposites

This paper describes the process of manufacturing a new nanocomposite material, which involves adding a carbon nanotube (CNT) to improve EVA's physical characteristics such as weak radiation resistance and thermal properties. We irradiated the prepared samples with doses of 50 kGy, 100 kGy and 200 kGy at a dose rate of 5 kGy/h and examined their thermogravimetric characteristics, activation energy, degradation progress, and CNT dispersion using a thermogravimetric analyzer (TGA), chemiluminescence (CL), and a field emission scanning electron microscope (FESEM). Experimental results indicated that the samples with a CNT had higher DTG 2nd peak temperatures than those without a CNT. Activation energy of the samples reduced as the irradiation dose and the CNT content increased. In the second CL experiment, the CL intensity rapidly declined as the temperature, irradiation dose and the CNT content increased. Finally, examination of the fracture surfaces in the FESEM experiment indicated that the lamella structure of the EVA changed as the irradiation dose increased. We were also able to observe that samples with a CNT were aggregated and dispersed in numerous lumps.     

Influence of gamma irradiation on the ageing characteristics of poly(ethylene-co-vinyl acetate) and poly(ethylene-co-vinyl acetate)/carbon black mixture

In this comparative study, the effect of gamma rays on the ageing characteristics of poly(ethylene-co-vinyl acetate) (EVA) and poly(ethylene-co-vinyl acetate)/carbon black mixture (EVA/CB) was investigated in terms of thermal stability. EVA, containing 13% vinyl acetate (VA), and EVA/CB, containing 13% VA and 1% carbon black (CB), were aged at 85°C in air up to 30 weeks for thermal ageing. Same substances were aged by means of UV light with a wavelength in the vicinity of 259 nm, in air, up to 400 h for UV ageing. Same substances were also irradiated with gamma rays at ambient conditions up to 400 kGy. Following these experiments, samples which had been irradiated with gamma rays, were subjected to thermal and UV ageing under the same conditions as for unirradiated samples. Dynamic thermogravimetry studies were performed for determination of the thermal stabilities of the samples. 10 and 50% mass losses were calculated for the samples from their respective curves. As a result of thermal analysis experiments, it was found that CB dramatically loses its protective property against thermal ageing of EVA after gamma irradiation. On the other hand, gamma irradiation does not have any significant effect on the UV ageing characteristics of EVA and EVA/CB in terms of thermal stability.     

Additive manufacturing of fire‐retardant ethylene‐vinyl acetate

Thermocompression (with also extrusion and injection molding) is a classical polymer shaping manufacturing, but it does not easily allow designing sophisticated shapes without using a complex mold, on the contrary to 3D printing (or polymer additive manufacturing), which is a very flexible technique. Among all 3D printing techniques, fused deposition modeling is of high potential for product manufacturing, with the capability to compete with conventional polymer processing techniques. This is a quite low cost 3D printing technique, but the range of filaments commercially available is limited. However, in some specific 3D printing processes, no filaments are necessary. Polymers pellets feed directly the printing nozzle allowing to investigate many polymeric matrices with no commercial limitation. This is of high interest for the design of flame‐retarded materials, but literature is scarce in that field. In this paper, a comparison between thermocompression and 3D printing processes was performed on both neat ethylene‐vinyl acetate (EVA) copolymer and EVA flame retarded with aluminum triHydroxyde (ATH) containing different loadings (30 or 65 wt%) and with expandable graphite (EG), ie, EVA/ATH (30 wt%), EVA/ATH (65 wt%), and EVA/EG (10 wt%), respectively. Morphological comparisons, using microscopic and electronic microprobe analyses, revealed that 3D printed plates have lower apparent density and higher porosity than thermocompressed plate. The fire‐retardant properties of thermocompressed and 3D printed plates were then evaluated using mass loss calorimeter test at 50 kW/m². Results highlight that 3D printing can be used to produce flame‐retardant systems. This work is a pioneer study exploring the feasibility of using polymer additive manufacturing technology for designing efficient flame‐retarded materials.     

Photocrosslinking and related properties of intumescent flame‐retardant LLDPE/EVA/IFR blends

The photoinitiated crosslinking of halogen‐free flame retarded linear low density polyethylene/poly(ethylene‐co‐vinyl acetate) blends (LLDPE/EVA) with the intumescent flame retardant (IFR) of phosphorous‐nitrogen compound (NP) in the presence of photoinitiator and crosslinker and their characterization of related properties have been investigated by gel determination, heat extension test, cone calorimeter test (CCT), thermogravimetric analysis (TGA), Fourier transfer infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), mechanical properties measurements, limiting oxygen index (LOI), UL‐94, and water resistance test. The data from the gel content and heat extension rate (HER) show that the LLDPE/EVA/IFR blends filled with NP are readily crosslinked to a gel content of above 75% and the HER values reach about 50% by UV‐irradiation of 5 sec under suitable amount of photoinitiator and crosslinker. The data obtained from the CCT and LOI indicate that photocrosslinking can considerably decrease the heat release rates (HRR) by 10–15%, prolongate the combustion time, and increase two LOI values for the LLDPE/EVA/NP blends UV irradiated for 5 sec. The results from TGA and the dynamic FTIR spectra give the evidence that the photocrosslinked LLDPE/EVA/NP samples show slower thermal degradation rate and higher thermo‐oxidative degradation temperature than the uncrosslinked LLDPE/EVA/NP samples. The morphological structures of charred residues observed by SEM give the positive evidence that the compact charred layers formed from the photocrosslinked LLDPE/EVA/NP samples play an important role in the enhancement of flame retardant and thermal properties. The data from the mechanical tests and water‐resistant measurements show that photocrosslinking can considerably improve the mechanical and water‐resistant properties of LLDPE/EVA/NP samples. Copyright © 2011 John Wiley & Sons, Ltd.     

Thermogravimetric Analysis and Thermal Ageing of Crosslinked Nitrile Rubber/Poly(ethylene-co-vinyl Acetate) Blends

The thermal behaviour of nitrile rubber (NBR)/poly(ethylene-co-vinyl acetate) (EVA) blends was studied by thermogravimetry. The effects of blend ratio, different crosslinking systems (sulphur, peroxide and mixed), various fillers (silica, clay and carbon black) and filler loading on the thermal properties were evaluated. It was found that the initial decomposition temperature increased with the addition of NBR to EVA. Among the various crosslinking systems studied, the peroxide cured system showed the highest initial decomposition temperature. This is associated with the high bond dissociation energy of C–C linkages. The addition of fillers improved the thermal stability of the blend. The mass loss at different temperatures and activation energy of degradation were also studied. The thermal ageing of these blends was carried out at 50 and 100°C for 72 h. It was seen that the properties are not affected by the mild ageing condition. Also, the peroxide cured system was found to exhibit better retention in properties, than other crosslinking systems. This revised version was published online in August 2006 with corrections to the Cover Date.