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.     

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.     

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.     

The effect of gamma irradiation and particle size of CaCO3 on the properties of HDPE/EPDM blends

Mechanical blends formed of 50 wt% of high-density polyethylene (HDPE) and 50 wt% of ethylene–propylene–diene-monomer (EPDM) elastomer have been loaded with 50 wt% of three different particle size of CaCO₃, namely CaCO₃ 300, CaCO₃ 700, and CaCO₃ 2000 whereby the latter has the smallest particle size of ～311, 82 μm. Mechanical, physico-chemical and thermal properties were followed up as a function of irradiation dose for loaded and unloaded blends. The results obtained indicated that the values of tensile strength, tensile modulus at 50% elongation, gel fraction and decomposition temperature increase with increasing irradiation dose. On the other hand elongation at break, permanent set and swelling number were found to decrease with increasing irradiation dose. Moreover, the effect of particle size of CaCO₃ was observed in a limited but apparent upgrading of mechanical, physico-chemical, and thermal properties. The order of semi-reinforcing capacity of three different types of CaCO₃ is as follow: CaCO₃ 2000 > CaCO₃ 700 > CaCO₃ 300 > unloaded blend. Whereby CaCO₃ 2000 has the smallest particle size.     

A comparative study of UV aging characteristics of poly(ethylene‐co‐vinyl acetate) and poly(ethylene‐co‐vinyl acetate)/carbon black mixture

In this comparative study, the effect of carbon black (CB) on the UV aging characteristics of poly(ethylene‐co‐vinyl acetate) (EVA) was investigated. EVA, containing 13% vinyl acetate (VA), and poly(ethylene‐co‐vinyl acetate)/carbon black mixture (EVA/CB), containing 13% VA and 1% CB, were aged by means of UV light with a wavelength in the vicinity of 259 nm, in air, up to 400 hr. Sol‐gel analyses were made to determine the percentage gelation of both virgin and aged samples. FT‐IR measurements were performed to follow the chemical changes which took place in the samples during aging. Dynamic and isothermal thermogravimetry studies were performed for determination of the thermal stabilities of virgin and aged samples. Sol‐gel analysis results showed that EVA itself has a tendency to form a gel under UV irradiation. EVA/CB, however, becomes a gel to a smaller extent, comparatively, under the same conditions. As a result of FT‐IR measurements, some oxidation products such as ketone, lactone and vinyl species were observed through UV ageing of EVA and EVA/CB. Thermal analysis experiments exhibited that the thermal stabilities of EVA and EVA/CB decreased, to a similar extent through UV aging. Copyright © 2004 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.     

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.     

Influence of the Particle Size of CaCO3 on the Adhesion of Filled EVA Materials

A surface treatment with corona discharge was used to improve the adhesion properties of ethylene vinyl acetate copolymer (EVA) containing small amounts of four CaCO₃ with different particle size. The nature of the surface modifications produced by the corona discharge treatment and the adhesion to a polychloroprene adhesive were assessed. Treatment of CaCO₃ filled EVA with corona discharge produced a decrease in water contact angle value, irrelevant to the different particle size of the calcium carbonates. The corona discharge treatment created C-O and C=O moieties on the EVA surface and also increased the peel strength, more markedly as the CaCO₃ particle size increased. In general, a mixed (adhesion + cohesive in the EVA) failure in the filled EVA material was produced (assessed by IR-ATR spectroscopy and SEM micrographs of the failed surfaces), but the failure was more cohesive in the EVA containing higher particle size CaCO₃. The durability of the joints was also studied.     

Structure,thermal stability,and photocrosslinking characterization of HDPE/LDH nanocomposites synthesized by melt‐intercalation

Structure, thermal properties, and influence of layered double hydroxide (LDH) fillers on photocrosslinking behavior of high‐density polyethylene (HDPE)/LDH nanocomposites have been studied in the present article. The X‐ray diffraction and transmission electron microscopy analysis demonstrate that the completely exfoliated HDPE/LDH nanocomposites can be obtained by controlling the organomodified LDH loading via melt‐intercalation. The data from the thermogravimetric analysis show that the HDPE/LDH nanocomposites have much higher thermal stability than HDPE sample. When the 50% weight loss was selected as a comparison point, the decomposition temperature of HDPE/LDH sample with 5 wt % LDH loading is ～40 °C higher than that of HDPE sample. The effects of UV‐irradiation on the HDPE/LDH nanocomposites show that the photoinitiated crosslinking can destroy the completely exfoliated structure to form the partially exfoliated structure, which decreased the thermal stability of the nanocomposites. However, the thermal stability of photocrosslinked samples can increase with increasing the UV‐irradiation time. The effect of LDH loading on the gel content of UV‐irradiated nanocomposites shows that the LDH materials can greatly absorb the UV irradiation and thus decrease the crosslinking efficiency. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3165–3172, 2006     

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.     

Effects of electrically inert fillers on the properties of poly(<Emphasis Type="Italic">m</Emphasis>-xylene adipamide)/multiwalled carbon nanotube composites

The effects of three types of electrically-inert fillers, calcium carbonate (CaCO₃), talc and glass fiber (GF), on electrical resistivity, crystallization behavior and dynamic mechanical properties of poly(m-xylene adipamide) (MXD6)/multiwalled carbon nanotube (MWCNT) composites are investigated. The electrical resistivity of MXD6/MWCNT composites is significantly reduced with the addition of inert fillers due to the volume-exclusion effect that leads to increased effective concentration of MWCNTs in MXD6 matrix and also due to improved MWCNT dispersion. The crystallization temperature of MXD6 increases with the addition of MWCNTs, indicating that MWCNTs can act as nucleating agent and induce crystallization of MXD6. The incorporation of inert fillers has no further effect on crystallization behavior of MXD6, but significantly improves the storage modulus of MXD6/MWCNT composite, demonstrating that CaCO₃, talc and GF filled MXD6/MWCNT composites are very promising materials with not only improved electrical property but also excellent mechanical properties.     

Combustion behavior and thermal stability of ethylene-vinyl acetate composites based on CaCO3-containing oil sludge and carbon black

CaCO₃-containing oil sludge (OS) is a by-product from petroleum industry, with great amount of production. Therefore, an effective processing methods for CaCO₃-containing OS is urgently needed. Herein, ethylene-vinyl acetate (EVA) composites based on CaCO₃-containing OS and carbon black (CB) were prepared by melt blending method. The combustion behavior and thermal stability of flame-retardant EVA/OS/CB composites were investigated by cone calorimeter test, limiting oxygen index (LOI), scanning electron microscopy (SEM), smoke density test (SDT), and thermogravimetry-Fourier infrared spectrometry. The heat release rate and smoke production rate of the ternary composites containing 3% CB significantly decreased compared with the EVA/OS composites and pure EVA. Moreover, addition of a certain amount of CB could evidently increase LOI values. The morphologies and structures of the residues, revealed by SEM, ascertained that a better carbonaceous protective layer was formed on the ternary composites than the EVA/OS composite. It was obtained from SDT that CB in the material could retard the smoke production with the application of the pilot flame. The EVA/OS/CB composites assumed a higher thermal stability than the EVA/OS composites and pure EVA.

     

The effect of the addition of talc on tribological properties of aramid fiber‐reinforced polyimide composites under high vacuum,ultraviolet or atomic oxygen environment

The aramid fibers‐reinforced polyimide composites filled with talc were fabricated by means of a hot press molding technique, and mechanical and tribological behaviors were comparatively investigated. Experimental results showed that the elastic modulus of the composites increased with an increase of the talc, but the impact intensity and loss factor decreased. Besides, the coefficient of friction decreased with the increase of the talc content. To contrast the effects of the ultrahigh vacuum (VC), ultraviolet (UV) or atomic oxygen (AO) on the composites, experiments without irradiation or after UV or AO irradiation were conducted. Scanning electron microscopy and X‐ray photoelectron spectroscopy (XPS) analysis showed that UV or AO irradiation can change the surface structure and chemical composition of the polymer because of the photooxidation and chemical erosion. Copyright © 2012 John Wiley & Sons, Ltd.     

Photobase generation from amineimide derivatives and their use for curing an epoxide/thiol system

The structural effects of amineimide derivatives on photobase generation and the use of the resultant base for thermal curing of an epoxide/thiol system are investigated. The results of UV spectral change and gas chromatographic‐mass spectrometric analysis indicated that amineimide derivatives undergo photolysis by UV irradiation and generate bases. The order of conversion of the photolysis for the functional groups introduced to amineimide derivatives was NO₂ > N(CH₃)₂ > CN > OCH₃ > H. By using aminimide derivatives with NO₂ and N(CH₃)₂ groups, the curing of the epoxide/thiol system was shifted to lower temperature after UV irradiation. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4045–4052, 2002     

Ultraviolet‐induced crosslinking of poly(butylene succinate) and its thermal property,dynamic mechanical property,and biodegradability

Crosslinking is an effective way to improve polymer properties. This paper focuses on ultraviolet‐induced crosslinking of poly(butylene succinate) (PBS) in the presence of a photoinitiator and a crosslinking agent at ambient temperature. The effects of the concentration of photoinitiator, the crosslinking agent content, and the irradiation time on the crosslink behavior were investigated. To obtain an appropriate gel fraction in different irradiation times, 3.0 wt% of photoinitiator and 10.0 wt% of crosslinking agent were proved to be the optimum choice. Furthermore, properties such as thermal properties, dynamic mechanical property, and enzymatic degradation of PBS before and after crosslinking were examined. Differential scanning calorimetry (DSC) analysis revealed that glass transition temperature (T_g) increased with increase in gel fraction, while melting temperature (T_m) and the degree of crystallinity decreased. This may be caused by the reduced molecular chain mobility and inhibited molecular motion for crystallization in crosslinked samples. The crosslinked polymer also showed improved thermal stability and dynamic mechanical property. In addition, the introduction of crosslinking retarded the enzymatic degradation rate of PBS, but it was still biodegradable. The improved properties of crosslinked PBS will extend the application of PBS. Copyright © 2009 John Wiley & Sons, Ltd.     

Photocrosslinking of polyethylene. I. Photoinitiators,crosslinking agent,and reaction kinetics

High density polyethylene has been photocrosslinked in the melt by using 4-chlorobenzophenone (4-CBP) as photoinitiator and triallylcyanurate (TAC) as crosslinking agent. Various factors affecting the crosslinking process (photoinitiator used and its concentration, irradiation temperature and time, atmosphere, UV light source, light intensity) were examined. By optimizing the irradiation conditions, it was found that samples up to 2 mm thick could readily be crosslinked to high gel content (≈ 90%) with satisfactory homogeneity within very short irradiation times (≈ 15 s). The kinetic analysis of the crosslinking process showed a linear relation between log S and log t (S is the sol fraction t is the irradiation time). An induction period was observed, the length of which decreased with increasing concentration of 4-CBP and increasing light intensity. An upper limit of gel content was also found for long irradiation times at a level depending on the concentration of 4-CBP. The crosslinking rate was proportional to the second order of light intensity at lower intensity and changed to first order at higher light intensity. A mechanism based on the recombination of chain radicals through both allyl and alkyl type radicals of TAC was proposed.     

Investigation of photo‐oxidative effect on morphology and degradation of mechanical and physical properties of nano CaCO3 silicone rubber composites

Photo‐oxidative degradation of treated and untreated nano CaCO₃: silicone rubber composite was studied under accelerated UV irradiation (≥290 nm) at different time intervals. Prolonged exposure to UV leads to a progressive decrease in mechanical and physical properties along with the change in behavior of filler‐matrix interaction. This was due to decrease in cross‐linking density with increase in mobility of rubber chains. Meanwhile, synthesized nano CaCO₃ was modified with stearic acid for uniform dispersion in rubber matrix. The increase in carbonyl (>CO), hydroxyl (? OH), CO₂, and alkene functional groups on the UV exposed surface of treated and untreated nano CaCO₃: silicone rubber composites at different time intervals was studied using Fourier transform infrared (FTIR) spectroscopy. The change in morphological behavior of filler‐matrix interaction after UV exposure was studied using SEM. Overall, the study showed that the treated nano CaCO₃: silicone composites were affected more by UV exposure than untreated nano CaCO₃: silicone composites and pristine composite after UV exposure. This effect was due to peeling of stearic acid from the surface of CaCO₃, which makes the rubber chains slippery and thus separation of filler and rubber chains takes place with initiation of fast‐degradation. Copyright © 2011 John Wiley & Sons, Ltd.     

UV aging behaviour of ethylene-vinyl acetate copolymers (EVA) with different vinyl acetate contents

The mild UV aging of ethylene-vinyl acetate copolymer (EVA) with two vinyl acetate (VAc) contents (14, 18 wt%) was performed in a xenon arc source chamber. The degradation mechanism was analyzed via attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), gel content and high temperature gel permeation chromatography (HTGPC). Photo-chemically induced deterioration was first initiated from vulnerable VAc units. Ketone formation preceded lactone generation, especially in EVA with high VAc content. Un-stable structures induced further degradation in the main chain. Competition between radiation induced cross-linking and chain scission in EVA was observed, and the later was confirmed to be dominant. Higher VAc content resulted in remarkable drop in molecular weight and growth in polydispersity. Apparent re-arrangement in crystallisation and consequent decrease in thermal stability are discussed through differential scanning calorimetry (DSC) and thermo-gravimetric analysis (TGA), which accorded well with the chain scission tendency. Interaction between photo-chemical degradation and physical annealing accounted for the first increasing then decreasing tendency in the mechanical properties of both EVAs.     

Novel amphiphilic triblocks fitted with photocrosslinkable termini,and their photocrosslinking to conetworks

Two new telechelic amphiphilic triblock copolymers, HE₃‐PEG‐b‐PDMS‐b‐PEG‐HE₃ and HE₃‐PEG‐b‐PDMS‐b‐PEG‐HE₃, i.e., sequence‐reversed triblocks of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic polydimethylsiloxane (PDMS) segments fitted with photocrosslinkable tri[2‐(3,4‐cyclohexane oxide)ethyl‐dimethylsiloxy]silane (HE₃) termini, were synthesized, characterized, photocrosslinked to amphiphilic conetworks (APCNs), and the properties of the APCNs were analyzed. APCNs in which the crosslinking sites are located in the hydrophobic domains exhibited significantly better mechanical properties than those in which the crosslinks were in the hydrophilic domains. The stiff domains formed of the UV‐crosslinkable HE₃ chain‐end substituents provide not only crosslinking but reinforcement as well. The crosslinking/reinforcement efficiency was greatly enhanced by the addition of excess HE₃. Water‐swollen APCNs were optically clear and exhibited mechanical properties appropriate for biomedical application. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 174–185, 2008     

Synergistic effect of combination of Irganox 1010 and zinc stearate on thermal stabilization of electron beam irradiated HDPE/EVA both in hot water and oven

Thermo-oxidative stability of HDPE/EVA blends can be considerably increased by combination of a high-molecular weight phenolic antioxidant and zinc stearate. In this work, the post-irradiation thermal stability of HDPE/EVA blends has been studied. High-density polyethylene and its blends with ethylene-vinylacetate copolymer in both pure form and mixed with Irganox 1010 and zinc stearate were exposed to electron beam radiation at doses between 80 and 150 kGy, at room temperature, in air. In order to evaluate the thermal stability of the samples, post-irradiation heat treatments were done in both hot water bath at 95 °C and in an oven at 140 °C. The mechanical properties and changes in the chemical structure were determined during thermal aging in hot water and oven. The gel content was enhanced by increasing EVA concentration in all applied doses. The stabilized blends have lower gel content than the unstabilized samples. From the results of heat aging treatments it was observed that the thermal stability of the unstabilized blend samples was lower than HDPE. Thermal stability of the samples has been improved by incorporation of Irganox 1010 and zinc stearate. Formation of hydroxyl group was insignificant for stabilized samples during heat aging in both conditions. Also, the changes in the value of oxidation induction time (OIT) for the stabilized samples were negligible after prolonged immersion in hot water.