Structure–property correlations of heat‐shrinkable polymer blends based on ethylene vinyl acetate/carboxylated nitrile rubber in the presence of different curatives

Elastic memory was introduced into heat‐shrinkable polymer blends in the form of an elastomeric phase and through subsequent crosslinking. Blends of ethylene vinyl acetate and carboxylated nitrile rubber with different curative systems were studied with respect to their shrinkability. With an increase in the cure time (the crosslinking density, or memory point), shrinkage increased for the blends with all the curative systems except dicumyl peroxide (DCP). Increasing the elastomer content increased shrinkability because of the increasing driving retraction force of the oriented elastomer phase. A sample stretched at a high temperature (HT) showed greater shrinkage than a sample stretched at room temperature (RT) because of the greater concentration and degree of orientation of the extended chains. Generally, the crystallinity of the stretched (RT and HT) samples was higher than that of ordinary unstretched and shrunk samples, and this increased the effectiveness of intermolecular interactions in the former. For all systems except DCP, RT‐stretched samples showed higher crystallinity than corresponding HT‐stretched samples. With RT stretching, rapid extension and subsequent recrystallization occurred in samples molten at high local values of the stored elastic energy. An increase in the crosslinking density and orientation of the blends increased the thermal stability because of the formation of strong networks and compact structures. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1414–1420, 2003     

Effect of rubber content on mechanical properties and heat shrinkage of ethylene vinyl acetate copolymer blended with epoxidized natural rubber

Ethylene vinyl acetate (EVA, 18 mol % vinyl acetate) and epoxidized natural rubber (ENR, 50 mol % epoxidation) were blended in an internal mixer and compared to EVA. Dicumyl peroxide (DCP) was used as a curing agent. The blends consisted of 10–50 wt % of ENR and were compared with crosslinked EVA in terms of heat shrinkage, mechanical properties, and degree of crystallinity. It is found that the blends showed a decrease in mechanical properties with increasing ENR content because DCP was not a good vulcanizing agent of ENR. The addition of ENR did not affect heat shrinkability of EVA. The maximum heat shrinkage obtained was 80% for EVA and the blends. ENR did not affect thermal properties of EVA investigated by the differential scanning calorimetry. The X‐ray diffractometry showed discrepancy in degree of crystallinity before and after specimen stretching and after heat shrinking. It is believed that ENR particles decreased molecular orientation of EVA resulting in a decrease in degree of crystallinity but the remained orientation was sufficient for heat shrinking. The blend showed better extrudability than EVA after increasing take‐up speed. Therefore, the extruded tube prepared from the blend provided higher heat shrinkage than EVA tube. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Shape memory effect of ethylene–vinyl acetate copolymers

Crosslinked ethylene–vinyl acetate (EVA) copolymers with VA content of 28% by weight were prepared by a two‐step method by evenly dispersing the crosslinking agent (dicumyl peroxide) into the EVA matrix and then crosslinking at elevated temperatures. The crosslinking features of the samples were analyzed by Soxhlet extraction with xylene and dynamic mechanical measurements. All the samples were crystalline at room temperature, and the chemical crosslinks seemed to have little effect on the melting behavior of polyethylene segment crystals in the EVA copolymers. The shape recovery results indicated that only those specimens that had a sufficiently high crosslinking degree (gel content higher than about 30%) were able to show the typical shape memory effect, a large recoverable strain, and a high final recovery rate. The degree of crosslinking can be influenced by the amount of the peroxide and the time and temperature of the reaction. The response temperature of the recovery effect (about 61°C) was related to the melting point of the samples. The EVA shape memory polymer was characterized by its low recovery speed that resulted from the wide melting range of the polyethylene segment crystals. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1063–1070, 1999     

Influence of heat‐setting temperature on the properties of a stretched polypropylene microporous membrane

The influence of heat‐setting temperature on the stress–strain curves, differential scanning calorimetry (DSC) curves and properties of a stretched polypropylene microporous membrane was studied. It was found that with an increase of heat‐setting temperature, a plastic plateau region in the stress–strain curves and a melting endotherm plateau in the DSC curves became apparent. The permeability and porosity firstly increased with the temperature to 145 °C and then decreased. The pore structure arrangement showed similar changing trend. On the one hand, higher heat‐setting temperature could decrease the shrinkage of the microporous membrane. On the other hand, the crystallization of some chains around separated lamellae during heat‐setting was unfavorable to the properties of the microporous membrane. The occurrence of crystallization during heat‐setting explained the origin of the plastic plateau. For the fabrication of microporous membranes based on the melt‐stretching mechanism with good dimensional stability, heat‐setting is necessary, but too high a heat‐setting temperature can destroy the permeability. © 2013 Society of Chemical Industry     

Crosslinking of poly[(3‐hydroxybutyrate)‐co‐(3‐hydroxyvalerate)] using dicumyl peroxide as initiator

In order to modify poly [(3‐hydroxybutyrate)‐co‐(3‐hydroxyvalerate)] (PHBV), the crosslinking of this copolymer was carried out at 160 °C using dicumyl peroxide (DCP) as the initiator. The torque of the PHBV melt showed an abrupt upturn when DCP was added. Appropriate values for the gel fraction and crosslink density were obtained when the DCP content was up to 1 wt% of the PHBV. According to the NMR spectroscopic data, the location of the free radical reaction was determined to be at the tertiary carbons in the PHBV chains. The melting point, crystallization temperature and crystallinity of PHBV decreased significantly with increasing DCP content. The effect of crosslinking on the melt viscosity of PHBV was confirmed as being positive. Moreover, the mechanical properties of PHBV were improved by curing with DCP. When 1 wt% DCP was used, the ultimate elongation of PHBV increased from 4 to 11 %. A preliminary biodegradation study confirmed the total biodegradability of crosslinked PHBV. Copyright © 2004 Society of Chemical Industry     

Thermal and mechanical properties of uncrosslinked and chemically crosslinked polyethylene/ethylene vinyl acetate copolymer blends

Uncrosslinked and chemically crosslinked binary blends of low‐ and high‐density polyethylene (PE), with ethylene vinyl acetate copolymer (EVA), were prepared by a melt‐mixing process using 0–3 wt % tert‐butyl cumyl peroxide (BCUP). The uncrosslinked blends revealed two distinct unchanged melting peaks corresponding to the individual components of the blends, but with a reduced overall degree of crystallinity. The crosslinking further reduced crystallinity, but enhanced compatibility between EVA and polyethylene, with LDPE being more compatible than HDPE. Blended with 20 wt % EVA, the EVA melting peak was almost disappeared after the addition of BCUP, and only the corresponding PE melting point was observed at a lowered temperature. But blended with 40% EVA, two peaks still existed with a slight shift toward lower temperatures. Changes of mechanical properties with blending ratio, crosslinking, and temperature had been dominated by the extent of crystallinity, crosslinking degree, and morphology of the blend. A good correlation was observed between elongation‐at‐break and morphological properties. The blends with higher level of compatibility showed less deviation from the additive rule of mixtures. The deviation became more pronounced for HDPE/EVA blends in the phase inversion region, while an opposite trend was observed for LDPE/EVA blends with co‐continuous morphology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3261–3270, 2007     

Effect of different curing systems on heat shrinkability and mechanical properties of ethylene vinyl acetate/epoxidized natural rubber blends

Ethylene vinyl acetate (EVA)/epoxidized natural rubber (ENR) blends containing 10 and 30 wt % ENR were prepared by using an internal mixer. Five different types of curing systems were employed: dicumyl peroxide (DCP), sulfur (S), phenolic resin (Ph), DCP + S, and DCP + Ph. DCP could crosslink with both EVA and ENR while S and Ph were curing agents for ENR. The DCP system provided the lowest tensile properties and tear strength because of low crosslinking in ENR phase. Addition of sulfur or phenolic resin increased the mechanical properties due to a better vulcanization of the rubber phase. The mechanical properties of the blends decreased with increasing ENR content. The rubber particle size in the blends containing 30% ENR played a more important role in the mechanical properties than the blends containing 10% ENR. ENR particle size did not affect heat shrinkability of EVA and a well vulcanized rubber phase was not required for high heat shrinkage. Furthermore, heat shrinkage of the blends slightly changed as the ENR content increased for all curing systems. With regard to the mechanical properties and heat shrinkability, the most appropriate curing system was DCP + Ph and in the case the 10 wt % ENR content produced a more favorable blend. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of the addition of depolymerised ethylene vinyl acetate on the mechanical,thermal, chemical and shrinkage properties of cured unsaturated polyester resins

Unsaturated polyester resins (UPRs) are versatile compounds. However, their major drawback is the high shrinkage exhibited on curing. An attempt was made to reduce the shrinkage of UPRs without affecting other properties. In the present study a commonly used iso‐reactive UPR was modified by the addition of ethylene–vinyl acetate (EVA; subjected to controlled depolymerisation to obtain samples of various molecular weights), and was cured at room temperature. The peak exotherm temperature and gel time were both observed to decrease with an increase in EVA content. The composition incorporating 0.5% of depolymerised EVA1 (highest degree of branching) showed maximum improvement in tensile and flexural properties with the heat deflection temperature and impact properties remaining almost unaffected. A uniform dispersion for the UPR containing 0.5% of EVA1 was observed. Addition of EVA reduced the percentage shrinkage in the modified matrix. Incorporation of depolymerised EVA can be an attractive option for the reduction of shrinkage in UPRs. The advantage of using depolymerised EVA is that generated waste EVA can be depolymerised and reused for this application making it cost effective. Copyright © 2010 Society of Chemical Industry     

Studies on biaxial stretching of polypropylene film. IX. Melting behavior of biaxially stretched film in one step

Melting temperature of a film biaxially stretched in one step in air at 152 or 140°C increases with increase of vA, whereas heat of fusion and density decrease with increase of vA, where vA is the degree of stretching in area. The rapid decrease in density occurs for vA > 10. Extrapolation of the plot of the density versus vA^?1/2 gives a value of 0.870 g/cm³ at infinite vA, which has been reported as the amorphous density of isotactic polypropylene by Farrow. This is so because the fine structure of the film becomes more and more amorphous with further stretching and reaches completely amorphous state at infinite vA. The temperature of stretching has a strong effect on the thermal behavior of a film; a low stretching temperature (140°C) brings about lower melting temperature, heat of fusion, and density. Crystallinity after melt press has not so large an effect on the melting behavior as the stretching temperature. Melting temperature and the shape of the thermogram also depend on the heating rate. There is an appropriate heating rate depending on vA which gives the minimum melting temperature. With stretched samples, a small side peak or a shoulder appears at a relatively low temperature in the thermogram when a high heating rate is used.     

Thermal characteristics and temperature profile changes of structurally different polyethylenes with peroxide modifications

Crosslinking and processing characteristics of polyethylenes (PEs) with different molecular architectures, namely high‐density polyethylene (HDPE), linear low‐density polyethylene (LLDPE), and low‐density polyethylene (LDPE), were studied with regard to the effects of peroxide modifications and coolant flow rates. Dicumyl peroxide (DCP) and di‐tert‐butyl peroxide (DTBP) were used as free‐radical inducers for crosslinking the PEs. The characteristics of interest included normalized gel content, real‐time temperature profiles and their cooling rates, exothermic period, crystallinity level, crystallization temperature, and heat distortion temperature. The experiments showed that LDPE exhibited the highest normalized gel content. The real‐time cooling rates, taken from the temperature profiles for all PEs before the crystallization region, were greater than those after the crystallization region. The cooling rate of the PEs increased with the presence of DCP, whereas the crystallization temperature of the PEs was lowered. The HDPE appeared to show the longest exothermic period as compared with those of the LLDPE and LDPE. The exothermic period showed an increase with increasing coolant flow rate, but it was decreased by the use of DCP. As for the effect of peroxide type, the gel content and cooling rate of the PE crosslinked by DCP were higher than those for the PE crosslinked by DTBP. The DTBP was the more effective peroxide for introducing crosslinks and simultaneously maintaining the crystallization behavior of the PE. J. VINYL ADDIT. TECHNOL., 20:80‐90, 2014. © 2014 Society of Plastics Engineers     

Melt functionalization of EVA copolymers with maleic anhydride

Ethylene vinyl acetate (EVA) copolymers with different amounts of vinyl acetate were melt‐functionalized with maleic anhydride. The effect of benzoyl peroxide, t‐butyl perbenzoate, and dicumyl peroxide (DCP) as free‐radical initiators on the functionalization performance was studied. The crosslinking reactions occur to a larger extent than in polyethylene, indicating that the vinyl acetate groups favor the formation of free radicals. From all the experiments performed in this study, the recommended initiation system to achieve the best values of the functionalization degree and the lower gel content involves the use of DCP in a concentration of about 0.3 wt % and a maleic anhydride concentration around 5.0 wt %. From FTIR and TGA analyses, it is suggested that the hydrogen abstraction in the EVA copolymers occurs both in the methyl group of the acetate moiety and in the tertiary C—H. The free radicals generated in the tertiary C—H react with maleic anhydride in a higher proportion. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1799–1806, 1999     

Crystallization and melting behavior of nano‐CaCO3/polypropylene composites modified by acrylic acid

Nano‐CaCO₃/polypropylene (PP) composites modified with polypropylene grafted with acrylic acid (PP‐g‐AA) or acrylic acid with and without dicumyl peroxide (DCP) were prepared by a twin‐screw extruder. The crystallization and melting behavior of PP in the composites were investigated by DSC. The experimental results showed that the crystallization temperature of PP in the composites increased with increasing nano‐CaCO₃ content. Addition of PP‐g‐AA further increased the crystallization temperatures of PP in the composites. It is suggested that PP‐g‐AA could improve the nucleation effect of nano‐CaCO₃. However, the improvement in the nucleation effect of nano‐CaCO₃ would be saturated when the PP‐g‐AA content of 5 phf (parts per hundred based on weight of filler) was used. The increase in the crystallization temperature of PP was observed by adding AA into the composites and the crystallization temperature of the composites increased with increasing AA content. It is suggested that the AA reacted with nano‐CaCO₃ and the formation of Ca(AA)₂ promoted the nucleation of PP. In the presence of DCP, the increment of the AA content had no significant influence on the crystallization temperature of PP in the composites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2443–2453, 2004     

Preparation of highly filled wood flour/recycled high density polyethylene composites by in situ reactive extrusion

Highly filled wood flour/recycled high density polyethylene (WF/RHDPE) composites were directly prepared by in situ reactive extrusion using a twin‐screw/single‐screw extruder system. The effects of dicumyl peroxide (DCP) content on extrusion pressure, rheological behavior, mechanical properties, fractured surface morphology of the composites, and melting temperature of RHDPE in the composites were investigated. The extrusion pressure and torque of WF/RHDPE composite melt increased with DCP content. Mechanical property tests and scanning electron microscopy analysis results confirmed that the interfacial interaction of the composites was improved by in situ reaction. The composites show lower melting peak temperature (T_m) than RHDPE. The cooling in profile extrusion shortened the crystallization time, resulting in decrease of crystalline order of RHDPE in the composites. There are no noticeable changes of T_m values with increasing DCP content. Comparative study on composites with maleic anhydride grafted polyethylene as compatibilizer demonstrated that mechanochemical treatment with DCP and maleic anhydride was an effective method to improve interfacial adhesion for WF/RHDPE composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Reactive compatibilization of the poly(butylene terephthalate)–EVA blend by maleic anhydride. II. Correlations among gel contents,grafting yields,and mechanical properties

Correlations among the degree of crosslinking of ethylene vinyl acetate copolymer (EVA), the grafting yield of maleic anhydride (MAH) onto EVA, and the mechanical properties of the blends of poly(butylene terephtalate) (PBT) with EVA‐g‐MAH were investigated. The EVA was functionalized by melt grafting reaction in the presence of MAH and dicumyl peroxide (DCP) using a plasticorder. The grafting yield of MAH was increased by increasing the concentration of MAH and DCP. The flexural strength of PBT–EVA‐g‐MAH blends depends on both the grafting yield of MAH and the degree of crosslinking of EVA, while the crosslinked parts of EVA‐g‐MAH hindered rather than improved the tensile strength regardless of the increase of the grafting yield of MAH. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1305–1310, 2003     

Effects of stretching on crystalline phase structure and morphology of hard elastic PVDF fibers

The phase characteristics and morphology of stretched hard elastic poly(vinylidene fluoride) (PVDF) fibers were investigated by X‐ray diffraction (XRD) and wide‐angle and small‐angel X‐ray scattering (WAXS and SAXS). It was indicated that α and β phases coexisted in stretched PVDF fibers, stretching assisted in α to β phase transformation. The β/α ratios of stretched PVDF fibers were affected by stretching temperature, rate, and ratio. The β phase content of stretched PVDF fibers had an abrupt increase when stretched near 70°C, and then it decreased with increasing stretching temperature. Besides, the β/α ratio of PVDF fibers increased with stretching rate and ratio. The total crystallinity of PVDF fibers did not change much even on different stretching conditions. WAXS results indicated that the unstretched and stretched PVDF fibers all exhibited three strong equatorial streaks, with d‐spacing (0.964, 0.488, and 0.439 nm) and (0.946, 0.494, and 0.480 nm), which suggested that PVDF fibers still remained the crystalline reflections of c‐axis orientation even after being stretched. The long periods of stretched PVDF fibers, calculated from SAXS curves, increased from 19.04 to 39.75nm. On the basis of these results, the β transformation mechanism of stretched PVDF fibers was also discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2254–2259, 2007     

Properties and curing behavior of reactive blended allyl novolak with bismaleimide using dicumyl peroxide as a novel curing agent

For reducing the cure temperature and improving the thermal stability and mechanical properties, a thermosetting resin system composed of novolak and bismaleimide (BMI) was developed by reactive blending and using dicumyl peroxide (DCP) as a novel curing agent. Novolak was allylated and reacted with BMI to produce bismaleimide allylated novolak (BAN), and the effect of DCP on flexural, impact and heat distortion temperature of cured resin were investigated. On the basis of improved mechanical and thermal properties at 0.5% DCP contents, the curing behavior of DCP/BAN resin system was evaluated by DSC analysis. Ene, Diels‐Alder, homo‐polymerization and alternating copolymerization which occurred in DCP/BAN resin system were further verified using FTIR at sequential cure conditions from 140 to 200°C. Kissinger and Ozawa‐Flynn‐wall methods were used to optimize the process and curing reactions of DCP/BAN resin system. The results showed that the addition of 0.5% DCP in BAN reduced the curing temperature and time of the modified resin. For evaluating process ability of the modified system, composite samples using polyvinyl acetyl fiber were molded and tested for flexural properties. The resulting samples showed better flexural properties when compared with the composite made with neat BAN. The modified 0.5% DCP/BAN resin system with good mechanical properties and manufacturability can be used for making bulk molding compounds and fiber reinforced composites required in various commercial and aerospace applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41829.     

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     

Cross‐linking of ethylene‐octene copolymer (EOC) by dicumyl peroxide (DCP)

Ethylene‐octene copolymer (EOC) was crosslinked by dicumyl peroxide (DCP) at various temperatures (150–200°C). Six concentrations of DCP in range 0.2–0.7 wt % were investigated. cross‐linking was studied by rubber process analyzer (RPA) and by differential scanning calorimetry (DSC). From RPA data analysis real part modulus s', tan δ, and reaction rate were investigated as a function of peroxide content and temperature. The highest s'_max and the lowest tan δ were found for 0.7% of DCP at 150°C. Chain scission was analyzed by slope analysis of conversion ratio, X in times after reaching the maximum. Less susceptible to chain scission are temperatures in range 150–170°C and peroxide levels 0.2–0.5%. Heat of reaction was analyzed by DSC at various heating rates (5–40°C min⁻¹). It was found to be exothermic. By projection to zero heating rate, the reaction was found to start at 128°C with the maximum at 168°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of organic peroxides on the morphology and properties of EVA/Cloisite 15A nanocomposites

This article describes the effect of the presence of organic peroxides on the morphology and properties of ethylene vinyl acetate copolymer (EVA)/Cloisite 15A nanocomposites. The results show that the presence of dicumyl peroxide (DCP) or dibenzoyl peroxide (DBP) during the preparation of EVA/Cloisite 15A clay nanocomposites gives rise to intercalated, exfoliated, or mixed morphologies, which are not normally observed for samples prepared in the absence of organic peroxides. In the absence of clay, both DCP and DBP initiate de‐acetylation and chain scission of EVA chains, but the influence of DBP is more pronounced. The presence of clay inhibits the initiation of EVA degradation by DCP free radicals, which can be observed in the higher tensile strength values for DCP treated samples, as well as in the de‐acetylation step in the TGA curves. DBP has a more significant influence on the polymer degradation, and this gives rise to reduced thermal stability and mechanical properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Molecular Sorption by Heterogeneous Natural Rubber/Poly(ethylene-co-vinyl acetate) Blend Systems

The sorption of n-alkanes, viz. hexane, heptane and octane by cross-linked natural rubber/poly(ethylene-co-vinyl acetate) (NR/EVA) blends has been studied at 28, 38, 48 and 58°C, with special reference to the effects of EVA content, cross-linking systems, penetrant nature and temperature. The solvent transport was found to decrease with increase in EVA content in the blends. The effects of blend ratio on the transport characteristics have been correlated with the phase morphology of the blends, using scanning electron micrographs and optical micrographs. Among the three vulcanising systems, viz. sulphur (S), dicumyl peroxide (DCP) and a mixed system (S + DCP) employed for the matrix, the DCP cross-linked blends exhibited the lowest solvent uptake. Octane has been found to show higher interaction with the blends than hexane and heptane, probably owing to the closer solubility parameter values. The computed transport coefficients, viz. diffusion coefficient and permeability coefficient, were found to decrease with increase in EVA content in the blends. At room temperature, the mechanism of diffusion was found to deviate slightly from the regular Fickian trend for all blend systems. The blend–solvent interaction parameter and the activation energy for transport were also determined from the sorption data.