Effects of cooling rates on crystallization behavior and melting characteristics of isotactic polypropylene as neat and in the TPVs EPDM/PP and EOC/PP

Non-isothermal crystallization behavior and melting characteristics of polypropylene (PP) in EPDM/PP and EOC/PP TPVs were studied at various cooling rates using differential scanning calorimetry (DSC). The results revealed that the crystallization of PP in the TPVs occurs at a lower degree of undercooling, relative to neat PP, with smaller size PP crystals. The vulcanized EPDM and EOC particles could accelerate the crystallization of the PP phase either by providing nucleation or by promoting interfacial crystallization. The crystallization exotherm and melting endotherm peaks of the TPVs were broad, and they shifted towards lower temperatures as the cooling rate was increased. The analysis of non-isothermal crystallization kinetics indicates that the crystallization of the PP in the TPVs is heterogeneous nucleation, with two or three-dimensional growth during primary and secondary crystallization. Furthermore, the vulcanized EPDM and EOC particles promote the initial crystallization activation energy of the PP in TPVs to exceed that of the neat PP. The developed mathematical models show an approximately power-law dependence on the cooling rate for the crystallization behavior and the melting characteristics of PP in the TPVs.     

Reactive EB Processing of Polymer Compounds

Polymer modification with high energy electrons is well-established in polymer industry and used for degradation, cross-linking, grafting, curing, and polymerization. These applications use local and temporal precise input of energy in order to generate excited atoms or molecules as well as ions for subsequent molecule changes via radical induced chemical reactions. Reactive electron beam (EB) processing combines melt mixing process and chemical reaction simultaneously. For this purpose, a 1.5 MeV electron accelerator was directly coupled to an internal mixer in order to induce chemical reactions by energy input via high energy electrons under dynamic conditions of melt mixing of different polymer compounds. In the present study, reactive EB processing was used for the development of a flame retardant polyethylene composite as well as Thermoplastic Vulcanizate. The influence of absorbed dose as well as electron energy and electron treatment time was studied. Increased values of both tensile strength and elongation at break of polymer compounds indicated in-situ compatibilization upon reactive EB processing.     

Morphology and properties of polypropylene/ethylene–octene copolymer/clay nanocomposites with double compatibilizers

The influence of nanoclay on the morphology and properties of the polypropylene (PP)/ethylene–octene block copolymer (EOC) blend with double compatibilizers of maleated PP (PP‐g‐MA) and maleated EOC (EOC‐g‐MA) was investigated and compared with the nanocomposites containing either PP‐g‐MA or EOC‐g‐MA as a compatibilizer. X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy were utilized for morphological characterization in conjunction with dynamic mechanical thermal analysis, mechanical testing, and rheological evaluation of these nanocomposites. The results suggested that in the nanocomposite including both compatibilizers of PP‐g‐MA and EOC‐g‐MA, clay was dispersed as a mixed structure of intercalation and exfoliation in both phases of the polymer blend. Comparing the mechanical properties of the studied nanocomposite with nanocomposites of PP/EOC/PP‐g‐MA/clay and PP/EOC/EOC‐g‐MA/clay also indicated that the nanocomposite containing mixed compatibilizers displayed higher tensile modulus, tensile strength, and complex viscosity because of the better dispersion of clay in both phases. The results also confirmed the increased structural stability and reduced dispersed phase size of PP/EOC/PP‐g‐MA/EOC‐g‐MA blend in the presence of clay that proposed the compatibilization role of clay in this nanocomposite. Copyright © 2014 John Wiley & Sons, Ltd.     

Prediction models for the key mechanical properties of EPDM/PP blends as affected by processing parameters and their correlation with stress relaxation and phase morphologies

The optimum condition of processing parameters (mixing temperature, rotor speed, fill factor, and blend ratio) and prediction models for the best key mechanical properties of ethylene propylene diene terpolymer/polypropylene thermoplastic vulcanizates (EPDM/PP TPVs) was investigated by using the Taguchi's optimization technique and data analysis. The results reveal that all of the processing parameters affected significantly the mechanical properties of the EPDM/PP TPVs, but specifically the blend ratio contributed more than 90% in effect size on tensile strength and tension set. There were three main factors, the mixing temperature, the fill factor, and the blend ratio, influencing the elongation at break. Furthermore, the mathematic models were effective and reliable in predicting the properties of TPVs. The correlation of mechanical properties, stress relaxation, and phase morphologies of the TPVs prepared from the predicted models was also investigated. It can be summarized that the morphological structure and stress relaxation of the TPVs were strongly governed by the EPDM content in the blend ratio. That is, the higher the EPDM content, the better phase morphology having smaller size of the vulcanized EPDM particles distributed in the PP matrix and the higher rate of stress relaxation. Moreover, these two properties were then principally pushing the mechanical characteristics of the EPDM/PP TPVs. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of β-phase on the fracture behavior of dynamically vulcanized PP/EPDM blends studied by the essential work of fracture approach

The effect of β phase polypropylene (PP), induced by β-nucleating agent (β-NA), on the fracture behavior in dynamically vulcanized thermoplastic elastomers (TPVs) based on dynamically vulcanized PP/ethylene-propylene-diene rubber (EPDM) blend was studied. Differential Scanning Calorimetry (DSC) and Wide-angle X-ray diffraction (WAXD) were employed to study the melting behavior and crystalline structures, and the results indicated that the β-NA induced β phase of PP effectively in TPVs. With the increasing dosage of the β-NA incorporated in, the content of β phase increased while the total crystallinity of the blend kept constant. The fracture behavior of the TPVs with different β phase content was studied with double edge notched tensile loaded specimens (DENT) using the essential work of fracture (EWF) approach. The specific essential work of fracture (w_e) increased with the increasing of β phase content, indicating that the presence of β phase could effectively enhance the fracture toughness of TPVs.     

Study on the toughening mechanism of PP/EVA dynamically crosslinked blend

The toughening mechanism of polypropylene (PP)/ethylene-co-vinyl acetate (EVA) dynamically crosslinked blend was investigated. The results indicated that dynamical crosslinking technology not only improved the interfacial adhesion between PP and EVA, but also increased the mechanical properties of PP/EVA blend. The quantitative and qualitative analysis of scanning electron microscopy (SEM) micrographs demonstrated that dynamical crosslinking technology could refine EVA particles in PP/EVA blend and promote the size distribution of EVA particles. The critical matrix ligament thickness of dynamically crosslinked and uncrosslinked blend was about 0.55 μm and 0.6 μm, respectively, indicating that the brittle-ductile transition occurred. Dynamic mechanical analysis (DMA) results illustrated that the tan δ peak of PP component in the dynamically crosslinked blend moved toward lower temperature compared with that of pure PP and the PP component in uncrosslinked blend; and the tan δ value of the dynamically crosslinked blend was higher than that of the uncrosslinked blend, which interpreted the toughening mechanism of dynamical crosslinking technology from the dynamic mechanical property of the blend.     

Transmission electron microscopy study of phase morphology in polypropylene/ethylene-octene copolymer blends

Blends of polypropylene (PP) and ethylene-octene copolymers (EOC) were investigated by transmission electron microscopy (TEM) and by differential scanning calorimetry (DSC). The EOC contained 28, 37, 40 or 52 wt% of octene. Only the 50/50 PP/EOC ratio was used for all blends. None of the blends was fully miscible, there was always two-phase morphology. TEM observation followed by image analysis by ImageJ software revealed that the largest particles were in blend containing EOC-28 and the smallest were in blend with EOC-52. The coarsening rate at 200 °C was evaluated by TEM. The glass transition temperature (T_g) shift indicated partial miscibility. Partial miscibility was then confirmed by direct observation of bright PP lamellae in EOC dark phase.     

Preparation and flammability of EPDM/PP/Mg(OH)2 dynamic vulcanizates

Magnesium hydroxide (MH) flame retardant dynamic vulcanized ethylene‐propylene‐diene terpolymer (EPDM)/polypropylene (PP) thermoplastic vulcanizates (TPVs) were prepared by a twin‐screw extruder. Influences of MH on their morphology, mechanical properties, flammability, and crystallization behavior have been investigated. Static tensile measurements exhibited that TPVs have higher mechanical properties than un‐vulcanized EPDM/PP/MH blends (UVBs). Scanning electron microscopy (SEM) studies showed that the formation of the larger‐size “micro‐encapsulated structure” where the MH aggregates were covered with a cross‐linked rubber phase improved the interaction between MH and polymer matrix. Results of limiting oxygen index (LOI) and microscale combustion calorimetry (MCC) confirmed that TPVs had superior fire‐resistant properties to UVBs. SEM images showed that more uniform and compact charred layers were generated in TPVs. The differential scanning calorimetry (DSC) results indicated that the crystallization behavior of the flame retardant TPVs changed marginally with increase in MH content. Copyright © 2009 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.     

Compatibilized blends of thermoplastic polyurethane (TPU) and polypropylene

Compatibilized blends of thermoplastic polyurethane (TPU) and polypropylene (PP) were developed using amine (primary or secondary) functionalized PP's (PP-g-NH₂ or PP-g-NHR). The strategy of reactive compatibilization is based on fast reactions between amine functional groups and urethane linkages or traces of free isocyanates released by thermal degradation of TPU. Excellent compatibilization between TPU and PP was confirmed by rheological, morphological, and mechanical properties. Much finer domain size, higher interfacial adhesion, and more stable morphologies were clearly observed by scanning electron microscopy. Significant improvements in the overall mechanical properties (tensile, tear, abrasion) imply significantly more reaction between TPU and PP phases in the two TPU/PP blends containing PP-g-NH₂ or PP-g-NHR than a TPU/PP blend using PP-g-MA as a compatibilizing agent.     

Preparation of polypropylene/ethylene‐propylene‐diene terpolymer/nitrile rubber ternary thermoplastics vulcanizates with good mechanical properties and oil resistance by core‐shell dynamic vulcanization

As the most successful commercialized thermoplastic vulcanizates (TPVs), polypropylene (PP)/ethylene propylene rubber (EPDM) TPVs exhibit poor oil resistance. In this work, we prepared PP/EPDM/butadiene acrylonitrile rubber (NBR) ternary TPVs with good oil resistance using core‐shell dynamic vulcanization. According to the theoretical analysis of the spreading coefficient and the transmission electron microscopy results, the rubber phases exhibited a special core‐shell structure, in which the cross‐linkedNBR‐core was encapsulated by the EPDM‐shell. The core‐shell structure effectively improved the interfacial compatibility between PP and NBR phase as the EPDM‐shell could avoid the direct contact of them, thus improving the mechanical properties of the TPVs. For example, the PP/EPDM/NBR (40/30/30) ternary TPV showed enhanced tensile strength of 12.57 MPa, compared with 10.71 MPa of PP/EPDM (40/60) TPV and 11.11 MPa of PP/NBR (40/60) TPV, respectively. Moreover, the oil resistance of the TPVs was also improved. Compared with PP/EPDM TPV, the change rates in mass, volume, tensile strength and elongation at break of PP/EPDM/NBR TPV after oil immersion decreased by 42.18%, 48.69%, 52.68% and 28.77%, respectively.     

Mechanical properties,surface morphology and failure mode of γ-ray irradiated blends of polypropylene and ethylene-vinyl acetate rubber

The effect of ⁶⁰Co γ-radiation on the mechanical properties, surface morphology and failure characteristics of blends of polypropylene [PP] and ethylene-vinyl acetate rubber [EVA] has been studied with specific reference to the effect of blend ratio, dynamic crosslinking of the rubber phase and absorbed radiation doses. Samples were subjected to radiation in the dose range of 1 to 100 Mrad in air at room temperature at the rate of 0·321 Mrad/h. Both chain scission and crosslinking occur simultaneously in the blend samples. PP and blends containing higher proportions of PP (≥50%) undergo predominant chain scission at lower doses (≤50 Mrad), which causes a drastic drop in tensile strength, followed by a levelling out at higher doses of 100 Mrad. EVA undergoes crosslinking at lower doses resulting in an increase in tensile strength in the dose range 1 to 10 Mrad followed by a decrease in the range 10–25 Mrad. Further increase in radiation dose has little effect on tensile strength. The effect of radiation on stress-strain behaviour, elongation at break, energy at rupture and hardness was also studied. The morphology of the irradiated surfaces after an absorbed dose of 100 Mrad has been examined by scanning electron microscopy (SEM). In order to understand the effect of γ-radiation on the failure mechanism, tensile failure surfaces of both unirradiated and irradiated samples have also been examined by SEM.     

Exploring the effect of radiation crosslinking on the physico‐mechanical,dynamic mechanical and dielectric properties of EOC–PDMS blends for cable insulation applications

This work focuses on the effect of electron beam irradiation on the physico‐mechanical, dynamic mechanical and dielectric properties of blends based on ethylene octene copolymer (EOC) and poly dimethyl siloxane (PDMS) rubber. It is found that electron beam irradiation caused considerable improvement in the physico‐mechanical properties; the tensile strength was enhanced by nearly 35% for 70:30 EOC:PDMS blend. Phase morphology of the blends analyzed before irradiation by scanning electron microscopy (SEM) exhibited droplet/matrix morphology with sizes of the PDMS rubber domain varying from 0.55 µm to 0.47 µm as the amount of PDMS rubber decreased from 30 wt% to 10 wt%. This reduction in the PDMS rubber domain has been correlated with the physico‐mechanical properties of the blends. Further, the dynamic mechanical properties and creep behavior of these EOC:PDMS blends before and after irradiation has been studied. It is inferred that the 70:30 blend after radiation crosslinking shows a 17% decrease in the creep compliance, i.e. higher creep resistance compared to neat blends. All the radiation crosslinked blends exhibited lower dielectric constant, lower dielectric loss and higher electrical resistivity as compared to the virgin blends which makes it suitable for cable insulating application. Copyright © 2016 John Wiley & Sons, Ltd.     

The compatibilizing effect of epoxy resin (EP) on polypropylene (PP)/recycled acrylonitrile butadiene rubber (NBRr) blends

A new method was used to prepare thermoplastic elastomers based on polypropylene (PP)/recycled acrylonitrile butadiene rubber (NBRr) with improved mechanical properties. An epoxy resin (EP) was used as a compatibilizing agent. The effect of EP on mechanical properties, swelling percentage and morphological characteristics of the blends was investigated with different blend compositions. The results showed that the incorporation of EP has improved the tensile strength, Young's modulus and elongation at break of PP/NBRr-EP blends compared with PP/NBRr blends. The enhancement of tensile properties of PP/NBRr-EP blends is due to the better adhesion between the two phases with the incorporation of EP. This is quite evident by scanning electron microscopy of tensile fractured surfaces. PP/NBRr-EP blend exhibits lower stabilization torque and swelling percentage than PP/NBRr blends. The lower stabilization torque is an indication of better processing characteristics.     

Superior heat‐resistant and oil‐resistant blends based on dynamically vulcanized hydrogenated acrylonitrile butadiene rubber and polyamide 12

High‐performance thermoplastic vulcanizates (TPVs) are the new generation of TPVs that provide superior heat and oil aging behavior. TPVs based on hydrogenated acrylonitrile butadiene rubber and polyamide 12 (PA12) have been first developed by the dynamic vulcanization process, in which selective cross‐linking of the elastomer phase during melt mixing with the thermoplastic phase (PA12) was carried out simultaneously. In this present investigation, hydrogenated acrylonitrile butadiene rubber (HNBR)/PA12 and partially hydrogenated carboxylated acrylonitrile butadiene rubber (XHNBR)/PA12 with blend ratio of 50:50, 60:40, and 70:30 wt% were prepared at 185°C at a rotor speed of 80 rpm for 5 min. Di‐(2‐tert‐butyl peroxy isopropyl) benzene was chosen as the suitable cross‐linking peroxide to pursue the dynamic vulcanization. TPV based on 50:50 HNBR/PA12 and XHNBR/PA12 show better physico‐mechanical properties, rheological behavior, thermal stability, dynamic mechanical analysis, and creep behavior among all the TPVs. Morphology study reveals that dispersed phase morphology has been formed with an average dimension of the rubber particles in the range of 0.8–1.5 µm. For aging test, TPVs were exposed to air and ASTM oil 3, respectively. Air aging tests were carried out in hot air oven for 72 hr at 125°C, while the oil aging tests were carried out after immersion of the samples into the oils in an aging oven. After aging, there is only slight deterioration in the physico‐mechanical properties of the TPVs. In case of 50:50 blends of HNBR/PA12 and XHNBR/PA12, the retention of the properties upon after aging was found excellent. These TPVs are designed to find potential application in automotive sector especially for under‐hood‐application, where high‐temperature resistance as well as high oil resistance is of prime importance. Copyright © 2016 John Wiley & Sons, Ltd.     

Radiation crosslinked Polyolefinic blends: exploring thermally tuned dual Shape Memory character

Shape memory behavior of thermally triggered polymeric materials based on ethylene octene copolymer (EOC) and ethylene propylene diene rubber (EPDM) has been studied in details. Investigation of the shape memory behavior of uncrosslinked EOC–EPDM and electron beam crosslinked EOC–EPDM blends have been pursued thoroughly. Shape memory study has been carried out at 60°C, which shows that with the effect of electron beam radiation shape fixity behavior of the crosslinked blends becomes poor as compared with its uncrosslinked blend system whereas the improvement in shape recovery behavior takes place after the exposure to electron beam radiation. Morphology study by Atomic Force Microscopy (AFM) and crystallinity study by X‐ray diffraction analysis also give the clear idea regarding the formation of crosslinked network structure. Improvement in gel content with increasing radiation dose supports the formation of network structure. Even after the crosslinking in presence of electron beam radiation also, it has been found that crosslinked EPDM rich blends is superior in terms of shape memory behavior point of view. Lower decay of stress value coupled with lower relaxation ratio of crosslinked EPDM rich blend support its superior shape memory behavior. Copyright © 2016 John Wiley & Sons, Ltd.     

Electron-beam treatment of poly(lactic acid) to control degradation profiles

Bioresorbable polymers such as polylactide (PLA) and polylactide-co-glycolide (PLGA) have been used successfully as biomaterials in a wide range of medical applications. However, their slow degradation rates and propensity to lose strength before mass have caused problems. A central challenge for the development of these materials is the assurance of consistent and predictable in vivo degradation. Previous work has illustrated the potential to influence polymer degradation using electron beam (e-beam) radiation. The work addressed in this paper investigates further the utilisation of e-beam radiation in order to achieve a more surface specific effect. Variation of e-beam energy was studied as a means to control the effective penetrative depth in poly-l-lactide (PLLA). PLLA samples were exposed to e-beam radiation at individual energies of 0.5 MeV, 0.75 MeV and 1.5 MeV. The near-surface region of the PLLA samples was shown to be affected by e-beam irradiation with induced changes in molecular weight, morphology, flexural strength and degradation profile. Moreover, the depth to which the physical properties of the polymer were affected is dependent on the beam energy used. Computer modelling of the transmission of each e-beam energy level used corresponded well with these findings.     

Design of PP/EPDM/NBR TPVs with tunable mechanical properties via regulating the core-shell structure

In this work, polypropylene (PP)/ethylene-propylene-diene monomer (EPDM)/butadiene acrylonitrile rubber (NBR) TPVs with different EPDM/NBR ratios were prepared by the core-shell dynamic vulcanization. The relationship between the core-shell structure and mechanical properties of the TPVs were thoroughly investigated. The formation of core-shell structure by adding NBR is conducive to the mechanical properties of the TPVs. The ratio of EPDM to NBR has an important effect on the structure and performances of the final products, and there is a critical ratio for this effect change. Transmission electron microscope (TEM), tensile test, reprocessing test, ageing test, rheological behavior test and stress relaxation were used to characterize the morphology and properties of the TPVs in detail. It was found that when the ratio of EPDM/NBR was 2:4, the tensile strength increased by ~14% compared with PP/EPDM TPV without NBR. Meanwhile, the reprocessing properties, rheological characteristics and instantaneous tensile deformation, etc. all exhibited sudden changes at this critical ratio.     

Morphologies and miscibilities of polypropene with random poly(ethene‐co‐1‐butene)

We investigated the miscibilities and morphologies of isotactic and syndiotactic polypropenes (i‐PP/s‐PP) with random poly(ethene‐co‐1‐butene) (PEB) as a function of 1‐butene content in PEB. The blend samples were studied by means of phase imaging atomic force microscopy, transmission electron microscopy, differential scanning calorimetry, dynamic mechanical analysis and X‐ray scattering. It was found that i‐PP is melt miscible with PEB for 1‐butene contents of ≈ 88 wt.‐% (miscibility window). Partial miscibility was found for s‐PP/PEB blends for 1‐butene contents ranging from 50‐88 wt.‐%.     

Micro construction of poly(epsilon-caprolactone)/poly(L-lactic acid) blend film by solution casting under microwave irradiation

The micro construction of poly(epsilon-caprolactone) (PCL) and poly(L-lactic acid) (PLLA) blend films fabricated by solution casting under microwave irradiation was investigated by selective enzymatic degradation and scanning electron microscopy (SEM). The results were totally different from the blends obtained by conventional methods. The blend was more homogeneous and the PCL continuous phase more compact as no spherulites and tiny zone separation were observed from the film surface and no PCL network was observed inside the film, and the degradation of a PCL plank by Pseudomonas lipase was significantly retarded. The distributed PLLA micro spheres were enlarged and amorphous. The thermal behavior of the blend by microwave heating revealed that PCL and PLLA underwent a melting process, which induced the variations of the PCL phase and PLLA spheres. The weight loss caused by degradation of the PCL/PLLA blend obtained by conventional methods (B50c) is greater than that of the blend obtained by microwave methods (B50m), which reflects the change in morphology from a loose PCL network (B50c) to a dense PCL plank (B50m).