Characterization of carbon black‐filled immiscible polypropylene/polystyrene blends

The electrical and rheological behaviors of carbon black (CB)‐filled immiscible polypropylene (PP)/polystyrene (PS) blends were investigated. The compounding sequence influences the phase morphology of the ternary CB/PP/PS composites and the distribution of CB aggregates. Simultaneous measurements of resistance and dynamic modulus were carried out to monitor the phase coalescence of the ternary composites and CB migration and agglomeration in the PS phase during annealing at temperatures above the melting point of PP. The variation of resistivity is mainly attributed to CB agglomeration in the PS phase and the interfacial region, while the variation of dynamic modulus is regarded as the superimposition of the phase coalescence and CB agglomeration in the PS phase. The ternary composites with the majority of CB particles distributed in the interfacial region show the lowest conductive percolation threshold and the most stable resistivity–temperature performance during heating–cooling cycles. Copyright © 2011 Society of Chemical Industry     

Effect of pellet size and compatibilization on thermal decomposition kinetic of recycled polyethylene terephthalate/recycled polypropylene blend

This study considers the effects of pellet geometry and compatibilization on its moisture absorption and thermal degradation behavior of recycled polyethylene terephthalate (RPET) and recycled polypropylene (RPP) blend with the ultimate goal of optimizing the design of pellets to enhance their processability. The isoconversion of Flynn–Wall–Ozawa (FWO) was used for the kinetic study, which was suitable for thermal degradation of RPET/RPP blend in N₂ while the second order polynomial function was fitted for thermal oxidative degradation in air. Finer geometries, such as powders, were found to have higher moisture absorption rates due to their large surface area although they could also be easily dried. Furthermore, large surface area of fine powder as well as good interaction between RPP disperse particles and RPET matrix eased to decompose in the presence of oxygen thus accelerated chain breaking during thermal oxidative degradation especially at low heating rate. Meanwhile, larger pellets exhibited higher degradation activation energies, which suggest that they are more resistant to thermal degradation than smaller grains. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of polypropylene‐grafted graphene and its compatibilization effect on polypropylene/polystyrene blends

Polypropylene‐graft‐reduced graphene oxide (PP‐g‐rGO) was synthesized and used as a novel compatibilizer for PP/polystyrene (PP/PS) immiscible polymer blends. SEM observation revealed an obvious reduction of the average diameter for the dispersed PS phase with the addition of PP‐g‐rGO into a PP/PS (70/30, w/w) blend. The compatibilization effect of PP‐g‐rGO will subsequently lead to the enhancement of the tensile strength and elongation at break of the PP/PS blends. The compatibilizing mechanism should be ascribed to the fact that PP‐g‐rGO can not only adsorb PS chains on their basal planes through π‐π stacking but also exhibit intermolecular interactions with PP through the grafted PP chains. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40455.     

Carbon black‐filled PET/HDPE blends: Effect of the CB structure on rheological and electric properties

The rheological and electric properties of blends of poly(ethylene terephthalate) (PET) and high‐density polyethylene (HDPE) filled with various types of carbon black (CB) were analyzed in detail in this project. Four types of CB samples with available values of surface area, particle size, porosity, density, and maximum packing fraction were considered. Blends were prepared using an internal mixing chamber at two different rotational speeds, prior to mold compression of the samples. The rheological properties of the blends with varying polymer composition and a constant amount of CB were recorded in terms of torque variation with time for two shear rates (in terms of rotational speed). Rheological data were related to the resistivity of blends. Results show that the CB structure (porosity, surface area, apparent bulk density, and particle size) largely determine the resulting equilibrium torque and electrical properties. Furthermore, since CB is preferentially located in the HDPE phase, higher conductivity is observed as the PET content decreases, since the relative CB content in this phase increases. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 562–569, 2001     

Effects of olefin‐based compatibilizers on the morphology,thermal and mechanical properties of ABS/polyamide‐6 blends

In this study, commercially available epoxidized and maleated olefinic copolymers, EMA‐GMA (ethylene‐methyl acrylate‐glycidyl methacrylate) and EnBACO‐MAH (ethylene‐n butyl acrylate‐carbon monoxide‐maleic anhydride), were used at 0, 5, and 10% by weight to compatibilize the blend composed of ABS (acrylonitrile‐butadiene‐styrene) terpolymer and PA6 (polyamide 6). Compatibilizing performance of these two olefinic polymers was investigated from blend morphologies, thermal and mechanical properties as a function of blend composition, and compatibilizer loading level. Scanning electron microscopy (SEM) studies showed that incorporation of compatibilizer resulted in a fine morphology with reduced dispersed particle diameter at the presence of 5% compatibilizer. The crystallization behavior of PA6 phase in the blends was explored for selected blend compositions by differential scanning calorimetry (DSC). At high compatibilizer level a decrease in the degree of crystallization was observed. In 10% compatibilizer containing blends, formation of γ‐crystals was observed contrary to other compatibilizer compositions. The behavior of the compatibilized blend system in tensile testing showed the negative effect of using excess compatibilizer. Different trends in yield strengths and strain at break values were observed depending on compatibilizer type, loading level, and blend composition. With 5% EnBACO‐MAH, the blend toughness was observed to be the highest at room temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 926–935, 2007     

Stability of electrical properties of carbon black‐filled rubbers

Conducting composites were prepared by melt mixing of ethylene–propylene–diene terpolymer (EPDM) or styrene‐butadiene rubber (SBR) and 35 wt % of carbon black (CB). Stability of electrical properties of rubber/CB composites during cyclic thermal treatment was examined and electrical conductivity was measured in situ. Significant increase of the conductivity was observed already after the first heating–cooling cycle to 85°C for both composites. The increase of conductivity of EPDM/35% CB and SBR/35% CB composites continued when cyclic heating‐cooling was extended to 105°C and 125°C. This effect can be explained by reorganization of conducting paths during the thermal treatment to the more conducting network. EPDM/35% CB and SBR/35% CB composites exhibited very good stability of electrical conductivity during storage at ambient conditions. The electrical conductivity of fresh prepared EPDM/35% CB composite was 1.7 × 10⁻² S cm⁻¹, and slightly lower conductivity value 1.1 × 10⁻² S cm⁻¹ was measured for SBR/35% CB. The values did not significantly change after three years storage. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Inner surface modification of halloysite nanotubes and its influence on morphology and thermal properties of polystyrene/polyamide‐11 blends

The asymmetry of halloysite surface chemistry was used to perform a selective modification of its inner surface via grafting of a synthesized styrene/(methacryloyloxy)methyl phosphonic acid copolymer. Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA) and pyrolysis gas chromatography/mass spectrometry were used to evidence and quantify the grafting. Then, raw and hybrid nanoparticles were incorporated in polystyrene (PS)/polyamide‐11 (PA11) blends (80/20 and 60/40 wt%). Scanning electron micrographs showed differences in localization of the halloysite nanotubes (HNTs), since raw halloysite is concentrated in the PA11 phase while modified halloysite is also located at the PS/PA11 interface, leading to a better interfacial adhesion between PS and PA11. An inhibiting effect of modified halloysite on PA11 coalescence was evidenced by measuring the particle size distribution of the extracted nodules. Moreover, the presence of modified halloysite at the interface shows an improvement in terms of thermal stability as observed by TGA, but with no significant effects on PA11 crystallization behaviour as shown by differential scanning calorimetry results. Rheological measurements were carried out to study the influence of the surface modification of halloysite on the blend morphology. A gel‐like behaviour was observed for the (60/40 wt%) HNTs reinforced composition that was enhanced in the case of 10% functionalized halloysite. © 2016 Society of Chemical Industry     

Effect of the type of nylon chain‐end on the compatibilization of PP/PP‐GMA/nylon 6 blends

Polyamide and polypropylene (PP) are two important classes of commercial polymers; however, their direct mixing leads to incompatible blends with poor properties. Polypropylene functionalized with glycidyl methacrylate (PP‐GMA) was used as a compatibilizer in blends of PP and nylon 6, because of the possible reaction of ? NH₂ and ? COOH groups with the epoxide group of GMA. Two types of nylon 6 with different ratios between ? NH₂ and ? COOH groups were used. The one with higher concentration of ? COOH groups was less compatible with PP in a binary blend. When PP‐GMA was used as a compatibilizer, a better dispersion of nylon in the PP matrix was obtained together with better mechanical properties for both nylons used in this work. © 2001 Society of Chemical Industry     

Preparation and reaction kinetics of polypropylene‐graft‐cardanol by reactive extrusion and its compatibilization on polypropylene/polystyrene

Polypropylene‐graft‐cardanol (CAPP) was prepared by reactive extrusion with polypropylene (PP) and natural renewable cardanol, which improved the inherent defects of PP such as its chemical inertness and hydrophobicity. Moreover, the cardanol grafted onto PP resolved the degradation of PP during reactive extrusion and use. The effects of reactive extrusion on the change of the molecular structure of PP, the change in the free‐radical concentration during processing, and the compatibilization of CAPP on the PP/polystyrene (PS) composite materials were examined in this study. The constants of the grafting reaction rate at the beginning of reactive extrusion were also deduced. The results show that cardanol was grafted onto PP, and the p–π conjugate system in cardanol was observed to stabilize free radicals. The grafting reaction rate (R_g) at the initial stage of the grafting reaction process was calculated through the equation R_g = k_g[M·][Cardanol], where k_g is the constant of the apparent grafting reaction rate and [M·] is the concentration of free radicals in the reaction system. k_g first increased with the growth of temperature and then began to decrease when the temperature exceeded the critical temperature of 200°C. The mechanical properties showed almost no change after the samples were aged for 72 h. This was due to CAPP, which changed PP/PS to a ductile material from a brittle one. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39911.     

Crystallization behavior of carbon black‐filled polypropylene and polypropylene/epoxy composites

The crystallization behavior of polypropylene (PP)/carbon black (CB) and PP/epoxy/CB composites was studied with differential scanning calorimetry (DSC). The effects of compatibilizer MAH‐g‐PP and dynamic cure on the crystallization behavior are investigated. The nonisothermal crystallization parameters analysis showed that CB particles in the PP/CB composites and the dispersed epoxy particles in the PP/epoxy composites could act as nucleating agents, accelerating the crystallization of the composites. Morphological studies indicated that the incorporation of CB into PP/epoxy resulted in its preferential localization in the epoxy resin phase, changing the spherical epoxy particles into elongated structure, and thus reduced the nucleation effect of epoxy particles. Addition of MAH‐g‐PP significantly decreased the average diameter of epoxy particles in the PP/epoxy and PP/epoxy/CB composites, promoting the crystallization of PP more effectively. The isothermal crystallization kinetics and thermodynamics of the PP/CB and PP/epoxy/CB composites were studied with the Avrami equation and Hoffman theory, respectively. The Avrami exponent and the crystallization rate of the PP/CB composites were higher than those of PP, and the free energy of chain folding for PP crystallization decreased with increasing CB content. Addition of MAH‐g‐PP into the PP/epoxy and PP/epoxy/CB composites increased the crystallization rate of the composites and decreased the chain folding energy significantly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 104–118, 2006     

Relationship between branch length and the compatibilizing effect of polypropylene‐g‐polystyrene graft copolymer on polypropylene/polystyrene blends

Three polypropylene‐g‐polystyrene (PP‐g‐PS) graft copolymers with the same branch density but different branch lengths were evaluated as compatibilizing agents for PP/PS blends. The morphological and rheological results revealed that the addition of PP‐g‐PS graft copolymers significantly reduced the PS particle size and enhanced the interfacial adhesion between PP and PS phases. Furthermore, it is verified that the branch length of PP‐g‐PS graft copolymer had opposite effects on its compatibilizing effect: on one hand, increasing the branch length could improve the compatibilizing effect of graft copolymer on PP/PS blends, demonstrated by the reduction of PS particle size and the enhancement of interfacial adhesion; on the other hand, increasing the branch length would increase the melt viscosity of PP‐g‐PS graft copolymer, which prevented it from migrating effectively to the interface of blend components. Additionally, the crystallization and melting behaviors of PP and PP/PS blends were compared. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40126.     

Effect of confinement on glass dynamics and free volume in immiscible polystyrene/high‐density polyethylene blends

The effect of confinement on glass dynamics combined with the corresponding free volume changes of amorphous polystyrene (PS) in blends with semi‐crystalline high‐density polyethylene (HDPE) have been investigated using thermal analyses and positron annihilation lifetime spectroscopy (PALS). Two different glass transition temperatures (T_g) were observed in a PS/HDPE blend due to the dissimilarity in the chemical structure, consistent with an immiscible blend. However, T_g of PS in the incompatible PS/HDPE blend showed an upward trend with increasing PS content resulting from the confinement effect, while T_g of the semi‐crystalline HDPE component became lower than that of neat HDPE. Moreover, the elevation of T_g of PS was enhanced with a decrease of free volume radius by comparing annealed and unannealed PS/HDPE blends. Positron results showed that the free volume radius clearly decreased with annealing for all compositions, although the free volume hole size agreed well with linear additivity, indicating that there was only a weak interaction between the two components. Combining PALS with thermal analysis results, the confinement effect on the glass dynamics and free volume of PS phase in PS/HDPE blends could be attributed to the shrinkage of HDPE during crystallization when HDPE acted as the continuous phase. © 2015 Society of Chemical Industry     

Effect of interface affinity on the performance of a composite of microcrystalline cellulose and polypropylene/polylactide blends

The effects of compatibilizer and fillers on the mechanical properties and dispersion state of droplets of polypropylene (PP)/polylactide (PLA) blends were investigated. Two blended composite systems, i.e. PP‐rich (80/20) containing microcrystalline cellulose (MCC) modified with silane (m‐MCC) and PLA‐rich (20/80) containing MCC were prepared by melt compounding using a twin‐screw extruder. The structural differences between MCC and m‐MCC were confirmed using Fourier transform infrared spectra. Universal testing machine results revealed that the tensile strength and Young's modulus increased with the addition of compatibilizer and filler, respectively. These results were supported by the reduction of domain size observed by scanning electron microscopy. Differential scanning calorimetric analysis showed a change of the melting and crystallization behavior of blends according to the presence of compatibilizer or filler. An increase of the dynamic storage modulus and a decrease in tan δ with addition of compatibilizer indicated that the interfacial adhesion between PP and PLA improved. © 2019 Society of Chemical Industry     

Toughening and compatibilization of polypropylene/polyamide‐6 blends with a maleated–grafted ethylene‐co‐vinyl acetate

In this article, maleated–grafted ethylene‐co‐vinyl acetate (EVA‐g‐MA) was used as the interfacial modifier for polypropylene/polyamide‐6 (PP/PA6) blends, and effects of its concentration on the mechanical properties and the morphology of blends were investigated. It was found that the addition of EVA‐g‐MA improved the compatibility between PP and PA6 and resulted in a finer dispersion of dispersed PA6 phase. In comparison with uncompatibilized PP/PA6 blend, a significant reduction in the size of dispersed PA6 domain was observed. Toluene‐etched micrographs confirmed the formation of interfacial copolymers. Mechanical measurement revealed that the addition of EVA‐g‐MA markedly improved the impact toughness of PP/PA6 blend. Fractograph micrographs revealed that matrix shear yielding began to occur when EVA‐g‐MA concentration was increased upto 18 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99:3300–3307, 2006     

Polymer blends of poly(trimethylene terephthalate) and polystyrene compatibilized by styrene‐glycidyl methacrylate copolymers

The compatibilizing effects of styrene‐glycidyl methacrylate (SG) copolymers with various glycidyl methyacrylate (GMA) contents on immiscible blends of poly(trimethylene terephthalate) (PTT) and polystyrene (PS) were investigated using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and ¹³C‐solid‐state nuclear magnetic resonance (NMR) spectroscopy. The epoxy functional groups in the SG copolymer were able to react with the PTT end groups (? COOH or ? OH) to form SG‐g‐PTT copolymers during melt processing. These in situ–formed graft copolymers tended to reside along the interface to reduce the interfacial tension and to increase the interfacial adhesion. The compatibilized PTT/PS blend possessed a smaller phase domain, higher viscosity, and better tensile properties than did the corresponding uncompatibilized blend. For all compositions, about 5% GMA in SG copolymer was found to be the optimum content to produce the best compatibilization of the blend. This study demonstrated that SG copolymers can be used efficiently in compatibilizing polymer blends of PTT and PS. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2247–2252, 2003     

Comparison of carboxylated and maleated polypropylene as reactive compatibilizers in polypropylene/polyamide‐6,6 blends

Using reactive extrusion, polypropylene is functionalized with maleic anhydride and compared on an equimolar basis to polypropylene that is functionalized with an asymmetric, carboxylic acid containing peroxide. The grafting efficiency for the asymmetric peroxide is double that obtained for the maleic anhydride system. Moreover, the asymmetric peroxide yields a functionalized material with minimal molecular weight degradation and desirable mechanical properties, relative to maleic anhydride‐grafted polypropylene. In compatibilized blends of polypropylene and nylon 6,6, the polypropylene that was functionalized with the asymmetric peroxide is found to be an improved compatibilizer compared to that of maleic anhydride‐grafted polypropylene. The differences in mechanical properties of the two different functionalized polypropylene materials and their respective blends are rationalized on the basis of the grafting efficiency, molecular weight degradation during reactive extrusion, and effect of free functional species on the ability to form graft copolymers in compatibilized blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2398–2407, 2001     

Effect of the mold temperature on the electrical properties of carbon-black-loaded polystyrene/SB block copolymer blends

The electrical resistivities of a carbon-black-filled styrene–butadiene block copolymer (SB) and their blends with polystyrene were measured as a function of carbon content for specimens compression-molded at 200 and 250°C. The insulator–conductor point transition was greatly influenced by the mold temperature. This behavior associated to the scanning electronic microscopy investigations suggests the presence of some amount of the filler at the interface. A strong interaction between the filler and the polymer was also observed. The formation of bound rubber and a coherent rubber–filler gel depend on the molding conditions and the carbon black content in the composites. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 825–833, 1998     

Time dependences of conduction and self‐heating in acetylene carbon black‐filled high‐density polyethylene composites

The time dependences of electrical conduction and self‐heating behaviors in high‐density polyethylene filled with acetylene carbon black of 0.082 in volume fraction are studied in relation to voltage and ambient temperature. The characteristic decay current constant τ_i, and the exponential growth time constant for self‐heating τ_g are determined for the samples under voltages U above the critical value U_c for the onset of self‐heating. The influences of voltage and ambient temperature on τ_i and τ_g as well as the amplitude of the low‐resistance to high‐resistance switching are discussed on the basis of the random resistor network (RRN) model and the relationship between U_c and the intrinsic resistivity. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1124–1131, 2006     

Electrical properties and morphology of carbon black‐filled HDPE/EVA composites

The sensitive effect of weight ratio of the high‐density polyethylene (HDPE)/ethylene‐vinylacetate copolymer (EVA) on the electrical properties of HDPE/EVA/carbon black (CB) composites was investigated. With the EVA content increasing from 0 wt % to 100 wt %, an obvious change of positive temperature coefficient (PTC) curve was observed, and a U‐shaped insulator‐conductor‐insulator transition in HDPE/EVA/CB composites with a CB concentration nearby the percolation threshold was found. The selective location of CB particles in HDPE/EVA blend was analyzed by means of theoretical method and scanning electron micrograph (SEM) in order to explain the U‐shaped insulator‐conductor‐insulator transition, a phenomenon different from double percolation in this composite. The first significant change of the resistivity, an insulator‐conductor transition, occurred when the conductive networks diffused into the whole matrix due to the forming of the conductive networks and the continuous EVA phase. The second time significant change of the resistivity, a conductor‐insulator transition, appeared when the amorphous phase is too large for CB particles to form the conductive networks throughout the whole matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Compatibilization of recycled poly(ethylene terephthalate) and polypropylene blends: Effect of compatibilization on blend toughness,dispersion of minor phase,and thermal stability

Blending of recycled polyethylene terephthalate (RPET) from waste bottles with polypropylene (PP) was performed in an attempt to enhance the processability of RPET. The idea of blending RPET with PP sprouted from the intention of recycling PET bottles together with their PP‐based caps. Therefore, preliminary blending of RPET with neat PP (RPET/PP) was performed at various PP and compatibilizer contents. Morphological analyses on the extruded pellets of uncompatibilized blends indicate that the PP particle size and state of dispersion at skin and core regions were vastly different. The particles at the skin were at least 10 times smaller than that at the core although the size distribution was very wide. With the incorporation of just 5 phr of compatibilizer, the particles at the core region became significantly smaller and appeared to emulate that of the skin region. Furthermore, the overall homogeneity of the blends was vastly improved irrespective of PP content in the blend. The reduction in particle size and improved homogeneity inherently reduced stress concentration points and enhanced the mechanical performance of the blends. More importantly, the incorporation of PP into RPET significantly increased the degradation temperature of the blends, provided the dispersion of PP phase in RPET was excellent. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011