Mechanical and rheological properties of silica-reinforced polypropylene/m-EPR blends

Rheological and mechanical properties (tensile and impact properties) as well as the mechanical profiles of ternary isotactic polypropylene/silica/elastomer (iPP/SiO₂/m-EPR metallocene catalyzed ethylene-propylene rubber) composites were investigated and discussed. The effects of two metallocene ethylene-propylene-based elastomers (m-EPR) differing in molecular weight/viscosity and their content on iPP/silica composites with different silica types differing in size (nano- vs. micro-) and surface properties (untreated vs. treated) were investigated. The two m-EPR elastomers were added to iPP/SiO₂ 96/4 composites as possible impact modifier and compatibilizer at the same time in 5, 10, 15, and 20 vol% per hundred volume parts of composites. The effects of different silica fillers and two m-EPR rubbers were discussed within the context of structure-morphology-mechanical property relationships of these iPP/SiO₂/m-EPR composites. Tensile and impact strength properties were mainly influenced by combined competetive effects of stiff filler and tough m-EPR elastomer so sinergistic effect was also observed. The ductility of these composites was affected additionally by spherulite size of the iPP matrix due to the difference in nucleation abilities of silica fillers enabled by prevailing separated morphology observed in iPP/SiO₂/m-EPR composites.     

Polypropylene/silica micro‐ and nanocomposites modified with poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene)

The effects of different silica loadings and elastomeric content on interfacial properties, morphology and mechanical properties of polypropylene/silica 96/4 composites modified with 5, 10, 15, and 20 vol % of poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) SEBS added to total composite volume were investigated. Four silica fillers differing in size (nano‐ vs. micro‐) and in surface properties (untreated vs. treated) were chosen as fillers. Elastomer SEBS was added as impact modifier and compatibilizer at the same time. The morphology of ternary polymer composites revealed by light and scanning electron microscopies was compared with morphology predicted models based on interfacial properties. The results indicated that general morphology of composite systems was determined primarily by interfacial properties, whereas the spherulitic morphology of polypropylene matrix was a result of two competitive effects: nucleation effect of filler and solidification effect of elastomer. Tensile and impact strength properties were mainly influenced by combined competetive effects of stiff filler and tough SEBS elastomer. Spherulitic morphology of polypropylene matrix might affect some mechanical properties additionally. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41486.     

Effects of EPDM and wollastonite on structure of isotactic polypropylene blends and composites

Polypropylene blends and composites with 5, 10, and 15 vol % of EPDM and 2, 4, and 6 vol % of untreated and treated wollastonite filler were examined by applying different techniques. Elastomeric ethylene/propylene/diene terpolymer (EPDM) component and wollastonite influenced the crystallization process of isotactic polypropylene (iPP) matrix in different ways. The nucleation of hexagonal β‐iPP, the increase of overall degree of crystallinity, and crystallite size of iPP were more strongly affected by wollastonite than the addition of EPDM was. Both ingredients also differently influenced the orientation of α‐form crystals in iPP matrix. Wollastonite increased the number of a*‐axis‐oriented α‐iPP lamellae plan parallel to the sample surface, whereas the addition of EPDM reoriented the lamellae. The orientation parameters of ternary composites exhibited intermediate values between those for binary systems because of the effects of both components. EPDM elastomer considerably affected well‐developed spherulitization of iPP, increasing the spherulite size. Contrary to EPDM, because of nucleating ability or crystal habit, wollastonite caused significantly smaller iPP spherulites. Small spherulites in ternary iPP/EPDM/wollastonite composites indicated that the wollastonite filler (even in smallest amounts) exclusively determined the morphology of ternary composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4072–4081, 2004     

Morphology and Mechanical Properties of iPP/Silica Composites Modified with (Styrene-b-ethylene-co-butylene-b-styrene) Grafted with Maleic Anhydride

The effects of different silica grades and elastomer content on interfacial properties, morphology and mechanical properties of polypropylene/silica 96/4 composites modified with added 5, 10, 15, and 20% of poly(styrene-b-ethylene-co-butylene-b-styrene) grafted with maleic anhydride (SEBS-g-MA) were investigated. The iPP/silica/SEBS-g-MA composites were designed by adding four silica fillers differing in size (nano- vs. micro-) and in surface properties (hydrophilic vs. hydrophobic) and SEBS-g-MA that was used as a proven effective impact modifier and compatibilizer simultaneously. The morphology of every composite was a spectrum of several morphologies rather than one exclusive morphology. Good concordance between observed and predicted morphology indicated that the morphology of a particular composite was controlled primarily by interfacial properties. Tensile and impact properties were influenced primarily by competitive effects of a stiff filler and tough SEBS-g-MA elastomer. Increased impact strength and strain at break caused by adding SEBS-g-MA indicated a significant overcoming of the elastomeric toughening effect in relation to the filler’s stiffening effect.     

Wollastonite-reinforced polypropylene composites modified with novel metallocene EPR copolymers. I. Phase structure and morphology

Supermolecular structure of isotactic polypropylene/wollastonite/metallocene propylene–ethylene copolymers (iPP/W/EPR) composites was studied as a function of elastomer content (from 0 to 20 vol%) by optical, scanning, and transmission electron microscopy, wide-angle X-ray diffraction, and differential scanning calorimetry. Both, wollastonite and dispersed EPR particles, homogeneously incorporated into the iPP matrix, and affected the final phase structure and morphology of the iPP/wollastonite/EPR composites. Wollastonite particles were orientated plane-parallel to the sample surface and hindered spherulite growth of the iPP matrix. EPRs enhanced plane-parallel orientation of wollastonite and simultaneously enhanced the spherulite and crystallite growth in the iPP matrix during the solidification of polymer melt. Ternary iPP/wollastonite/EPR composites exhibited significant prevalence of separated microphase morphology (over core-shell morphology) because of constitution similarity of P-E and iPP chains. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers.     

Phenolic rigid organic filler/isotactic polypropylene composites. I. Preparation

A novel phenolic rigid organic filler (KT) was melt-mixed with an isotactic polypropylene (iPP) to prepare a series of PP/KT composites, with or without maleic anhydride grafted polypropylene (MAPP) as compatilizer. The evolution of filler morphology during melt-mixing and melt-pressure processes was monitored by scanning electron microscope (SEM) and polarized optical microscope (POM). The influences of shear force, pressure time, filler content and MAPP concentration on the final filler dispersion were studied. We found that this rigid organic filler readily melted and dispersed homogenously into the iPP matrix through a fission-fusion process during the melt-mixing process. Thus a balanced dispersion, which was closely related to shear force and MAPP concentration, can be achieved. During the meltpressure process, parts of the filler particles combined gradually through a coalescence process. However, the incorporation of MAPP can effectively inhibit the tendency to coalesce and refine the filler particles sizes into nanoscale. Thus, a series of PP/KT composites with controllable filler particles size and narrow size distribution can be obtained just by adjusting process conditions and MAPP concentration. In addition, due to the in-situ formation mechanism, the filler phase possessed a typical solid true-spherical shape.     

Phenolic rigid organic filler/isotactic polypropylene composites. I. Preparation

A novel phenolic rigid organic filler (KT) was melt-mixed with an isotactic polypropylene (iPP) to prepare a series of PP/KT composites, with or without maleic anhydride grafted polypropylene (MAPP) as compatilizer. The evolution of filler morphology during melt-mixing and melt-pressure processes was monitored by scanning electron microscope (SEM) and polarized optical microscope (POM). The influences of shear force, pressure time, filler content and MAPP concentration on the final filler dispersion were studied. We found that this rigid organic filler readily melted and dispersed homogenously into the iPP matrix through a fission-fusion process during the melt-mixing process. Thus a balanced dispersion, which was closely related to shear force and MAPP concentration, can be achieved. During the melt-pressure process, parts of the filler particles combined gradually through a coalescence process. However, the incorporation of MAPP can effectively inhibit the tendency to coalesce and refine the filler particles sizes into nanoscale. Thus, a series of PP/KT composites with controllable filler particles size and narrow size distribution can be obtained just by adjusting process conditions and MAPP concentration. In addition, due to the in-situ formation mechanism, the filler phase possessed a typical solid true-spherical shape.     

Effects of organic nucleating agents and zinc oxide nanoparticles on isotactic polypropylene crystallization

Organic nucleating agents and inorganic nanoparticles, as well as their hybrid composites, affect the crystallization temperature and morphology of the monoclinic α-form of isotactic polypropylene (iPP). Techniques such as differential scanning calorimetry, hot-stage optical microscopy with cross polars, wide angle X-ray diffraction, and transmission electron microscopy were employed. Nanoparticles of zinc oxide function as efficient supports for 1,3,5-benzene tricarboxylic-(N-2-methylcyclohexyl)triamine because the temperature at which the maximum rate of iPP crystallization occurs during 10 °C/min cooling from the molten state increases from 111 °C for the pure polymer to 125 °C at low concentrations of this hybrid nucleating agent. In the absence of zinc oxide, 0.06 wt% of this aliphatic triamine recrystallizes near 165 °C and increases the crystallization temperature of iPP by 7 °C, relative to the pure polymer. Fluorinated aromatic triamines, such as 1,3,5-benzene tricaboxylic-(N-4-fluorophenyl)triamine, are weak nucleating agents that reduce spherulite size in isotactic polypropylene but only increase the crystallization temperature marginally when the polymer is cooled from the molten state. Both micro- and nanoparticles of zinc oxide reduce spherulite size in isotactic polypropylene, but smaller spherulites are observed when the inorganic nanoparticles exhibit dimensions on the order of 40-150 nm relative to micron-size particles. In contrast, 0.06 wt% of the aliphatic triamine in iPP yields a distorted birefringent texture under cross polars that is not spherulitic. Non-spherulitic birefringent textures in iPP are also observed when the aliphatic triamine nucleating agent is coated onto micro- or nanoparticles of zinc oxide. This study demonstrates that the nonisothermal crystallization temperature of isotactic polypropylene increases by an additional 7 °C when an aliphatic triamine is distributed efficiently within the polymeric matrix by coating this nucleating agent onto zinc oxide nanoparticles.     

Effect of pimelic acid treatment on the crystallization,morphology, and mechanical properties of isotactic polypropylene/mica composites

Pimelic acid (PA) is used as a new surface modifier for mica (MC). The effects of PA treatment on the crystallization, morphology, and mechanical properties of isotactic polypropylene (iPP)/MC composites have been investigated. FTIR analysis reveals that PA reacted with phlogopite MC, and pimelates are formed during the treatment. The results of wide angle X‐ray diffraction, differential scanning calorimetry, and polarized light microscopy prove that PA‐treated MC induces a large amount of β‐iPP and decreases the spherulite size of iPP. The results of SEM show that PA treatment improves the orientation and dispersion of MC plates in the matrix. The notched impact strength of the composites is improved dramatically by PA‐treated MC. The superior toughness is ascribed to the more ductile β spherulites, preferential orientation of MC plates, small spherulite size, and improved dispersion of MC plates in the matrix. POLYM. COMPOS., 31:1572–1584, 2010. © 2009 Society of Plastics Engineers     

Electrical conductivity of carbon‐filled polypropylene‐based resins

Adding conductive carbon fillers to insulating thermoplastic resins increases composite electrical conductivity. Often, as much of a single type of carbon filler is added to achieve the desired conductivity and still allow the material to be molded into a bipolar plate for a fuel cell. In this study, various amounts of three different carbons (carbon black, synthetic graphite particles, and carbon nanotubes) were added to polypropylene resin. The resulting single‐filler composites were tested for electrical resistivity (1/electrical conductivity). The effects of single fillers and combinations of the different carbon fillers were studied via a factorial design. The percolation threshold was 1.4 vol % for the composites containing only carbon black, 2.1 vol % for those containing only carbon nanotubes, and 13 vol % for those containing only synthetic graphite particles. The factorial results indicate that the composites containing only single fillers (synthetic graphite followed closely by carbon nanotubes and then carbon black) caused a statistically significant decrease in composite electrical resistivity. All of the composites containing combinations of different fillers had a statistically significant effect that increased the electrical resistivity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Phenolic rigid organic filler/isotactic polypropylene composites. III. Impact resistance property

A novel phenolic rigid organic filler (KT) was used to modify isotactic polypropylene (iPP). The influence of KT particles on the impact resistance property of PP/KT specimens (with similar interparticles distance, 1.8 μm) was studied by notched izod impact tests. It was found that the brittle-ductile transition (BDT) of the PP/KT microcomposites took place at the filler content of about 4%, and the impact strength attains the maximum at 5% (with filler particles size of 1.5 μm), which is about 2.5 times that of unfilled iPP specimens. The impact fracture morphology was investigated by scanning electron microscopy (SEM). For the PP/KT specimens and the highdensity polyethylene/KT (HDPE/KT) specimens in ductile fracture mode, many microfibers could be found on the whole impact fracture surface. It was the filler particles that induced the plastic deformation of interparticles ligament and hence improved the capability of iPP matrix on absorbing impact energy dramatically. The determinants on the BDT were further discussed on the basis of stress concentration and debonding resistance. It can be concluded that aside from the interparticle distance, the filler particles size also plays an important role in semicrystalline polymer toughening. Keywords rigid organic filler, polypropylene, impact     

Comparison on the Properties of Nickel-Coated Graphite (NCG) and Graphite Particles as Conductive Fillers in Polypropylene (PP) Composites

The present study was carried out to evaluate the performance of nickel-coated graphite (NCG) in comparison with graphite as conductive fillers in polypropylene (PP) matrix. Graphite exhibits smaller particle size and higher aspect ratio (length/thickness) than NCG particles. The results showed that the additions of graphite filler in PP exhibits higher tensile properties and electrical conductivity compared to NCG filled PP composites. The electrical results showed that the percolation threshold of graphite and NCG filled PP composites occurred in the range of 10 to 20 vol.% and 15 to 25 vol.%, respectively.     

Isothermal crystallization kinetics and morphology development of isotactic polypropylene blends with atactic polypropylene

The crystallization kinetics and morphology development of pure isotactic polypropylene (iPP) homopolymer and iPP blended with atactic polypropylene (aPP) at different aPP contents and the isothermal crystallization temperatures were studied with differential scanning calorimetry, wide‐angle X‐ray diffraction, and polarized optical microscopy. The spherulitic morphologies of pure iPP and larger amounts of aPP for iPP blends showed the negative spherulite, whereas that of smaller amounts of aPP for the iPP blends showed a combination of positive and negative spherulites. This indicated that the morphology transition of the spherulite may have been due to changes the crystal forms of iPP in the iPP blends during crystallization. Therefore, with smaller amounts of aPP, the spherulitic density and overall crystallinity of the iPP blends increased with increasing aPP and presented a lower degree of perfection of the γ form coexisting with the α form of iPP during crystallization. However, with larger amounts of aPP, the spherulitic density and overall crystallinity of the iPP blends decreased and reduced the γ‐form crystals with increasing aPP. These results indicate that the aPP molecules hindered the nucleation rate and promoted the molecular motion and growth rate of iPP with smaller amounts of aPP and hindered both the nucleation rate and growth rate of iPP with larger amounts of aPP during isothermal crystallization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1093–1104, 2007     

Effect of silica particle size on chain dynamics and frictional properties of styrene butadiene rubber nano and micro composites

Size and curvature of filler particles affect dynamics of polymer chains in composites. In this work, effects of filler particle size, in two scales of nano- and micro-meters, on dynamics of rubbery chains and frictional properties of composites were studied. Surface modification of nano- and micro-fumed silica by grafting low molecular weight hydroxyl-terminated polybutadiene (HTPB) guaranteed similar surface energy for fillers as measured by their surface tension. Nano- and micro-composites of styrene butadiene rubber were prepared by solvent assisted mixing and progressively increasing volume fraction of fillers. Achievement of nano and micro-composites was confirmed by the scanning electron microscopy. Effect of silica aggregate size on the dynamics of rubber chains was measured by dynamic-mechanical-thermal analyzer and compared through calculation of the activation energy for mobilization of slow-dynamic chains in the rubbery region. It was shown that nano-silica immobilizes the rubber chains more than micro-silica even at equal total interfacial area between filler aggregates and rubber matrix, especially above the percolation limit. Similar trend was seen for the coefficient of friction of composites against rough surfaces, showing the strong effect of chain dynamics on friction properties of rubber vulcanizates.     

Flow behaviour and microstructure evolution in novel SiO2/PP/LCP ternary composites: effects of filler properties and mixing sequence

When silica (SiO₂) fillers were introduced into the polypropylene (PP) and liquid‐crystalline polymer (LCP) blend, it was found that the mixing sequence, the filler size, and the filler surface nature affected the rheology of the composites and the morphology of the LCP phase in the ternary composite. In particular, the compatibility between the filler and the PP matrix was found to exert a strong influence on the droplet‐fibril transition. The incorporation of the hydrophobic silica to the LCP/PP blend facilitated the fibrillation of LCP because the hydrophobic filler demonstrated affinity towards the hydrophobic PP matrix. The preferential residence of the hydrophobic silica in the PP phase would minimise the LCP domain disruption leading to the formation of LCP fibrils with high aspect ratios. The use of fine filler and in situ blending, which promoted the filler–LCP interaction, could prevent coalescence, inhibit deformation and hinder fibril development as well. © 2003 Society of Chemical Industry     

Structures and Performance of White Clay-Filled Isotactic-Polypropylene Composites Prepared by Double-Molding Techniques

Various contents of Bangladeshi white clay (WC)-filled Isotactic polypropylene (iPP) composites were fabricated by double-molding techniques. Scanning electron micrographs shows a good impact between iPP matrix and fillers. X-diffraction and IR spectroscopic measurements reveal that inclusion of fillers develops an additional γ-crystal along with the α- and β-crystals that are merely observed in the neat iPP. Young's modulus and microhardness are found to increase with increasing WC content. Thermal analyses represent a considerable increase of thermal stability of the composites with filler addition. Appearance of new crystalline phase by filler inclusion and performances of the composites are discussed in detail.     

Effects of SBS on phase morphology of iPP/aPS blends

The supermolecular structure of binary isotactic polypropylene/poly(styrene‐b‐butadiene‐h‐styrene) (iPP/SBS) and isotactic polypropylene/atactic polystyrene (iPP/aPS) compression molded blends and that of ternary iPP/aPS/SBS blends were studied by optical microscopy, scanning and transmission electron microscopy, wide‐angle X‐ray diffraction and differential scanning calorimetry. Nucleation, crystal growth, solidification and blend phase morphology are affected by the addition of amorphous components (SBS and aPS). As a compatiblizer in immiscible iPP/aPS blends, SBS formed interfacial layer between dispersed honeycomb‐like aPS/SBS particles and the iPP matrix, thus influencing the crystallization process in iPP. The amount of SBS and aPS, and compatibilizing efficiency of SBS, determine the size of dispersed aPS, SBS, and aPS/SBS particles and, consequently, the final blend phase morphologies: well‐developed spherulitic morphology, cross‐hatched structure with blocks of sandwich lamellae and co‐continuous morphology. The analysis of the relationship between the size of spherulites and dispersed particles gave the criterion relation, which showed that, in the case of a well‐developed spherulitization, the spherulites should be about fourteen times larger than the incorporated dispersed particles; i.e. to be large enough to engulf dispersed inclusions without considerable disturbing of the spherulitic structure.     

Dispersion of a novel phenolic rigid organic filler in isotactic polypropylene matrix by solution-mixing and melt-mixing

A novel phenolic rigid organic filler (named KD) with a high melting point was dispersed in an isotactic polypropylene (iPP) matrix by solution-mixing and/or melt-mixing. A series of KD/iPP blends was prepared with or without addition of maleic anhydride-grafted polypropylene (MAPP) as a compatibilizer. Influences of MAPP and mixing methods on the filler dispersion were studied using polaried optical microscope (POM), scanning electron microscope (SEM) and tensile test. The filler particles are always inclined to form large irregular aggregates in the iPP matrix due to their significant differences in polarity and solubility in solvent. However, an iPP/MAPP/KD (PMK) blend containing filler particles with a quasi-spherical shape (~97.8 nm in diameter) and narrow particle size distribution (polydispersity index= 1.076) was successfully prepared by incorporating MAPP to reduce the interfacial tension and surface free energy between the dispersion phase and the continuous phase, and adopting a spray-drying method after solution-mixing to suppress the increase of the size of the dispersed phase during the removal of solvent.     

Experiment and simulation of foaming injection molding of polypropylene/nano-calcium carbonate composites by supercritical carbon dioxide

Microcellular injection molding of neat isotactic polypropylene (iPP) and isotactic polypropylene/nano-calcium carbonate composites (iPP/nano-CaCO₃H) was performed using supercritical carbon dioxide as the physical blowing agent. The influences of filler content and operating conditions on microstructure morphology of iPP and iPP/nano-CaCO₃H microcellular samples were studied systematically. The results showed the bubble size of the microcellular samples could be effectively decreased while the cell density increased for iPP/nano-CaCO₃H composites, especially at high CO₂ concentration and back pressure, low mold temperature and injection speed, and high filler content. Then Moldex 3D was applied to simulate the microcellular injection molding process, with the application of the measured ScCO₂ solubility and diffusion data for iPP and iPP/nano-CaCO₃H composites respectively. For neat iPP, the simulated bubble size and density distribution in the center section of tensile bars showed a good agreement with the experimental values. However, for iPP/nano-CaCO₃H composites, the correction factor for nucleation activation energy F and the pre-exponential factor of nucleation rate f0 were obtained by nonlinear regression on the experimental bubble size and density distribution. The parameters F and f0 can be used to predict the microcellular injection molding process for iPP/nano-CaCO₃H composites by Moldex 3D.     

Nielsen thermal conductivity model for single filler carbon/polypropylene composites

In this study, three different carbon fillers (Thermocarb TC‐300 synthetic graphite, Ketjenblack EC‐600 JD carbon black, and Hyperion Catalysis International's FIBRIL? carbon nanotubes) were added to a polypropylene matrix to produce single filler composites with filler concentrations of up to 80 wt % synthetic graphite (61.6 vol %), 15 wt % carbon black (8.1 vol %), and 15 wt % carbon nanotubes (7.4 vol %). The through‐plane thermal conductivity for each formulation was measured. For the synthetic graphite, carbon black, and carbon nanotubes composites, the Nielsen model was applied to the experimental through‐plane thermal conductivity data. The Nielsen Model presented in this work showed very good agreement with experimental data. The model parameters were similar to those used in the literature for these fillers in other polymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009