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.     

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.     

Phenolic rigid organic filler/isotactic polypropylene composites. II. Tensile properties

A novel phenolic rigid organic filler (KT) was used to modify isotactic polypropylene (iPP). The influence of KT particles on the tensile properties of PP/KT microcomposites was studied by uniaxial tensile test and the morphological structures of the stretched specimens were observed by scanning electron microscopy (SEM) and polarized optical microscopy (POM). We found that the Young’s modulus of PP/KT specimens increased with filler content, while the yield and break of the specimens are related to the filler particles size. The yield stress, the breaking stress and the ultimate elongation of PP/KT specimens were close to those of unfilled iPP specimens when the maximal filler particles size is less than a critical value, which is 7 μm at a crosshead speed of 10 mm/min and 3 μm at 200 mm/min, close to that of glass bead but far more than those of other rigid inorganic filler particles. The interfacial interaction was further estimated from yield stress, indicating that KT particles have a moderate interfacial interaction with iPP matrix. Thus, the incorporation of small KT particles can reinforce iPP matrix and simultaneously cause few detrimental effects on the other excellent tensile properties of iPP matrix, due to their organic nature, higher specific area, solid true-spherical shape and the homogenous dispersion of the ROF particles in microcomposites.     

Phenolic rigid organic filler/isotactic polypropylene composites. II. Tensile properties

A novel phenolic rigid organic filler (KT) was used to modify isotactic polypropylene (iPP). The influence of KT particles on the tensile properties of PP/KT microcomposites was studied by uniaxial tensile test and the morphological structures of the stretched specimens were observed by scanning electron microscopy (SEM) and polarized optical microscopy (POM). We found that the Young’s modulus of PP/KT specimens increased with filler content, while the yield and break of the specimens are related to the filler particles size. The yield stress, the breaking stress and the ultimate elongation of PP/KT specimens were close to those of unfilled iPP specimens when the maximal filler particles size is less than a critical value, which is 7 ?m at a crosshead speed of 10 mm/min and 3 ?m at 200 mm/min, close to that of glass bead but far more than those of other rigid inorganic filler particles. The interfacial interaction was further estimated from yield stress, indicating that KT particles have a moderate interfacial interaction with iPP matrix. Thus, the incorporation of small KT particles can reinforce iPP matrix and simultaneously cause few detrimental effects on the other excellent tensile properties of iPP matrix, due to their organic nature, higher specific area, solid true-spherical shape and the homogenous dispersion of the ROF particles in microcomposites.     

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     

Effect of sodium dodecylbenzene sulphonate modifier and PP-g-MA on the morphology and thermal conductivity of PP/EG composites

This study investigates the influence of expanded graphite (EG) and sodium dodecylbenzene sulfonate (SDBS) treated EG (SDBS/EG) on the structure, thermal stability and thermal conductivity of polypropylene (PP) and polypropylene/maleic anhydride-grafted polypropylene (PP/MAPP) blend. The dispersion of EG and SDBS/EG was characterized by scanning electron microscopy (SEM). The SDBS-EG showed a crushed and randomly deformed structure. There was an improved interfacial adhesion between the polymer and the SBDS-EG particles. The graphite dispersed much better with less restacking for PP/MAPP/SDBS/EG system. The better dispersion also contributed towards the improved compatibility between the PP or PP/MAPP and SBDS/EG. The SDBS functionalised EG composites showed better thermal stability than the non-functionalized SDBS composites. It was further shown that the functionalized graphite significantly improved the thermal conductivity of the PP and PP/MAPP. This is because the functionalized SDBS/EG seemed to improve the interfacial heat transfer between the conductive filler (EG) and PP matrix.     

Microstructural characteristics of glass bead‐ and wollastonite‐filled isotactic‐polypropylene composites modified with thermoplastic elastomers

Microstructural characteristics of isotactic‐polypropylene/glass bead (iPP/GB) and iPP/wollastonite (iPP/W) composites modified with thermoplastic elastomers, poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) copolymer (SEBS) and corresponding block copolymer grafted with maleic anhydride (SEBS‐g‐MA), were investigated. Scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and dynamic mechanical analyses (DMA) showed that the iPP/SEBS and iPP/SEBS‐g‐MA blends were partially compatible two‐phase systems. Well‐dispersed spherical GB and acicular W particles without evidence of interfacial adhesion were observed in the iPP/GB and iPP/W binary composites respectively. Contrary to the blends, melt flow rates of the iPP/GB and PP/W composites decreased more with SEBS‐g‐MA than with SEBS because of enhanced interfacial adhesion with SEBS‐g‐MA elastomer. The SEM analyses showed that the ternary composites containing SEBS exhibited separate dispersion of the rigid filler and elastomer particles (i.e., separate microstructure). However, SEBS‐g‐MA elastomer not only encapsulated the spherical GB and acicular W particles completely with strong interfacial adhesion (i.e., core‐shell microstructure) but also dispersed separately throughout iPP matrix. In accordance with the SEM observations, the DSC and DMA revealed quantitatively that the rigid filler and SEBS particles in iPP matrix acted individually, whereas the rigid filler particles in the ternary composites containing SEBS‐g‐MA acted like elastomer particles because of the thick elastomer interlayer around the filler particles. The Fourier transform infrared analyses revealed an esterification reaction inducing the strong interfacial adhesion between the SEBS‐g‐MA phase and the filler particles. POLYM. COMPOS., 31:1265–1284, 2010. © 2009 Society of Plastics Engineers     

Effects of silane coupling agent and maleic anhydride‐grafted polypropylene on the morphology and viscoelastic properties of polypropylene–mica composites

In this study, morphology, and dynamic and mechanical properties of polypropylene–mica (PP–Mica) composites were investigated. To enhance the adhesion between PP and mica, maleic anhydride‐grafted PP (MAPP) and treated mica with silane coupling agent were used. MAPP (as a compatibilizer) and silane coupling agent (as a filler surface modifier) caused an interfacial bonding in the mica filled polypropylene composites. The effect of mica content, MAPP, and treated mica with silane coupling agent on the morphological properties were investigated by Scanning Electron Microscopy (SEM). The results showed that with increasing MAPP or silane coupling agent, dispersion of filler and adhesion between PP and filler were improved. Mechanical data showed that with increasing MAPP and mica treated with silane coupling agent, tensile modulus and flextural strength of composites were enhanced. Dynamic rheological behavior of composites was also investigated within the domain of linear viscoelasticity. The rheological observations indicated that the complex viscosity, storage and loss moduli increased, and tan δ decreased with increasing mica content. POLYM. COMPOS. 27:491–496, 2006. © 2006 Society of Plastics Engineers.     

Melt rheology of polypropylene reinforced with polyaniline‐coated short glass fibers

This research deals with the melt rheology of isotactic polypropylene (iPP) reinforced with short glass fibers (SGF) coated with electrically conductive polyaniline (PAn). Composites containing 10, 20, and 30 wt % PAn‐SGF were studied. Moreover, a composite of 30 wt % PAn‐SGF was also prepared with a blend of iPP and PP‐grafted‐maleic anhydride (iPP/PP‐gMA). The composites showed linear viscoelastic regime at small strain amplitudes. The onset of nonlinearity decreased as the concentration of filler increased. The time‐temperature superposition principle applied to all composites. The filler increased the shear moduli (G′, G″) and the complex viscosity η*. Steady‐state shear experiments showed yield stress for the composites with 20 and 30 wt % PAn‐SGF. Strikingly, the 10 wt % composite showed higher steady state viscosity than the 20 wt %. Rheo‐optics showed that shear induced disorder of microfibers at a concentration of 10 wt %. However, at 20 wt % concentration shear aligned the microfibers along the flow axis, this would explain the anomalous steady state viscosity values. The viscosity exhibited a shear thinning behavior at high shear rates for all composites. Creep experiments showed that the filler induced greater strain recovery in the composites and that the amount of strain recovery increased as the PAn‐SGF concentration increased. However, the enhancement of strain recovery (as well as shear viscosity) was more significant when using the iPP/PP‐gMA blend, suggesting greater adhesion between this matrix and the filler PAn‐SGF. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and physical properties of wood/polypropylene/clay nanocomposites

Wood plastic composites (WPCs) are attracting a lot of interests because they are economic, environmentally friendly, and show fairly good performance. To improve the performance of a wood/polypropylene (PP) composite, an organoclay was incorporated as a nanosize filler in this work. WPCs were prepared by melt blending followed by compression molding, and their performance was investigated by universal testing machine, izod impact tester, dynamic mechanical analyzer, thermal mechanical analyzer, differential scanning calorimetry, and TGA. Maleic anhydride polypropylene copolymer (MAPP) was used to increase compatibility between the PP matrix and wood particles and also improve the dispersion and exfoliation of the organoclay in the PP matrix. XRD analysis showed that the matrix of the WPCs with organoclay had intercalated structure. The SEM images of the WPCs with MAPP showed improved interfacial adhesion between the matrix and wood particles. The degree of water absorption increased with immersion time, but it could be restrained by incorporating MAPP. The performance of the WPCs was improved by the incorporation of the organoclay. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of lanthanum-modified magnesium silicate on isotactic polypropylene crystallization in composite materials during shear flow

The activity of isotactic polypropylene (iPP) nucleating additives during shear flow of composite materials is still not entirely explained. In current work the sol-gel method was employed to synthesize MgO·SiO₂ filler, surface-modified with trivalent lanthanum. The crystallization of commercial iPP in the presence of 0.5% by weight La³⁺ modified or unmodified silicates was analyzed. The wide angle X-ray scattering analysis proved that the presence of even small amount of filler influences significantly on supermolecular structure of iPP. The results of microscope observations confirmed that the lanthanum-modified filler shows the nucleating ability for iPP. In that case a significant reduction of crystallization induction time was noticed. The investigation of iPP crystallization in composites after shear treatment confirmed that the increase of shear rate reduces the nucleating ability of additives. Moreover, the flow of filler particles during shearing may impede the shear-induced crystallization phenomenon.     

Polypropylene composites. I. Studies of the effect of grafting of acrylic acid and silane coupling agent on the performance of polypropylene mica composites

To improve adhesion between polypropylene (PP) and mica in PP composites, acrylic acid (AA) is graft-copolymerized onto PP by a melt-mixing method. At the same time, applying a silane coupling agent to treat the surface of inorganic filler enhances the mechanical, thermal, and electrical properties, as well as decreases mold shrinkage and color difference of the composites.     

Impact behavior of sawdust/recycled–PP composites

The instrumented Izod and Charpy tests were performed on the sawdust–polypropylene (PP) composites to study the nature of impact resistance in the thermoplastic wood composites. The notched Izod strength was found to increase with filler content in composites containing the Maleic–anhydride–grafted PP (MAPP) additive. The Izod strength even exceeds that of the neat matrix resin at higher filler contents, indicating a methodology for applying the recycled PP and also for reinforcing the thermoplastics with wood powders. While the static tensile results show evidences for the reinforcing role of the wood filler, a fracture mechanics characterization through the Charpy impact tests effects of MAPP under the impact loading rates. The choice of MAPP as the additive was discussed accordingly for application of the sort of materials. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1420–1428, 2001     

Maleic anhydride grafted polypropylene as a coupling agent for polypropylene composites filled with ink‐eliminated waste paper sludge flour

Ink‐eliminated sludge flour (IESF), a waste residue from the recycling treatment of waste paper, is a promising new kind of filler for thermoplastic polymers with a good price/performance ratio and advantages for environmental protection. In this study, high‐impact polypropylene (PP) and maleic anhydride grafted polypropylene (MAPP) were chosen as a polymer matrix and a coupling agent, respectively, for the preparation of IESF/PP composites, and the structures and properties of the obtained composites were also investigated. The experimental results revealed that IESF not only induced the crystallization orientation of PP along the b axis but also had a restraining effect on the formation of the β phase during the recrystallization of PP from the melt; the addition of MAPP further strengthened this effect to some extent. In addition, the proper addition of MAPP was helpful for improving the thermal stability of the IESF/PP composites. With the strengthening of the interfacial interaction between the IESF and PP matrix by MAPP, the resultant efficient stress transfer from the PP matrix to the IESF particles led to increased tensile and flexural strength. However, the original greater rigidity of MAPP, with respect to PP, reduced the toughness of the composites and caused some negative effects on the impact strength and the elongation at break. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2320–2325, 2004     

Morphological,mechanical, and physical properties of composites made with wood flour‐reinforced polypropylene/recycled poly(ethylene terephthalate) blends

Wood flour (WF)‐filled composites based on a polypropylene (PP)/recycled polyethylene terephthalate (r‐PET) matrix were prepared using two‐step extrusion. Maleic anhydride grafted polypropylene (MAPP) was added to improve the compatibility between polymer matrices and WF. The effects of filler and MAPP compatibilization on the water absorption, mechanical properties, and morphological features of PP/r‐PET/WF composites were investigated. The addition of MAPP significantly improved mechanical properties such as tensile strength, flexural strength, tensile modulus, and flexural modulus compared with uncompatibilized composites, but decreased elongation at break. Scanning electron microscopic images of fracture surface specimens revealed better interfacial interaction between WF and polymer matrix for MAPP‐compatibilized PP/r‐PET/WF composites. MAPP‐compatibilized PP/r‐PET/WF composites also showed reduced water absorption due to improved interfacial bonding, which limited the amount of absorbable water molecules. These results indicated that MAPP acts as an effective compatibilizer in PP/r‐PET/WF composites. POLYM. COMPOS., 38:1749–1755, 2017. © 2015 Society of Plastics Engineers     

A strategy of fabricating exfoliated thermoplastic polyurethane/clay nanocomposites via introducing maleated polypropylene

By reducing the attraction between the platelets of octadecylammonium chloride modified montmorillonite (OMMT-C18) via pre-intercalation of maleated polypropylene (MAPP), OMMT-C18 was exfoliated in thermoplastic polyurethane (TPU) matrix during melt-mixing. Wide angle X-ray diffraction, transmission electron microscopy and thermogravimetric analysis were used to investigate the microstructure of TPU nanocomposites. Three factors (including introducing sequence, the kind and the content of MAPP) showed important effects on the dispersion degree of OMMT-C18 in TPU matrix. The results confirmed that the pre-intercalation of MAPP was necessary for the exfoliation of OMMT-C18; however, the role of MAPP in TPU nanocomposites was different from that in polypropylene nanocomposites. In addition, the investigation on the morphology evolution of TPU nanocomposites showed that shear force played a key role in the formation of exfoliated TPU nanocomposites. TPU nanocomposites with exfoliated structure showed better properties compared with TPU and its nanocomposites with intercalated structure.     

Effect of maleated polypropylene as a compatibilizer and hyperbranched polyester as a processing aid on polypropylene‐wood flour biocomposites

This work focused on two difficulties associated with preparation of polypropylene/wood flour (PP/WF) composites, viz. the compatibility of PP with WF and processing of the composites with high melt viscosity. Maleic anhydride‐grafted polypropylene (MAPP) was used in the preparation of PP composites to provide the compatibility between polymer and filler. Hyperbranched polyester (HBPE) was incorporated to check feasibility of it as a processing aid in the same. The PP/WF composites were formulated by melt compounding on a Brabender Plastograph EC. Blending effect of compatibilizer and processing aid HBPE on PP/WF biocomposites have been carried out on the basis of torque analysis, mechanical properties, morphology, and thermal stability. The investigation showed that HBPE improves the processibility of PP/WF composites than MAPP with respective to torque value. The mechanical and thermal properties slightly vary with change in relative proportion of MAPP and HBPE. J. VINYL ADDIT. TECHNOL., 24:179–184, 2018. © 2016 Society of Plastics Engineers     

Dynamic rheology,mechanical performance,shrinkage, and morphology of chemically coupled talc‐filled polypropylene

The oscillatory shear rheological properties, mechanical performance, shrinkage, and morphology of polypropylene (PP)‐talc composites chemically coupled by maleic‐anhydride‐grafted polypropylene (MAPP) were studied. The samples were prepared in a co‐rotating L/D = 40, 25 mm twin‐screw extruder. Tensile tests carried out on injection‐molded samples showed a reinforcing effect of talc up to 20 wt% on PP. Upon using MAPP, the mechanical performance of PP‐30% talc showed a maximum of about 10% increase in tensile strength at 1.5 wt% of MAPP. A Newtonian plateau (η₀) at the terminal zone was observed for the complex viscosity curve of pure PP and PP‐talc composites plotted against frequency up to 30 wt%. Upon increasing the talc content to 40 and 50 wt%, the complex viscosity at very low shear rates sharply increased and showed yield behavior that might be due to the formation of a network of filler agglomerates in the melt. Analysis of viscosity behavior in the power‐law region revealed that the flow behavior index‐n‐decreased from 0.45 for 10 wt% of talc down to about 0.4 for 40 wt% of talc. Upon increasing the talc content to 50 wt%, n decreased to a value even lower than that of the neat PP resin. The frequency of the crossover point represents molecular mobility and relaxation‐time behavior. The crossover frequency of the composites was nearly constant up to 30 wt% of talc and decreased at higher filler loadings. The optimum amount of coupling agent could be correlated with the minimum point in crossover frequency and crossover modulus. The shrinkage behavior of the composites with and without MAPP resin was studied and correlated with the rheological properties. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Optical,rheological, and thermal properties of hollow glass bead filled isotactic polypropylene

Hollow glass beads (HGB) were mixed into isotactic polypropylene (iPP) by an internal mixer and the effect of HGB concentration on optical, rheological, and thermal properties of iPP/HGB composites was studied. The dispersion of treated and nontreated HGB in the iPP matrix and the crystal habit of iPP in the composites were examined by phase contrast microscopy. Dynamic rheological measurements were carried out in the melt state in the oscillatory shear mode. The data were analyzed to yield the variations of rheological properties of the composites when the HGB were added. The influence of HGB concentration on the thermal properties including the crystallization and melting behaviors of the composites was studied by means of differential scanning calorimeter and wide angle X‐ray diffraction. It was found that the addition of HGB had effect on the crystallization and melting behaviors of the composites, including that HGB had a weak nucleating effect in the matrix and promoting the formation of β‐crystals of iPP. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Preparation and characteristics of composites of high‐crystalline cellulose with polypropylene: Effects of maleated polypropylene and cellulose content

Binary composites of high‐crystalline fibrous cellulose with polypropylene (PP) or maleic anhydride‐grafted polypropylene (MAPP) were prepared by melt‐mixing with different contents of cellulose from 0 to 60 wt %. Ternary composites of cellulose with PP and MAPP were also prepared to investigate the effects of MAPP as a compatibilizer between cellulose and PP. Scanning electron microscopy revealed that the addition of MAPP generates strong interactions between a PP matrix and cellulose fibers: All cellulose fibers are encapsulated by layers of the matrix and connected tightly within the matrix. Thus, the tensile strength and Young's modulus of MAPP‐containing composites increase with an increase in MAPP and cellulose content, in contrast to the decrease in tensile strength of a PP‐based binary composite with an increase in cellulose. Cellulose fibers act as a nucleating agent for the crystallization of PP, which is promoted by the addition of MAPP through an increase of the crystallization temperature of PP in the composite. Accordingly, both cellulose and MAPP facilitate the thermooxidative stability of PP composites in the following order: MAPP/cellulose > PP/MAPP/cellulose > PP/cellulose > PP. Relative water absorption increases with an increase in cellulose content, decreasing with the addition of MAPP. MAPP‐containing cellulose composites have high potential for applications as environmentally friendly materials. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 337–345, 2003