In situ dynamic vulcanization process in preparation of electrically conductive PP/EPDM thermoplastic vulcanizate/expanded graphite nanocomposites: Effects of state of cure

In situ melt dynamic vulcanization process has been employed to prepare electrically conductive polypropylene (PP)/ethylene–propylene–diene rubber (EPDM) (40/60 wt %) thermoplastic vulcanizates (TPVs) incorporated by expanded graphite (EG) as a conductive filler. Maleic anhydride grafted PP (PP‐g‐MAH) was used as compatibilizer and a sulfur curing system was designed and incorporated to vulcanize the EPDM phase during mixing process. Developed microstructures were characterized using scanning electron microscopy (SEM), melt rheomechanical spectroscopy (RMS), X‐ray diffraction (XRD), and transmission electron microscopy (TEM) and were correlated with electrical conductivity behavior. For comparison, another class of TPV/EG nanocomposites was fabricated using a commercially available PP/EPDM‐based TPV via both direct and masterbatch melt mixing process. Conductivity of the nanocomposites prepared by in situ showed no significant change during dynamic vulcanization till the mixing torque reached to the stationary level where micro‐morphology of the cured rubber droplets was fully developed, and conductivity abrupt was observed. In situ cured nanocomposites showed higher insulator to conductor transition threshold (3.15 vol % EG) than those based on commercially available TPV. All electrically conductive in situ prepared TPV nanocomposites exhibited reinforced melt elasticity with pseudosolid‐like behavior within low frequency region in dynamic melt rheometry indicating formation of physical networks by both EG nanolayers and crosslinked EPDM droplets. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The influence of matrix viscosity and composition on the morphology,rheology, and mechanical properties of thermoplastic elastomer nanocomposites based on EPDM/PP

The morphological and rheological properties of thermoplastic elastomer nanocomposites (TPE nanocomposites) were studied using different viscosities of polypropylene (PP) and ethylene‐propylene‐diene monomer (EPDM) rubber content (20, 40, 60 wt%). The components, namely EPDM, PP, Cloisite 15A, and maleic anhydride‐modified PP as compatibilizer, were compounded by a one‐step melt mixing process in a laboratory internal mixer. The structure of the nanocomposites was characterized with X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, and rheometry in small amplitude oscillatory shear. The distribution state of the clay between the two phases (PP and EPDM) was found to be dependent on the viscosity ratio of PP to EPDM. In the nanocomposites prepared based on low viscosity PP (LVP) and EPDM, the clay was mostly dispersed into the PP phase and the size of the dispersed rubber particles decreased in comparison with unfilled but otherwise similar blends. However, the dispersed elastomer droplet size in the high viscosity PP (HVP) blends containing 40 and 60% EPDM increased with the introduction of the clay. For TPE nanocomposites, the dependence of the storage modulus (G′) on angular frequency (ω) followed a clear nonterminal behavior. The increase in the storage modulus and the decrease in the terminal zone slope of the elastic modulus curve were found to be larger in the LVP nanocomposite in comparison with the HVP sample. The yield stress of nanoclay‐filled blends prepared with LVP increased more than that of HVP samples. The tensile modulus improved for all nanocomposites but a higher percentage of increase was observed in the case of LVP samples. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Melt processing and characterization of polypropylene/pristine montmorillonite nanocomposite: Influence of compatibilizer and hyperbranched polymer

In the present investigation, nanocomposites of polypropylene (PP)‐montmorillonite (MMT) clay were prepared by a single‐step compounding method to study the influence of hyperbranched polyester (HBPE) on rheological and mechanical properties of PP composites in the presence of a compatibilizer. In service of this objective, polyvinylchloride‐grafted‐maleic anhydride (PP‐g‐MA) was used as a compatibilizer for hydrophobic PP and hydrophilic clay. Rheological property in terms of melt viscosity was examined by a Brabender torque rheometer. The composite's morphology was studied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), whereas the dispersion state of nanoparticles in the PP matrix was studied by X‐ray diffraction (XRD). The thermal behavior of nanocomposites was examined by differential scanning calorimetry (DSC). The analysis of results confirmed that the interactions among both additives significantly influenced the morphology, rheology, and thermomechanical properties of the nanocomposites. J. VINYL ADDIT. TECHNOL., 22:72–79, 2016. © 2014 Society of Plastics Engineers     

Effects of clay on the morphology of poly(acrylonitrile-butadiene-styrene) and polypropylene nanocomposites

The effects of clay on the morphology of the poly(acrylonitrile-butadiene-styrene) (ABS)/polypropylene (PP) nanocomposites were investigated. From the studies of wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM) analysis of the ABS/PP (70/30) nanocomposites with clay, it was observed that most of the clay existed in the ABS matrix because of the good affinity between the ABS and clay which contained benzyl group. From the studies of the scanning electron microscopy (SEM) analysis, the size of the PP droplet decreased with clay from 16.7 to 5.6 μm when the clay was added up to 4.0 phr. When the clay content was increased, the droplet of the dispersed phase (PP) was shown to elongated structure. The elongated structure could be explained by the decrease of the viscosity ratio of the PP and continuous phase (ABS) with clay, which corresponded to the increase of the viscosity of the continuous phase (ABS/clay). From the results of the SEM, TEM, and WAXD analysis, it is suggested that the increase of the viscosity of the continuous phase (ABS/clay) is mainly due to the location of clay in the ABS matrix. POLYM. ENG. SCI., 47:1671–1677, 2007. © 2007 Society of Plastics Engineers     

Phase morphology and clay distribution of poly(trimethylene terephthalate)/polypropylene/montmorillonite nanocomposites

Poly(trimethylene terephthalate) (PTT)/polypropylene (PP) blend nanocomposites were prepared by melt mixing of PTT, PP, and organically modified clay. The phase morphologies of the PTT/PP nanocomposites and the distribution of the clay in the nanocomposites were investigated using scanning electron microscopy, transmission electron microscopy (TEM), and wide angle X‐ray diffraction. When PP is the dispersed phase, the domain size of the PP phase is decreased significantly with increasing the clay content from 0 to 5 wt %. In contrast, when PTT is the dispersed phase, the dimension of the PTT phase is a little larger in the presence of 2 wt % clay compared with the case of without clay. TEM observations indicate that the clay is mainly distributed at the phase interfaces along the phase borderlines. In addition, some intercalated clay tactoids (multilayer particles) are observed in the PTT matrix whereas no discernable clay particles can be found in the PP phase, indicating that the affinity of clay with PTT is higher than with PP. In the presence of 5 wt % PP‐graft‐maleic anhydride, the phase morphology is much finer, and most clay is exfoliated and distributed at the phase interfaces forming phase borderlines in polygonal shape. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphological evolution and properties of thermoplastic vulcanizate/organoclay nanocomposites

Nanocomposites composed of organoclay and thermoplastic vulcanizates (TPVs) based on uncompatibilized or compatibilized polypropylene (PP)/ethylene–propylene–diene rubber (EPDM) blends were prepared in this study. The morphology of the nanocomposites was studied with wide‐angle X‐ray diffraction and transmission electron microscopy, which suggested that the addition of the compatibilizer played a key role in determining the morphology of the composites because of their interaction with the clay surface. Scanning electron microscopy study indicated the changes in the morphology of the rubber particles. Dynamic mechanical analysis was also applied to the analysis of these phenomena. Moreover, for nanocomposites with uncompatibilized PP/EPDM blends as the matrix, the samples showed tensile enhancement compared with neat TPV. Although the addition of the compatibilizer changed tensile properties of the composites in a rather different trend, the tensile modulus increased dramatically when the compatibilizer was added. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40618.     

Morphology and mechanical properties of polypropylene/organoclay nanocomposites

Polypropylene (PP) nanocomposites were prepared by melt intercalation in an intermeshing corotating twin‐screw extruder. The effect of molecular weight of PP‐MA (maleic anhydride‐ modified polypropylene) on clay dispersion and mechanical properties of nanocomposites was investigated. After injection molding, the tensile properties and impact strength were measured. The best overall mechanical properties were found for composites containing PP‐MA having the highest molecular weight. The basal spacing of clay in the composites was measured by X‐ray diffraction (XRD). Nanoscale morphology of the samples was observed by transmission electron microscopy (TEM). The crystallization kinetics was measured by differential scanning calorimetry (DSC) and optical microscopy at a fixed crystallization temperature. Increasing the clay content in PP‐ MA330k/clay, a well‐dispersed two‐component system, caused the impact strength to decrease while the crystallization kinetics and the spherulite size remained almost the same. On the other hand, PP/PP‐MA330k/clay, an intercalated three‐component system containing some dispersed clay as well as the clay tactoids, showed a much smaller size of spherulites and a slight increase in impact strength with increasing the clay content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1562–1570, 2002     

Structure and properties of peroxide dynamically vulcanized polypropylene/ethylene–propylene–diene/zinc dimethacrylate composites

Peroxide dynamically vulcanized thermoplastic olefin (TPO) based on polypropylene (PP)/ethylene–propylene–diene (EPDM) loaded with zinc dimethacrylate (ZDMA) was prepared. The addition of ZDMA improved the complex viscosity of the resulting materials in the melt state significantly, as determined from oscillatory rheology analyses. Dynamic mechanical analysis (DMA) and transmission electron microscopy (TEM) examinations were performed to evaluate the structure of the PP/EPDM/ZDMA composite. Atomic force microscope (AFM) and scanning electron microscopy (SEM) were used to study the morphology. The degree of crystallinity was evaluated using X‐ray diffraction method (XRD). The results revealed that incorporation of ZDMA resulted in a size reduction of the rubber droplets and improved the compatibility between rubber and PP phases. The nanoparticles of the polymerized ZDMA (PZDMA) served as an effective nucleating agent for the crystallization of PP. The rheological properties and mechanical properties were improved by ZDMA. Particularly, the izod impact strength of the PP/EPDM/ZDMA (80/20/6, w/w) composite is nearly 2 times higher than the PP/EPDM (80/20, w/w) and 12 times higher than the PP; besides, the elongation at break of the PP/EPDM/ZDMA (80/20/6, w/w) is 3 times higher than that of the PP/EPDM (80/20, w/w) and 6 times higher than the PP. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Preparation of dynamically vulcanized thermoplastic elastomer nanocomposites based on LLDPE/reclaimed rubber

Dynamically vulcanized thermoplastic elastomers nanocomposites (TPV nanocomposites) based on linear low density polyethylene (LLDPE)/reclaimed rubber/organoclay were prepared via one‐step melt blending process. Maleic anhydride grafted polyethylene (PE‐g‐MA) was used as a compatibilizing agent. The effects of reclaimed rubber content (10, 30, and 50 wt %), nanoclay content (3, 5, and 7 wt %), and PE‐g‐MA on the microstructure, thermal behavior, mechanical properties, and rheological behavior of the nanocomposites were studied. The TPV nanocomposites were characterized by X‐ray diffraction, transmission electron microscopy, scanning electron microscopy (SEM), differential scanning calorimeter, mechanical properties, and rheometry in small amplitude oscillatory shear. SEM photomicrographs of the etched samples showed that the elastomer particles were dispersed homogeneously throughout the polyethylene matrix and the size of rubber particles was reduced with introduction of the organoclay particles and compatibilizer. The effects of different nanoclay contents, different rubber contents, and compatibilizer on mechanical properties were investigated. Increasing the amount of nanoclay content and adding the compatibilizer result in an improvement of the tensile modulus of the TPV nanocomposite samples. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Dynamically vulcanized polypropylene/ethylene‐propylene diene monomer/organoclay nanocomposites: Effect of mixing sequence on structural,rheological, and mechanical properties

Dynamically vulcanized thermoplastic elastomer (TPE) nanocomposites based on polypropylene (PP), ethylene‐propylene diene monomer (EPDM) and cloisite 15A were prepared via direct melt mixing in a co‐rotating twin‐screw extruder. The mixing process was carried out with optimized processing parameters (barrel temperature = 180°C; screw speed = 150 rpm; and feeding rate = 0.2 kg/hr). The formulation used to prepare the nanocomposites was fixed to 75/20/5 (PP/EPDM/Cloisite^©15A), expressed in mass fraction. Effect of mixing sequence on the properties of vulcanized and unvulcanized (TPE) nanocomposites prepared under similar conditions was investigated using X‐ray diffraction (XRD) and a tensile testing machine. Results showed that the sequence of mixing does affect the properties of final TPE nanocomposites. Accordingly, nanocomposite samples prepared through mixing the preblended PP/clay masterbatch with EPDM phase, show better clay dispersion within the polymer matrix. J. VINYL ADDIT. TECHNOL., 22:320–325, 2016. © 2014 Society of Plastics Engineers     

三元乙丙橡胶/聚丙烯动态硫化热塑性弹性体的相态结构

用扫描电镜研究了三元乙丙橡胶(EPDM)聚/丙烯(PP)动态硫化热塑性弹性体(TPV)相态结构的形成过程,探讨了交联密度、制备工艺、螺杆转速对EPDM/PP TPV相态结构的影响。结果表明,采用以酚醛树脂为硫化剂的动态硫化工艺制备的EPDM/PP TPV,其相态结构实现了由EPDM和PP组成的双连续相到以EPDM为分散相、PP为连续相的转变;当硫化剂用量为7份时,橡胶相硫化速率和交联密度最大;当螺杆转速为180 r/m in时,反应性挤出工艺较之密炼机工艺制备的EPDM/PP TPV的橡胶粒子更细小、分散更均匀。     

The effect of organoclay on the mechanical properties and morphology of injection‐molded polyamide 6/polypropylene nanocomposites

Nanocomposites containing a thermoplastic blend and organophilic layered clay (organoclay) were produced by melt compounding. The blend composition was kept constant [polyamide 6 (PA6) 70 wt % + polypropylene (PP) 30 wt %], whereas the organoclay content was varied between 0 and 10 wt %. The mechanical properties of the nanocomposites were determined on injection‐molded specimens in both tensile and flexural loading. Highest strength values were observed at an organoclay content of 4 wt % for the blends. The flexural strength was superior to the tensile one, which was traced to the effect of the molding‐induced skin‐core structure. Increasing organoclay amount resulted in severe material embrittlement reflected in a drop of both strength and strain values. The morphology of the nanocomposites was studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy‐dispersion X‐ray analysis (EDX), and X‐ray diffraction (XRD). It was established that the organoclay is well dispersed (exfoliated) and preferentially embedded in the PA6 phase. Further, the exfoliation degree of the organoclay decreased with increasing organoclay content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 175–189, 2004     

The effect of clay type and of clay–masterbatch product in the preparation of polypropylene/clay nanocomposites

Clay containing polypropylene (PP) nanocomposites were prepared by direct melt mixing in a twin screw extruder using different types of organo‐modified montmorillonite (Cloisite 15 and Cloisite 20) and two masterbatch products, one based on pre‐exfoliated clays (Nanofil SE 3000) and another one based on clay–polyolefin resin (Nanomax‐PP). Maleic anhydride‐grafted polypropylene (PP‐g‐MA) was used as a coupling agent to improve the dispersability of organo‐modified clays. The effect of clay type and clay–masterbatch product on the clay exfoliation and nanocomposite properties was investigated. The effect of PP‐g‐MA concentration was also considered. Composite morphologies were characterized by X‐ray diffraction (XRD), field emission gun scanning electron microscopy (FEG‐SEM), and transmission electron microscopy (TEM). The degree of dispersion of organo‐modified clay increased with the PP‐g‐MA content. The thermal and mechanical properties were not affected by organo‐modified clay type, although the masterbatch products did have a significant influence on thermal and mechanical properties of nanocomposites. Intercalation/exfoliation was not achieved in the Nanofil SE 3000 composite. This masterbatch product has intercalants, whose initial decomposition temperature is lower than the processing temperature (T ～ 180°C), indicating that their stability decreased during the process. The Nanomax‐PP composite showed higher thermal and flexural properties than pure PP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of new EPDM/vermiculite nanocomposites

Novel nanocomposites based on ethylene‐propylene‐diene rubber (EPDM) and maleic anhydride‐modified vermiculite (VMT) were prepared. Maleic anhydride (MA) acts both as the intercalation agent for VMT and as a vulcanizing agent for EPDM matrix. It also acts as a compatibilizer for EPDM and VMT phases. From analysis by X‐ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), the silicate layers of the VMT were exfoliated and dispersed uniformly in the EPDM matrix as monolayers. The thermal properties of the nanocomposites were investigated by dynamic mechanical thermal analysis and thermogravimetric analysis; a strong rubber‐filler interaction in the nanocomposites was manifested in the measured temperature range by the result of storage modulus. At the same time, there was some enhancement in degradation behavior between the nanocomposites and EPDM matrix. The nanocomposites exhibited a great improvement in tensile strength and modulus, as well as elongation at break. Finally, the effects of MA addition on the formation of nanometric reinforcement and on the mechanical properties of nanocomposites are discussed. POLYM. COMPOS., 26:706–712, 2005. © 2005 Society of Plastics Engineers     

Exfoliation targeted toughness enhancement in polypropylene‐blend‐ montmorillonite nanocomposites

BACKGROUND: Both exfoliated and toughened polypropylene‐blend‐montmorillonite (PP/MMT) nanocomposites were prepared by melt extrusion in a twin‐screw extruder. Special attention was paid to the enhancement of clay exfoliation and toughness properties of PP by the introduction of a rubber in the form of compatibilizer toughener: ethylene propylene diene‐based rubber grafted with maleic anhydride (EPDM‐g‐MA). RESULTS: The resultant nanocomposites were characterized using X‐ray diffraction, atomic force microscopy, scanning electron microscopy, thermogravimetric analysis, dynamic mechanical analysis and Izod impact testing methods. It was found that the desired exfoliated nanocomposite structure could be achieved for all compatibilizer to organoclay ratios as well as clay loadings. Moreover, a mechanism involving a decreased size of rubber domains surrounded with nanolayers as well as exfoliation of the nanolayers in the PP matrix was found to be responsible for a dramatic increase in impact resistance of the nanocomposites. CONCLUSION: Improved thermal and dynamic mechanical properties of the resultant nanocomposites promise to open the way for highly toughened super PPs via nanocomposite assemblies even with very low degrees of loading. Copyright © 2008 Society of Chemical Industry     

Effect of spatial confinement on the development of β phase of polypropylene

The focus of this study was the effect of spatial confinement on the development of nucleating agent-induced β phase polypropylene (PP) in the dynamically vulcanized thermoplastic elastomers (TPVs) based on dynamically vulcanized PP/ethylene-propylene-diene rubber (EPDM) blend. The melting behaviors, crystalline structures and the morphologies of the blends were studied by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and scanning electron microscopy (SEM). The results indicate that the EPDM phase undergoes a series of changes from the dispersed phase to a continuous one, and again to the dispersed phase with increased content of curing agent, and the PP component always shows itself in a continuous phase. In this process, with the content of the nucleating agent unchanged, the content of β phase PP in the blends initially increases a little and then decreases with increasing PF (Phenolic resin) content. We believe spatial confinement provides a good explanation for the development of β phase PP.     

Polypropylene/montmorillonite composites and their application in hybrid fiber preparation by melt‐spinning

Polypropylene (PP)/organomontmorillonite (OMMT) nanocomposites have been successfully prepared by melt intercalation by using the conventional method of twin‐screw extrusion and subsequently submitted for melt‐spinning. The structure and properties of the PP/clay nanocomposites and hybrid fibers were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD), differential scanning calorimetry (DSC), and crystallization dynamics, etc. The organoclay layers were found to disperse in the PP resin at the nanometer level. The nanoscaled OMMT layers, dispersed in the PP matrix, actually played the role of heterogeneous nuclei species in the process of PP crystallization and increased the nucleation speed of the composites, hereby leading to the increase of crystallization rate of the as‐spun fiber. Meanwhile, it was found that the crystallinity of PP/OMMT hybrid fibers is much higher than that of pure PP fiber at the same draw ratios, whereas the orientation of PP/OMMT hybrid fibers is much lower than that of pure PP fiber at the same draw ratios. Because of the effective intercalation of OMMT into PP matrix, the nanocomposites have good spinnability, and the moisture absorption of the final PP fiber is improved. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 552–558, 2004     

Morphology and crystallization behavior of the PP/PET nanocomposites

Nanocomposites containing polypropylene (PP), PET, and montmorillonite were prepared in a twin‐screw extruder. X‐ray diffraction, transmission electron microscopy, scanning electron microscopy, atomic force microscopy, polarized optical microscopy, and differential scanning calorimetry were used to characterize the samples. Intercalated and exfoliated morphology were observed in the nanocomposites. The PET domains usually presented spherical shapes and they were the start point to PP crystallization. The average diameter and number of PET domains was evaluated. The influence of addition of PP‐MA as compatibilizer on PP/PET was investigated. The interconnected morphology was observed in the nanocomposite containing PP‐MA. The clay located predominantly in the interphase and in the PET phase. The crystallization process was monitored and the PET crystallization rate was slower in the nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polymer nanocomposites based on needle‐like sepiolite clays: Effect of functionalized polymers on the dispersion of nanofiller,crystallinity, and mechanical properties

Polypropylene (PP)/sepiolite (Sep) nanocomposites are prepared by melt compounding in a mini‐extruder apparatus. The often used maleic anhydride‐modified polypropylene (PP‐g‐MA) is compared with two custom‐made functionalized polymers, PP‐acid and the di‐block copolymer PP‐PEO, with respect to the filler dispersion and filler reinforcement efficiency. For that purpose, morphological and mechanical studies are carried out by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and mechanical tensile tests. In addition, the nanocomposites are characterized by wide‐angle X‐ray scattering (WAXS) and differential scanning calorimetric (DSC) techniques, to assess the effect of the nanofiller on the crystalline structure of the PP matrix nano‐filler. The use of PP‐PEO and PP‐acid resulted in a better nanofiller dispersion compared with traditional PP‐g‐MA‐modified systems. Sepiolite acts as nucleating agent for the crystallization of PP and seems to lead to an orientation of the α‐phase crystals. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Synthesis and characterization of polypropylene/clay nanocomposites

Polypropylene/clay (PP/clay) nanocomposites were synthesized via intercalative polymerization. The nanostructure of the composites was investigated by wide‐angle X‐ray diffractometry (WAXD) and transmission electron microscopy (TEM). The WAXD patterns of the PP/clay nanocomposites indicated that the characteristic diffraction peak of the clay disappeared. The TEM image showed the clay was exfoliated into nanometer size and dispersed uniformly in the PP matrix. The composites exhibited much higher storage modulus compared to that of pure PP. At temperatures higher than T_g, the storage modulus of the PP/clay nanocomposites with 8.1 wt % clay content increased three times that of the pure PP. Additionally, the thermal stability of the nanocomposites significantly increased. The maximum decomposition temperature was increased by 44°C with the introduction of about 10 wt % clay. The heat‐distortion temperatures (HDTs) of the nanocomposites also increased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3611–3617, 2001