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     

Strategy for the preparation of lightweight polypropylene/polyethylene-octene elastomer composite foams with different phase morphologies using supercritical carbon dioxide

Polypropylene (PP)/polyethylene-octene elastomer (POE) composites with a “sea-island” structure and a cocontinuous structure were prepared. With the selection of a suitable foaming temperature, the supercritical carbon dioxide foaming of PP/POE composites with different phase morphologies occurred only in the POE phase. The effects of the POE content, foaming temperature, pressure, and number of layers on the cell size, cell density, apparent density, foaming layer density, and foaming ratio under different phase morphologies were investigated by scanning electron microscopy, polarized optical microscopy, differential scanning calorimetry, and dynamic thermomechanical analysis. This article provides a novel approach for foaming PP at a low temperature. For PP/POE-blended composites with a “sea-island” structure, the foaming temperature is as low as 80 °C, and for PP/POE alternating multilayered composites with a cocontinuous structure, foaming can occur at 40 °C. Compared with the conventional methods for foaming PP, this method avoids the problems of a high foaming temperature, a narrow range of the foaming temperature, and a low melt strength of the PP. Thus, the PP foaming method was successfully improved, yielding a new technique for the preparation of lightweight PP. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48157.     

Crystallization of Polypropylene in PP/PDMS/Nano-SiO2 Ternary Composite

Effect of dispersion morphology, resulting from different mixing sequences used in making ternary composite polypropylene (PP)/poly(dimethylsiloxane) (PDMS)/nano SiO₂, on the crystallization of PP phase is studied. Mixing sequence is found to have significant effect on the dispersion morphology of the ternary composite, which in turn affected the crystallization of the PP matrix of the ternary composite. Crystallization behaviour of PP, studied by the differential scanning calorimetry, is discussed for the effect of different dispersion morphologies on overall crystallization process rate, nucleation rate, crystal size distribution and crystallinity.     

Influences of compatibilization and compounding process on electrical conduction and thermal stabilities of carbon black‐filled immiscible polypropylene/polystyrene blends

The influences of styrene–butadiene–styrene (SBS) copolymer compatibilizer and compounding process on the electrical conduction and thermal stabilities of carbon black (CB)‐filled immiscible polypropylene (PP)/polystyrene (PS) (1/1) blends were investigated. The immiscible CB/PP/PS composite with CB homogeneously located in the PS phase exhibited the highest resistivity and the fastest variation amplitudes of electrical resistivity (ρ) and rheological parameters upon annealing. An optimal content of 5 vol% SBS could significantly lower ρ of the composites by partially trapping CB particles in the PP/PS interfacial region and by reducing the phase size. The compatibilizer markedly slowed down the variation amplitudes of ρ and rheological parameters and the phase coalescence of the composites submitted to thermal annealing. The (SBS/CB)/PP/PS composite with CB located at the PP/PS interface and in the PP phase prepared by blending a (SBS/CB) masterbatch with PP and PS exhibited lower ρ and better thermal stability in comparison with the CB/SBS/PP/PS composite with CB mainly within the PS phase and partially at the PP/PS interface prepared by direct blending. Spreading and wetting coefficients were used to explain the CB distribution and the phase morphology of the composites. © 2012 Society of Chemical Industry     

聚丙烯/聚苯乙烯/超支化聚酰胺酯共混物及其纤维性能

以原位悬浮聚合法制备聚苯乙烯/超支化聚酰胺酯(PS/HBP)复合粒子,通过双螺杆共混挤出制备系列聚丙烯(PP)/PS/HBP三元共混物。运用傅里叶变换红外光谱仪对PS/HBP复合粒子进行分析,以偏光显微镜、差示扫描量热仪和锥板流变仪等仪器研究了PP/PS/HBP共混体系的相容性、聚集态结构、结晶性和流变性等性能,以万能材料试验机、红外染色机和电脑测色仪研究纤维的力学性能和染色性能。结果表明:PP、PS为热力学不相容体系,少量HBP的加入即可改变PP球晶结构,使球晶小而密,同时PS均匀分散在PP中;引入HBP使得PP的结晶结构有所完善,结晶温度和结晶度升高;引入PS/HBP复合粒子对PP纤维可纺性影响不大,表现为结构化黏度指数轻微升高,但共混纤维可拉伸性较纯PP有极大提高,力学性能有明显改善,染色性能也有显著提高。     

Effect of high content of carbon black on non-isothermal crystallization behavior of poly(ethylene terephthalate)

With the aid of co-rotating twin screw extruder, poly(ethylene terephthalate) (PET)/carbon black (CB) masterbatches were fabricated through melt-compounding using a separate feeding and metering technique and their homogeneous dispersion morphologies were confirmed by scanning electron microscopy and transmission electron microscopy. Moreover, the ultimate content of CB in the masterbatches was verified via thermogravimetric analysis method. The non-isothermal crystallization process of pristine PET and PET/CB masterbatch were investigated by differential scanning calorimetry and the different methods such as Jeziorny modified Avrami equation, Ozawa equation, and the method developed by Mo were employed to analyze their non-isothermal crystallization kinetics. The results show that CB particles uniformly dispersed in PET matrix act as heterogeneous nucleating agents, while crystallization activation energy (ΔE) of PET/CB masterbatch is much greater than that of virgin PET according to Kissinger formula, Takhor model, and Augis-Bennett model. Whereas, the results obtained from the above mentioned three methods simultaneously demonstrate the addition of CB greatly increases crystallization temperature and crystallinity and accelerates crystallization rate. The results reveal that crystal growth has little effect on the crystallization rate and crystal nucleation dominates the crystallization process of PET/CB masterbatch containing very high CB loading (20 wt%).     

Effect of silicon dioxide on crystallization and melting behavior of polypropylene

The crystallization and melting behavior of isotactic polypropylene (iPP) and polypropylene copolymer (co‐PP) containing silicon dioxide (SiO₂) were investigated by differential scanning calorimeter (DSC). SiO₂ had a heterogenous nucleating effect on iPP, leading to a moderate increase in the crystallization temperature and a decrease in the half crystallization time. However, SiO₂ decreased the crystallization temperature and prolonged the half crystallization time of co‐PP. A modified Avrami theory was successfully used to well describe the early stages of nonisothermal crystallization of iPP, co‐PP, and their composites. SiO₂ exhibited high nucleation activity for iPP, but showed little nucleation activity for co‐PP and even restrained nucleation. The iPP/SiO₂ composite had higher activation energy of crystal growth than iPP, indicating the difficulty of crystal growth of the composite. The co‐PP/SiO₂ composite had lower activation energy than co‐PP, indicating the ease of crystal growth of the composite. Crystallization rates of iPP, co‐PP, and their composites depended on the nucleation. Because of its high rate of nucleation, the iPP/SiO₂ composite had higher crystallization rate than iPP. Because of its low rate of nucleation, the co‐PP/SiO₂ composite had lower crystallization rate than co‐PP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1889–1898, 2006     

Crystallization and dynamic mechanical properties of polypropylene/polystyrene blends modified with maleic anhydride and styrene

Polypropylene (PP)/polystyrene (PS) blends modified with reactive monomers, such as maleic anhydride (MAH) and styrene (St), and in situ formed PP/PS blends were prepared by melting extrusion. The crystallization and melting behavior and the dynamic mechanical properties of the PP/PS blends, including the structure of the grafted copolymer, were investigated with differential scanning calorimetry, dynamic mechanical analysis, and Fourier transform infrared. The results indicated that the addition of MAH hardly influenced the crystallization temperature of PP in the blends, but the addition of MAH and St increased the crystallization temperature of PP in its blends. The blends showed no remarkable variety for the melting temperature, but the shapes of the melting peaks were influenced by the addition of the reactive monomers. In addition, a significant increase in the storage and loss moduli of all the modified PP/PS blends was observed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2038–2045, 2005     

Effects of maleated styrene–(ethylene‐co‐butene)–styrene on the morphology and mechanical and thermal properties of polystyrene/polyamide 1212 blends

Polystyrene (PS)/polyamide 1212 (PA 1212) blends were compatibilized with a maleated triblock copolymer of styrene–(ethylene‐co‐butene)–styrene (SEBS‐g‐MA). Scanning electron microscopy revealed that the addition of SEBS‐g‐MA was beneficial to the dispersion of PA 1212 in the PS matrix because of the reaction between them. The variation of the fraction of SEBS‐g‐MA in the blends allowed the manipulation of the phase structure, which first formed a sheetlike structure and then formed a cocontinuous phase containing PA 1212/SEBS‐g‐MA core–shell morphologies. As a result, the mechanical properties, especially the Charpy notched impact resistance, were significantly improved with the addition of SEBS‐g‐MA. Differential scanning calorimetry (DSC) data indicated that the strong interaction between SEBS‐g‐MA and PA 1212 in the blends retarded the crystallization of PA 1212. The heat distortion temperature of the compatibilized blends was improved in comparison with that of the unmodified blend, probably because of the apparent increase in the glass‐transition temperature with an increasing concentration of SEBS‐g‐MA. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1354–1360, 2005     

The physical and mechanical properties of beta‐nucleated polypropylene/montmorillonite nanocomposites

Polypropylene (PP) and polypropylene/polypropylene‐g‐maleic anhydride/ organomontmorillonite (PP/PP‐g‐MA/OMMT) nanocomposites were modified with 0.05 to 0.3% (w/w) of the aryl amide β‐nucleator to promote the formation of hexagonal crystal modification (β‐phase) during melt crystallization. The nonisothermal crystallization behavior of PP, PP/PP‐g‐MA/OMMT and β‐nucleated PP/PP‐g‐MA/OMMT nanocomposites were studied by means of differential scanning calorimetry. Structure‐property relationships of the PP nanocomposites prepared by melt compounding were mainly focused on the effect and quantity of the aryl amide nucleator. The morphological observations, obtained from scanning electron microscopy, transmission electron microscopy and X‐ray diffraction analyses are presented in conjunction with the thermal, rheological, and mechanical properties of these nanocomposites. Chemical interactions in the nanocomposites were observed by FT‐IR. It was found that the β‐crystal modification affected the thermal and mechanical properties of PP and PP/PP‐g‐MA/OMMT nanocomposites, while the PP/PP‐g‐MA/OMMT nanocomposites of the study gained both a higher impact strength (50%) and flexural modulus (30%) compared to that of the neat PP. β‐nucleation of the PP/PP‐g‐MA/OMMT nanocomposites provided a slight reduction in density and some 207% improvement in the very low tensile elongation at break at 92% beta nucleation. The crystallization peak temperature (T_cp) of the PP/PP‐g‐MA/OMMT nanocomposite was slightly higher (116°C) than the neat PP (113°C), whereas the β‐nucleation increased the crystallization temperature of the PP/PP‐g‐MA/OMMT/aryl amide to 128°C, which is of great advantage in a commercial‐scale mold processing of the nanocomposites with the resulting lower cycle times. The beta nucleation of PP nanocomposites can thus be optimized to obtain a better balance between thermal and mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Crystallization kinetics of polypropylene composites filled with nano calcium carbonate modified with maleic anhydride

The subject of this study was the crystallization behavior and thermal properties of polypropylene (PP)/maleic anhydride (MAH) modified nano calcium carbonate (nano‐CaCO₃) composites. In this study, 5 wt % nano‐CaCO₃ modified with different contents of MAH was filled into a PP matrix. X‐ray diffraction and differential scanning calorimetry were used to characterize the crystal morphology and crystallization kinetics of a series of composites. The results demonstrate that the nano‐CaCO₃ modified with MAH had an important effect on the thermal and morphological properties of the nanocomposites. The Avrami exponent of the pure PP was an integer, but those of the composites were not integers, but the crystallization rate constant decreased as the content of MAH in the nano‐CaCO₃ filler increased in isothermal crystallization. In nonisothermal crystallization, the kinetic parameter F(T) and the degree of crystallinity of pure PP were compared with those of the PP composites filled with nano‐CaCO₃. We suggest that heterogeneous nucleation existed in the PP composites and that the transformation and retention of the β‐form crystal into the α‐form crystal took place in the composite system and the β‐form crystal had a higher nucleation rate and growth process than the α‐form crystal in the PP composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Carbon black‐filled immiscible polypropylene/epoxy blends

Carbon black‐ (CB) filled immiscible thermoplastic/thermosetting polymer blends consisting of polypropylene (PP) and epoxy resin were reported in this paper. The PP/epoxy/CB blends with varied compositions and different processing sequences were prepared by melt‐mixing method. The CB distribution and the relationship between morphology and electrical properties of the PP/epoxy/CB blends were investigated. Scanning electron microscopy (SEM), optical microscopy, and extraction experimental results showed that in PP/epoxy blends CB particles preferentially localized in the epoxy phase, indicating that CB has a good affinity with epoxy resin. The incorporation of CB changed the spherical particles of the dispersed epoxy phase into elongated structure. With increasing epoxy content, the elongation deformation of epoxy phase became more obvious and eventually the blends developed into cocontinuous structure. When CB was initially blended with PP and followed by the addition of epoxy resin, the partial migration of CB from PP to the epoxy phase was observed. When the PP/epoxy ratio was 40/60, the percolation threshold was reduced to about 4 phr CB, which is half of the percolation threshold of the PP/CB composite. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 461–471, 2006     

Surface modification of carbon black to facilitate suspension polymerization of styrene and carbon black

To carry out suspension polymerization of styrene in the presence of carbon black, an effective method was introduced to modify carbon black using nitric acid for oxygen treatment. The surface modification of carbon black with oxidation was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy (SEM), which demonstrated that the chemical structure of carbon black has clearly changed. Compared with pristine carbon black (CB), SEM illustrates that the aggregation phenomenon of modified carbon black (MCB) was clearly weakened. After modification, the aggregation and inhibition effects of MCB on the polymerization of polystyrene/modified CB (PS/MCB) composite particles are obviously weakened. The lipophilicity of CB after modification was also increased during the synthesis of PS/MCB. The oxidized CB was successfully dispersed by polystyrene using in situ suspension polymerization. The dispersion and dosage of MCB in PS/MCB composite particles was greatly improved over that of CB in PS/CB composite particles. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46387.     

Effect of morphology on the electric conductivity of binary polymer blends filled with carbon black

Several carbon black (CB)‐filled binary polymer blends were prepared in Haake rheometer. Distribution states of CB and effect of morphology on the electric conductivity of different ternary composites were investigated. Under our experimental condition CB particles located preferentially at the interface between polymethyl methacrylate (PMMA) and polypropylene (PP) in PMMA/PP/CB composites, in high‐density polyethylene (HDPE) phase in PP/HDPE/CB composites, and in Nylon6 (PA6) phase in polystyrene (PS)/PA6/CB, PP/PA6/CB, PMMA/PA6/CB, and polyacrylonitrile (PAN)/PA6/CB composites; the ternary composites in which CB particles locate at the interface of two polymer components have the highest electric conductivity when the mass ratio of the two polymers is near to 1 : 1. The ternary composites in which CB particles located preferentially in one polymer have the highest electric conductivity usually when the amount of the polymer component having CB particles is comparatively less than the amount of the polymer component not having CB particles; if the formulations of PS/PA6/CB, PP/PA6/CB, and PMMA/PA6/CB composites equaled and PA6/CB in them is in dispersed phase, PS/PA6/CB composites have the highest electric conductivity and PP/PA6/CB composites have the lowest electric conductivity; suitable amount of PS or PAN in PA6/CB composites increase the electric conductivity due in the formation of a parallel electrocircuit for electrons to transmit. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Crystallization Behavior in Poly(propylene) Containing Wollastonite Microfibrils

The structure development and crystallization behavior of poly(propylene) (PP) filled with wollastonite mineral was studied with respect to different particle sizes of the filler. The decrease in particle size led to increase in crystallization rates and decrease of crystallization half time, indicating greater nucleation efficiency for smaller sizes of the wollastonite particles. This was also reflected in the higher crystallinity values obtained for small filler particles. The WAXD analysis of PP/wollastonite revealed significant changes in the relative intensity of certain peaks (110 reflection) at small particle size, indicating preferential growth of PP on wollastonite. The exact co‐relationship of nucleation rate/crystallization rate and the additive particle size (d) was determined which showed that for any given concentration of the additive, it was proportional to (1/d)³.     

Developing electrically conductive polypropylene/polyamide6/carbon black composites with microfibrillar morphology

We have established that the PP/PA6/CB composite with 3D microfibrillar conducting network can be prepared in situ using melt spinning process. CB particles preferably were localized at the interface between polypropylene as the matrix and PA6 microfibrils, which act as the conducting paths inside the matrix. The percolation threshold of the system reduced when aspect ratio of the conducting phase was increased by developing microfibrillar morphology. The effect of annealing process on the conductivity of PP/PA6/CB composite with co‐ continuous and microfibrillar morphologies was studied. It was observed that, annealing process forces CB particles towards the interface (2D space) of PP and PA6 co‐continuous phases, and percolation threshold and critical exponent of classical percolation theory will be decreased, while the conductivity of conducting composite with microfibrillar morphology was not affected considerably by annealing process at temperatures either higher or lower than the melting point of the PA6 microfibrils. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of interfacial interaction on the crystallization and mechanical properties of PP/nano‐CaCO3 composites modified by compatibilizers

To investigate the effect of interfacial interaction on the crystallization and mechanical properties of polypropylene (PP)/nano‐CaCO₃ composites, three kinds of compatibilizers [PP grafted with maleic anhydride (PP‐g‐MA), ethylene–octene copolymer grafted with MA (POE‐g‐MA), and ethylene–vinyl acetate copolymer grafted with MA (EVA‐g‐MA)] with the same polar groups (MA) but different backbones were used as compatibilizers to obtain various interfacial interactions among nano‐CaCO₃, compatibilizer, and PP. The results indicated that compatibilizers encapsulated nano‐CaCO₃ particles, forming a core–shell structure, and two interfaces were obtained in the compatibilized composites: interface between PP and compatibilizer and interface between compatibilizer and nano‐CaCO₃ particles. The crystallization and mechanical properties of PP/nano‐CaCO₃ composites were dependent on the interfacial interactions of these two interfaces, especially the interfacial interaction between PP and compatibilizer. The good compatibility between PP chain in PP‐g‐MA and PP matrix improved the dispersion of nano‐CaCO₃ particles, favored the nucleation effect of nano‐CaCO₃, increased the tensile strength and modulus, but reduced the ductility and impact strength of composites. The partial compatibility between POE in POE‐g‐MA and PP matrix had little effect on crystallization and mechanical properties of PP/nano‐CaCO₃ composites. The poor compatibility between EVA in EVA‐g‐MA and PP matrix retarded the nucleation effect of nano‐CaCO₃, and reduced the tensile strength, modulus, and impact strength. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electromagnetic Interference (EMI) Shielding Effectiveness of PP/PS Polymer Blends Containing High Structure Carbon Black

The morphological, electrical resistivity (ER), and electromagnetic interference (EMI) shielding effectiveness (SE) properties of poly(propylene) (PP), polystyrene (PS), PP/PS, and PP/PS/styrene–butadiene–styrene (SBS) blends filled with 10 vol.‐% high structure carbon black (CB) were studied. For the CB/PP/PS blends, TEM and SEM observations indicated that CB is preferentially localized in the PS phase. ER and EMI SE of the CB/PP/PS and CB/PP/PS/SBS blends were bounded between those of the PS composite (lower bound) and the PP composite (upper bound). In the PP/PS volume ratio ranging from (75/25) to (25/75), ER and EMI SE of the CB‐filled blends were independent of the PP/PS volume ratio. The EMI SE obtained by the 2 mm thick plates made of 10 vol.‐% CB‐filled (100/0)–(10/90) PP/PS blends are adequate for computers shielding applications.

     

Effect of double percolation on the electrical properties and electromagnetic interference shielding effectiveness of carbon‐black‐loaded polystyrene/ethylene vinyl acetate copolymer blends

In this study, the concept of double percolation and selective location of a conducting additive was used to develop conducting polymer composites composed of polystyrene (PS) and ethylene vinyl acetate copolymer (EVA) filled with carbon black (CB). Scanning and transmission electron microscopy suggested that the CB was preferentially located in the EVA phase. By combining a cocontinuous morphology and selective location of CB in the EVA phase, we achieved the highest conductivity values and better electromagnetic interference shielding effectiveness in the X‐band frequency range for the 70:30 w/w PS/EVA blend. Electromagnetic attenuation occurred by both reflection and absorption mechanisms, although the first was predominant for composites with a higher amount of CB. The percolation thresholds of the PS, EVA, and 70:30 w/w PS/EVA blend loaded with CB were estimated from the dependence of the alternating‐current and direct‐current conductivities. The rheological properties were also used to relate the electrical behavior to the microstructure of the composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43013.     

Nonisothermal crystallization kinetics of polypropylene/polypropylene‐g‐polystyrene/polystyrene blends

The nonisothermal crystallization kinetics of polypropylene (PP), PP/polystyrene (PS), and PP/PP‐g‐PS/PS blends were investigated with differential scanning calorimetry at different cooling rates. The Jeziorny modified Avrami equation, Ozawa method, and Mo method were used to describe the crystallization kinetics for all of the samples. The kinetics parameters, including the half‐time of crystallization, the peak crystallization temperature, the Avrami exponent, the kinetic crystallization rate constant, the crystallization activation energy, and the F(T) and a parameters were determined. All of the results clearly indicate that the PP‐g‐PS copolymer accelerated the crystallization rate of the PP component in the PP/PP‐g‐PS/PS blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011