Structure and properties of polypropylene/clay nanocomposites compatibilized by solid‐phase grafted polypropylene

Polypropylene/organic‐montmorillonite (PP/OMMT) nanocomposites were prepared via a solid‐phase PP graft (TMPP) with a higher grafting level as the compatibilizer. The effects of the compatibilizer on the structure and properties of PP/OMMT nanocomposites were investigated. The structure of the nanocomposites were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results showed that when the weight ratio of TMPP and OMMT is greater than 1:1, the OMMT can be dispersed in PP matrix uniformly at the nanoscale. The mechanical properties of the nanocomposites reached a maximum when the weight ratio of TMPP and OMMT is 1:1, although more uniform dispersion was achieved at a higher content of TMPP. The mechanical properties of the nanocomposites decrease with the content of TMPP. The crystallization behavior, dynamic rheological property, and thermal stability of the nanocomposites were investigated by differential scanning calorimetry (DSC), dynamic rheological analysis, and thermal gravimetric analysis (TGA), respectively. Due to the synergistic effects of TMPP and OMMT on the crystallization of PP, the crystallization peak temperature of the nanocomposites increased remarkably compared with that of the neat PP. TMPP shows β‐phase nucleating ability and OMMT promotes the development of β‐phase crystallite. The nanocomposites show restricted melt flow and enhanced temperature sensitivity compared with the neat PP. The thermal stability of the nanocomposites is obviously improved compared with that of the neat PP. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers.     

Poly(ethylene terephthalate) nanocomposite fibers with new organomica via in situ intercalation

Poly(ethylene terephthalate) (PET) nanocomposites with a newly synthesized organomica (C₁₆BIMD‐Mica) were obtained by using the in situ interlayer polycondensation of ethylene glycol with dimethylterephthalic acid. The PET hybrids were melt‐spun to produce monofilaments with various organoclay contents and draw ratios. The thermomechanical properties and morphologies of the PET hybrid fibers were determined using differential scanning calorimetry, thermogravimetric analysis, wide angle X‐ray diffraction, electron microscopy (SEM and TEM), and a universal tensile machine. The XRD analyses and TEM micrographs showed that the levels of exfoliation and intercalation could be controlled by varying the clay content. The thermomechanical properties of the PET hybrid fibers were found to be better than those of pure PET fibers. POLYM. ENG. SCI., 47:1820–1826, 2007. © 2007 Society of Plastics Engineers     

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.     

Preparation and properties of ethylene–propylene–diene rubber/organomontmorillonite nanocomposites

Ethylene–propylene–diene rubber (EPDM)/organomontmorillonite (OMMT) nanocomposites were prepared with a maleic anhydride grafted EPDM oligomer as a compatibilizer via melt intercalation. X‐ray diffraction and transmission electron microscopy indicated that the silicate layers of OMMT were exfoliated and dispersed uniformly as a few monolayers in nanocomposites. The change in the crystallization behavior of the nanocomposites was examined. The nanocomposites exhibited great improvements in the tensile strength and tensile modulus. The incorporation of OMMT gave rise to a considerable reduction of tan δ and an increase in the storage modulus. Moreover, the solvent resistance of the nanocomposites increased remarkably. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 440–445, 2004     

New toughened polypropylene/organophilic montmorillonite nanocomposites

A new toughened polypropylene (PP)/organophilic montmorillonite (OMMT) nanocomposite was obtained by melt intercalation extrusion in a twin‐screw extruder without any compatibilizer. The nanocomposites were characterized by transmission electron microscopy (TEM) observation, melt flow rate (MFR) testing, mechanical properties measurement, melting and crystallization behaviors, and thermal stability determination. TEM images revealed the existence of intercalated OMMT layers dispersed throughout the PP matrix. A clear reduction in MFR was observed as the OMMT content increased. The yield strength, elongation at yield, and initial modulus of the PP/OMMT nanocomposites increased slightly as the result of the reinforcement of the OMMT nanofiller. The ultimate value of notched impact strength of the nanocomposites was over twofold that of neat PP after incorporation with 4 wt % OMMT; meanwhile, the heat deflection temperature values showed that the thermal stability increased a little. This is a new approach for preparation for the production of a toughened PP material with a high thermal stability and rigidity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

PP/黏土纳米复合材料的结构与性能

采用熔体插层法制备聚丙烯（PP）/有机黏土（OMMT）纳米复合材料。XRD和TEM的测试结果表明,采用熔体插层法制备的PP/OMMT复合材料是剥离型纳米复合材料。力学性能实验结果表明,相容剂的加入提高了PP与OMMT之间的相互作用,使其各项力学性能都得到了提高;PP/OMMT纳米复合材料的各项力学性能在有机黏土含量较小的情况下,就可以有较大幅度的提高;与纯PP相比,相容剂含量为10 phr、有机黏土用量为1 phr的聚丙烯基纳米复合材料具有最好的各项力学性能。     

Study of polypropylene/montmorillonite nanocomposites prepared by solid‐state shear compounding (S3C) using pan‐mill equipment: the morphology of montmorillonite and thermal properties of the nanocomposites

In this paper, polypropylene (PP)/organophilic montmorillonite (OMMT) nanocomposites were successfully prepared without any compatibilizers by solid‐state shear compounding (S³C) using pan‐mill equipment. X‐ray diffraction (XRD) patterns show that the OMMT characteristic (001) peak at 2θ equal to 4.59 degrees disappeared for the milled OMMT and corresponding composites. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) photographs show that the thickness of pan‐milled OMMT decreased from ca 100–200 nm to ca 30–50 nm, and OMMT was partly exfoliated in the PP matrix because the pan‐type mill can exert fairly strong squeezing force in the normal direction and shearing force in both radial and tangential directions on milled materials. PP/OMMT nanocomposites at low OMMT loading have higher melting point, crystallization temperature, thermal degradation temperature and heat distortion temperature than those of neat PP. Moreover, addition of OMMT accelerates crystallization of PP significantly. S³C is a novel approach to prepare polymer/layered silicate nanocomposites with high performances at low filler loading. Copyright © 2004 Society of Chemical Industry     

Mechanical,thermal and dynamic‐mechanical behavior of banana fiber reinforced polypropylene nanocomposites

Natural fiber‐reinforced nanocomposites based on polypropylene/nanoclay/banana fibers were fabricated by melt mixing in a twin‐screw extruder followed by compression molding in this current study. Maleic anhydride polypropylene copolymer (MA‐g‐PP) was used as a compatibilizer to increase the compatibility between the PP matrix, clay, and banana fiber to enhance exfoliation of organoclay and dispersion of fibers into the polymer matrix. Variation in mechanical, thermal, and physico‐mechanical properties with the addition of banana fiber into the PP nanocomposites was investigated. It was observed that 3 wt% of nanoclay and 5 wt% of MA‐g‐PP within PP matrix resulted in an increase in tensile and flexural strength by 41.3% and 45.6% as compared with virgin PP. Further, incorporation of 30 wt% banana fiber in PP nanocomposites system increases the tensile and flexural strength to the tune of 27.1% and 15.8%, respectively. The morphology of fiber reinforced PP nanocomposites has been examined by using scanning electron microscopy and transmission electron microscopy. Significant enhancement in the thermal stability of nanocomposites was also observed due to the presence of nanoclay under thermogravimetric analysis. Dynamic mechanical analysis tests revealed an increase in storage modulus (E′) and damping factor (tan δ), conforming the strong interaction between nanoclay/banana fiberand MA‐g‐PP in the fiber‐reinforced nanocomposites systems. POLYM. COMPOS., © 2011 Society of Plastics Engineers.     

Effect of polymer matrix/montmorillonite compatibility on morphology and melt rheology of polypropylene nanocomposites

In this study, Ca²⁺‐montmorillonite (Ca²⁺‐MMT) and organo‐montmorillonite (OMMT) were modified by three compatibilizers with different degrees of polarity [poly(ethylene glycol) (PEG), alkyl‐PEG, and polypropylene (PP)‐g‐PEG]. PP/MMT nanocomposites were prepared by melt blending and characterized using X‐ray diffraction and transmission electron microscopy. The results showed the degree of dispersion of OMMT in the PP/PP‐g‐PEG/OMMT (PMOM) nanocomposite was considerably higher than those in the PP/PEG/OMMT and PP/alkyl‐PEG/OMMT nanocomposites, which indicated that the dispersion was relative to the compatibility between modified OMMT and PP matrix. Linear viscoelasticity of PP/MMT nanocomposites in melt states was investigated by small amplitude dynamic rheology measurements. With the addition of the modified MMT, the shear viscosities and storage modulus of all the PP/MMT nanocomposites decreased. It can be attributed to the plasticization effect of PEG segments in the three modifiers. This rheological behavior was different from most surfactant modified MMT nanocomposites which typically showed an increase in dynamic modulus and viscosity relative to the polymer matrix. The unusual rheological observations were explained in terms of the compatibility between the polymer matrix and MMT. In addition, the mechanical properties of PP/MMT nanocomposites were improved. A simultaneous increase in the tensile strength and toughness was observed in PP/PMOM nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

PP/PP-g-MAH/OMMT纳米复合材料流变性能

采用自制聚丙烯(PP)接枝马来酸酐(PP-g-MAH)作为相容剂,与经有机化改性的蒙脱土(OMMT)通过熔融插层法制备了PP/PP-g-MAH/OMMT纳米复合材料,对其加工和流变性能进行了研究.结果发现,随着OMMT用量增加,PP/OMMT和PP-g-MAH/OMMT纳米复合材料的熔体流动速率(MFR)有下降的趋势;...     

Influence of Processing Conditions on the Properties of Polystyrene (PS)/organomontmorillonite (OMMT) Nanocomposites Prepared via Solvent Blending Method

A series of polystyrene (PS)/organomontmorillonite (OMMT) clay nanocomposites was prepared by effectively dispersing the inorganic nanolayers of OMMT clay in the organic PS matrix via the solvent blending method using xylene as a solvent. The resulting samples were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The XRD and TEM results show that the intercalation/exfoliation of OMMT can be divided into solvent swelling and layer breaking processes and is affected by several reaction parameters such as nanofiller loading, refluxing temperature, and refluxing time. TGA data show that the PS/OMMT nanocomposites have significant enhanced thermal stability. When 50% weight loss is selected as a point of comparison, the thermal decomposition temperature of PS/OMMT nanocomposite with 7 wt% of OMMT is 15°C higher than that of pure PS. The glass transition temperature (T_g) of PS/OMMT nanocomposites is about 5.0–6.2°C higher than that of pure PS. The water uptake capacity of PS/OMMT nanocomposites is negligible when compared with pure PS.     

Mesua ferrea L. seed oil based highly branched polyester/epoxy blends and their nanocomposites

Mesua ferrea L. seed oil based highly branched polyester and epoxy resins blends were prepared by mechanical mixing at different weight ratios. The best performing blend was used as the matrix for the preparation of nanocomposites with different dose levels of organophilic montmorillonite (OMMT) nanoclay. The prepared nanocomposites were characterized by X‐ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and transmission electron microscopy. Data resulting from the mechanical and thermal studies of the blends and nanocomposites indicated improvements in the tensile strength and thermal stability to appreciable extents for the nanocomposites with OMMT loading. The nanocomposites were characterized as well‐dispersed, partially exfoliated structures with good interfacial interactions. From the X‐ray diffraction analysis, the absence of d₀₀₁ reflections of the OMMT clay in the cured nanocomposites indicated the development of an exfoliated clay structure, which was confirmed by transmission electron microscopy. The homogeneous morphologies of the pure polyester/epoxy blend and clay hybrid systems were ascertained with scanning electron microscopy. The tensile strength of the 5 wt % clay‐filled blend nanocomposite system was increased by 2.4 times compared to that of the pure blend resin system. The results suggest that the prepared nanocomposites have the potential to be used as active thin films for different applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of functionalized SWCNTs on microstructure of PP‐g‐MA/OMMT/f‐SWCNTs nanocomposite

The aim of this work was to study the effect of functionalized single‐walled carbon nanotubes (f‐SWCNTs) on the microstructure of PP‐g‐MA/organic modified montmorillonite (OMMT)/f‐SWCNTs ternary nanocomposite. Pristine SWCNTs were chemically modified by maleic anhydride to improve the interaction between PP‐g‐MA and nanotubes. The dispersion states of OMMT in the different nanocomposites were investigated by wide angle X‐ray diffraction. The morphologies of the nanocomposites were characterized by scanning electron microscopy. Crystallization behaviors of nanocomposites were studied through differential scanning calorimetry and polarizing optical microscopy. Different than the PP‐g‐MA/OMMT binary nanocomposite, in which the OMMT is mainly in an exfoliated state, the ternary PP‐g‐MA/OMMT/f‐SWCNTs nanocomposite exhibits mostly intercalated OMMT. Furthermore, in the ternary nanocomposite, the crystallization of polymer is mainly induced by f‐SWCNTs rather than by OMMT. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

PP/PA6/OMMT复合材料力学性能与结晶性能的研究

采用3种不同有机改性过的蒙脱土(牌号为DK2,DK3,DK5)熔融插层法制备了PP/PA6/OMMT纳米复合物材料,在此基础上使用1%～7%的DK2的蒙脱土再次制备PP/PA6/OMMT纳米复合物材料,借助力学性能测试和差示扫描量热法(DSC)对体系的力学性能和结晶性能进行了研究。结果表明:使用DK2制备的复合材料的力学性能优于使用DK3和DK5制备的复合材料的力学性能;相对于纯PP,PP/PA6/OMMT纳米复合物材料随OMMT含量的增加,拉伸强度和弯曲强度是先增加后降低,最大下降幅度分别为8.7%和5.3%;冲击韧性一直上升达到9.61kJ/m2。OMMT的加入,对PP/PA6有异相成核的作用,提高PP/PA6的结晶速率和结晶度。     

PP/有机改性蒙脱土纳米复合材料的性能

采用熔融插层法制备了聚丙烯/有机改性蒙脱土(PP/OMMT)纳米复合材料,研究了OMMT用量对PP基体力学性能和阻燃性能的影响,利用透射电镜(TEM)分析了OMMT在PP基体中的分散性。结果表明:OMMT的加入有助于提高PP基体的力学性能和阻燃性能;熔融插层法可以使PP的大分子链有效地插入OMMT的片层之间;随着OMMT用量的增加,其在PP基体中的分散性变差。     

Fabrication and properties of nano‐ZnO/glass‐fiber‐reinforced polypropylene composites

Polypropylene (PP) is widely used in many fields, such as automobiles, medical devices, office equipment, pipe, and architecture. However, its high brittle transformation temperature, low mechanical strength, dyeing properties, antistatic properties, and poor impact resistance, considerably limit its further applications. Nano‐ZnO treated by KH550 coupling agent and glass fibers (GFs) were introduced in order to improve the mechanical performance and flowability of PP in this research. The crystallization behavior and microstructure of nano‐ZnO/GFs/PP hybrid composites were analyzed by differential scanning calorimetry, transmission electron microscopy, and scanning electron microscopy. The effect of crystallization behavior on the mechanical properties of the nanocomposites was investigated and analyzed. The results indicated that nano‐ZnO surface‐coupled by KH550 could be uniformly dispersed in the PP matrix. The incorporation of nano‐ZnO and GFs resulted in increases of the crystallization temperature and crystallization rate of PP and a decrease of the crystallization degree. The introduction of nano‐ZnO and GFs also enhanced the tensile strength and impact toughness of the hybrid composites and improved their fluidity. Composites containing 2% of nano‐ZnO and 40% of GFs possessed the optimum mechanical properties. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Crystallization,mechanical, and fracture behavior of mullite fiber‐reinforced polypropylene nanocomposites

This study describes the reinforcement effect of surface modified mullite fibers on the crystallization, thermal stability, and mechanical properties of polypropylene (PP). The nanocomposites were developed using polypropylene‐grafted‐maleic anhydride (PP‐g‐MA) as compatibilizer with different weight ratios (0.5, 1.0, 1.5, 2.5, 5.0, and 10.0 wt %) of amine functionalized mullite fibers (AMUF) via solution blending method. Chemical grafting of AMUF with PP‐g‐MA resulted in enhanced filler dispersion in the polymer as well as effective filler‐polymer interactions. The dispersion of nanofiller in the polymer matrix was identified using scanning electron microscopy (SEM) elemental mapping and transmission electron microscopy (TEM) analysis. AMUF increased the Young's modulus of PP in the nanocomposites up to a 5 wt % filler content, however, at 10 wt % loading, a decrease in the modulus resulted due to agglomeration of AMUF. The impact strength of PP increased simultaneously with the modulus as a function of AMUF content (up to 5 wt %). The mechanical properties of PP‐AMUF nanocomposites exhibited improved thermal performance as compared to pure PP matrix, thus, confirming the overall potential of the generated composites for a variety of structural applications. The mechanical properties of 5 wt % of AMUF filled PP nanocomposite were also compared with PP nanocomposites generated with unmodified MUF and the results confirmed superior mechanical properties on incorporation of modified filler. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43725.     

Effects of thermoplastic polyurethane on the properties of poly(lactic acid)/organo‐montmorillonite nanocomposites based on novel vane extruder

Polylactic acid (PLA)/organo‐montmorillonite (OMMT) nanocomposites toughened with thermoplastic polyurethane (TPU) were prepared by melt‐compounding on a novel vane extruder (VE), which generates global dynamic elongational flow. In this work, the mechanical properties of the PLA/TPU/OMMT nanocomposites were evaluated by tensile, flexural, and tensile tests. The wide‐angle X‐ray diffraction and transmission electron microscopy results show that PLA/TPU/OMMT nanocomposites had clear intercalation and/or exfoliation structures. Moreover, the particles morphology of nanocomposites with the addition of TPU was investigated using high‐resolution scanning electronic microscopy. The results indicate that the spherical TPU particles dispersed in the PLA matrix, and the uniformity decreased with increasing TPU content (≤30%). Interestingly, there existed abundant filaments among amount of TPU droplets in composites with 30 and 40 wt% TPU. Furthermore, the thermal properties of the nanocomposites were examined with differential scanning calorimeter and dynamic mechanical analysis. The elongation at break and impact strength of the PLA/OMMT nanocomposites were increased significantly after addition of TPU. Specially, Elongation at break increased by 30 times, and notched impact strength improved 15 times when TPU loading was 40 wt%, compared with the neat PLA. Overall, the modified PLA nanocomposites can have greater application as a biodegradable material with enhanced mechanical properties. POLYM. ENG. SCI., 54:2292–2300, 2014. © 2013 Society of Plastics Engineers     

Investigation on polypropylene and polyamide-6 alloys/montmorillonite nanocomposites

Propropylene (PP) and polyamide-6 (PA6) alloys nanocomposites were prepared using melt intercalation technique by blending PP and PA6 while used organophilic montmorillonite (OMT). The melt intercalation of PP and PA6 alloys was carried out in the presence of a compatibilizer such as maleic anhydride-g-polypropylene (MAPP). Their structures were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and High Resolution Electronic Microscope (HREM). It was found different blend sequences have influence on the dispersibility of OMT and self-assembled structures of OMT appeared in PP and PA6 alloys. The crystallization behavior and crystal structure of PP and PA6 alloys/montmorillonite nanocomposites were investigated by X-ray diffraction. It showed that the blend sequences have influence on crystal structure and a higher cooling rate results in increasing of γ-crystalline phase. Flammability properties are characterized by Cone Calorimeter, which show an unusual phenomenon.     

Effect of exfoliated organophilic montmorillonite on the structure and conductivity of polypropylene/polyaniline composites

This study concentrates on the effect of organophilic montmorillonite (OMMT) nanolayers on conductivity, structure, morphology, and mechanical properties of the polypropylene/polyaniline (PP/PANI) composites. The composite was prepared by in situ polymerization of aniline at different composition ratios in the presence of PP powder. The structure and conductivity of ternary PP/PANI/OMMT nanocomposites were compared with those of PP/PANI composites. DC electrical conductivity measurements indicated that electrical conductivity decreased in the presence of OMMT layers. Scanning electron microscopy showed that the surface of ternary nanocomposites have more rough regions. The interaction between PANI and OMMT was confirmed by Fourier transform infrared spectroscopy. The distribution of OMMT layers in the polymer matrix, as an effective parameter on the properties of nanocomposite, was investigated and confirmed using X‐ray diffraction and transmission electron microscopy. The results showed an exfoliated array for OMMT layers in the nanocomposite structure. The shear storage modulus for PP/PANI composites was lower than that for pure PP; however, it was increased for PP/PANI/OMMT nanocomposites. The data from the tensile and izod impact strength showed that the Young's modulus and izod impact strength were increased slightly by the addition of OMMT, whereas the elongation at break was decreased. POLYM. COMPOS., 38:699–707, 2017. © 2015 Society of Plastics Engineers