Investigation of the morphology of polypropylene − nanoclay nanocomposites

The morphology development in polypropylene ? nanoclay composites with different weight percentages of nanoclay additives was studied using a combination of wide‐angle X‐ray diffraction, small‐angle X‐ray scattering (SAXS), polarized optical microscopy and transmission electron microscopy. SAXS studies showed an increase in long period with increase in additive weight percentage. Thermal analysis showed that even if the clay platelets are not completely exfoliated they can act as effective nucleating agents. Studies indicated that the ultimate morphology formation is influenced by both the thermodynamics of mixing and crystallization and spherulite formation. During spherulite growth, unenclosed clay platelets were excluded at the spherulite boundaries. From the observed results, a schematic model of morphology formation in polypropylene ? nanoclay composites is proposed. © 2013 Society of Chemical Industry     

Structure–thermomechanical property correlation of moisture cured poly(urethane-urea)/clay nanocomposite coatings

A series of poly(urethane-urea)/clay nanocomposite coatings were prepared by moisture curing of isophorone diisocyanate (IPDI) capped hydroxyl terminated polybutadiene (HTPB)/clay dispersions in a relative humidity (RH) of 50% at 25 °C. The curing progress was studied by periodic measurement of gel fraction of the coating samples. The studies revealed tortuosity effects of clay toward moisture diffusion, thus delaying the induction period of gelation, time for complete cure and rate of gel formation of the nanocomposite coatings. The clay platelets were found to be intercalated in the poly(urethane-urea) matrix, evidenced from wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). Effects of nanoclay on state of the hard and soft segments were investigated by WAXD, differential scanning calorimetry (DSC), temperature modulated DSC (MDSC) and solid-state nuclear magnetic resonance spectroscopy (NMR). WAXD studies revealed unusually ordered hard segment morphology of the moisture cured poly(urethane-urea) and its nanocomposites. Slower soft segment dynamics upon clay addition was evident from concentration dependant broadening of the line widths of the NMR peaks, and decreasing reversible heat capacity changes at soft segment glass transition. The volume fraction of immobilized soft segments of the nanocomposites was determined from MDSC and was found to increase linearly with clay loading. The mechanical property analysis showed simultaneous reinforcement and toughening effect of nanoclay on the MCPU matrix. The increment in mechanical property of the nanocomposites varied proportionately with the volume fraction of immobilized soft segments.     

Uniaxial compression and stretching deformation of an i-PP/EPDM/organoclay nanocomposite

In this study, the morphology and rheological properties of nanocomposites prepared by melt mixing of isotactic polypropylene (i-PP), ethylene-propylene-diene terpolymer rubber (EPDM), and Cloisite 15A organoclay, were investigated at rest and under of uniaxial compression and stretching deformations at room temperature. Transmission electron microscopy (TEM) and wide-angle X-ray diffraction (WAXD) experiments revealed that intercalation took place between the clay and the blend. The lamellar long period (L) of the polymeric structure determined by small-angle X-ray scattering (SAXS) was found to increase upon the addition of nanoclay, which also resulted in variations in the angle of rotation (?) between the polymer and clay lamellae. The intercalated nanoclay improved the storage and loss modulus of the resulting materials in the melt state significantly, as determined from oscillatory rheology analyses. Finally, we verified that the uniaxial plane deformation caused by compression of the nanocomposites contributed to the reduction of crystalline domains in the blend, while the crystallinity remained almost constant in the case of uniaxial stretching deformation.     

Morphological influence on mechanical characterization of ethylene‐vinyl acetate copolymer–clay nanocomposites

Ethylene‐vinyl acetate copolymer (EVA)/montmorillonite (MMT) clay nanocomposites with varying degree of intercalation and exfoliation have been prepared using direct melt blending techniques with various degrees of polarity (9, 18, and 28 wt% vinyl acetate [VA]) and two different types of clay modification. Morphological characterization using wide‐angle X‐ray scattering (WAXS) and transmission electron microscopy (TEM) have indicated/confirmed the presence of intercalation and/or a combination of intercalation and exfoliation existing in the nanocomposites. The effects of these (simple intercalation or mixed intercalation/exfoliation) states and the effect of changing matrix polarity (by changing VA wt% content) on the nanocomposite mechanical behavior were studied. There is sufficient evidence from the mechanical studies that 1) the presence of nanoclay can simultaneously improve modulus and strength of the nanocomposites, and 2) the mechanical properties are a combined function of the clay concentration and the nanocomposite morphology (due to the VA wt% and presence of clay). It is shown here that interrelation between the VA wt% content and the clay exfoliation affects the mechanical properties in a way that has a positive and increasing slope with increasing loading of clay. It is shown that a clear understanding of the nanocomposite mechanical properties can be obtained from its morphological analysis. POLYM. ENG. SCI., 45:889–897, 2005. © 2005 Society of Plastics Engineers     

Morphology and properties of nylon 6 and high density polyethylene blends in presence of nanoclay and PE‐g‐MA

In this study, we report the synergistic effect of nanoclay and maleic anhydride grafted polyethylene (PE‐g‐MA) on the morphology and properties of (80/20 w/w) nylon 6/high density polyethylene (HDPE) blend. Polymer blend nanocomposites containing nanoclay with and without compatibilizer (PE‐g‐MA) were prepared by melt mixing, and their morphologies and structures were examined with scanning electron microscopy (SEM) and wide angle X‐ray diffractometer (WAXD) study. The size of phase‐separated domains decreased considerably with increasing content of nanoclay and PE‐g‐MA. WAXD study and transmission electron microscopy (TEM) revealed the presence of exfoliated clay platelets in nylon 6 matrix, as well as, at the interface of the (80/20 w/w) nylon 6/HDPE blend–clay nanocomposites. Addition of PE‐g‐MA in the blend–clay nanocomposites enhanced the exfoliation of clays in nylon 6 matrix and especially at the interface. Thus, exfoliated clay platelets in nylon 6 matrix effectively restricted the coalescence of dispersed HDPE domains while PE‐g‐MA improved the adhesion between the phases at the interface. The use of compatibilizer and nanoclay in polymer blends may lead to a high performance material which combines the advantages of compatibilized polymer blends and the merits of polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of clay addition on the morphology and thermal behavior of polyamide 6

The nanostructure, morphology, and thermal properties of polyamide 6 (PA6)/clay nanocomposites were studied with X‐ray scattering, differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). The wide‐angle X‐ray diffraction (WAXD) and TEM results indicate that the nanoclay platelets were exfoliated throughout the PA6 matrix. The crystallization behavior of PA6 was significantly influenced by the addition of clay to the polymer matrix. A clay‐induced crystal transformation from the α phase to the γ phase for PA6 was confirmed by WAXD and DSC; that is, the formation of γ‐form crystals was strongly enhanced by the presence of clay. With various clay concentrations, the degree of crystallinity and crystalline morphology (e.g., spherulite size, lamellar thickness, and long period) of PA6 and the nanocomposites changed dramatically, as evidenced by TEM and small‐angle X‐ray scattering results. The thermal behavior of the nanocomposites was investigated with DSC and compared with that of neat PA6. The possible origins of a new clay‐induced endothermic peak at high temperature are discussed, and a model is proposed to explain the complex melting behavior of the PA6/clay nanocomposites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1191–1199, 2007     

Effect of clay content and clay/surfactant on the mechanical, thermal and barrier properties of polystyrene/organoclay nanocomposites

In the present paper, three ammonium salts namely, tetraethylammonium bromide (TEAB), tetrabutylammonium bromide (TBAB), and cetyltrimethylammonium bromide (CTAB) were employed to prepare organoclay by cation exchange process. Polystyrene (PS) /clay nanocomposites were prepared by melt blending using commercial nanoclay and organoclays prepared using above mentioned salts. X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis indicated that the modified clays were intercalated and/or exfoliated into the polystyrene matrix to a higher extent than the commercial nanoclay. Further, amongst the modified organoclays, TBAB modified clay showed maximum intercalation of clay layers and also exfoliation to some extent into the polystyrene matrix. TEM micrograph exhibited that TBAB modified clay had the best nanoscale dispersion with clay platelet thickness of ∼6–7 nm only. The mechanical properties of the nanocomposites such as tensile, flexural and izod impact strength were measured and analyzed in relation to their morphology. We observed a significant improvement in the mechanical properties of polystyrene/clay nanocomposites prepared with modified clays as compared to commercial organoclay, which followed the order as; PS/TBAB system > PS/CTAB system > PS/TEAB system. Thermogravimetric analysis (TGA) demonstrated that T₁₀, T₅₀ and Tmax were more in case of polystyrene nanocomposites prepared using modified organoclays than nanoclay [nanolin DK4] and maximum being in the case of PS/CTAB system. The results of Differential Scanning Calorimetry (DSC) confirmed that the glass transition temperature of all the nanocomposites was higher as compared to neat polystyrene. The nanocomposites having 2% of TBAB modified clay showed better oxygen barrier performance as compared to polystyrene.     

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.     

Epoxy‐clay nanocomposites: Influence of the clay surface modification on structure

In this article, the effect of four different clay surface modifiers on the structure of epoxy‐clay nanocomposites was studied. Various organoclays were prepared via cation exchange reaction between inorganic cations naturally occuring in the clay gallery and different alkylammonium ions. Epoxy‐clay nanocomposites were prepared by in situ intercalative polymerization using a hardener of polyoxypropylenediamine type. It was found that various clay surface modifiers exhibit different catalytic effect on curing of epoxy inside the clay gallery as observed by measuring of the gel time with dynamic mechanical analysis. This was confirmed by monitoring the change in the d‐spacing by wide angle X‐ray scattering performed in situ during curing. Morphology of the cured systems was probed by transmission electron microscopy (TEM) and wide angle X‐ray scattering (WAXS). The degree of dispersion observed by TEM and WAXS corresponds with achieved mechanical properties of cured composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology and mechanical properties of heterophasic PP–EP/EVA/organoclay nanocomposites

The effect of vinyl acetat (VA) on the morphological, thermal stability, and mechanical properties of heterophasic polypropylene–(ethylene‐propylene) copolymer (PP–EP)/poly(ethylene vinyl acetate) (EVA)/organoclay nanocomposites was studied. Tailored organoclay C20A was selected to enhance the exfoliation of the clay platelets. Depending on the VA content, there were two morphological organoclay populations in the systems. Both populations were directly observed by scanning transmission electron microscopy and measured by wide‐angle X‐ray diffraction and small‐angle X‐ray scattering. The content of VA in EVA originated spherical and elongated morphologies in the resultant nanocomposites. High‐VA content led to a better intercalation of the organoclay platelets. Measurement of thermal properties suggested that higher VA decreases thermal stability in samples both with and without organoclay, although nanocomposites had higher thermal stability than samples without clay. The storage modulus increased both with nanoclay and VA content. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Morphological,rheological and thermal studies in melt processed compatibilized PA6/ABS/clay nanocomposites

Multicomponent compatibilized blends of polyamide 6 (PA6) and styrene-butadiene-acrylonitrile (ABS) with co-continuous morphology are among commercial alloys with an interesting combination of properties. To further enhance the properties different amounts of nanoclay were incorporated into these blends through a one step melt mixing process. The effect of nanoclay addition on rheological, thermal stability, crystallization and morphological properties of the nanocomposites were investigated and compared with those of the neat blends. The nanoscale dispersion of the clay layers in the blends were confirmed through X-ray diffraction and transmission electron microscopy methods. Rheological investigation indicated an increased viscosity and melt elasticity for the nanocomposite systems. The viscosity of nanocomposites followed a shear thinning flow behavior and decreased with increasing shear rates. The changes in the rheological properties were accompanied by refinement of the co-continuous morphology. For thermal degradation under N₂ atmosphere, the onset and maximum of degradation temperatures for the nanocomposites were as high as the neat blends, while significant improvement in thermal stability (about 60 °C by 3 wt% clay addition) was observed in the air environment. In addition agglomerated clay particles did not significantly affect thermal stability of the polymer matrix. Non-isothermal crystallization results indicated that the clay layers had a retarding effect on the crystal growth rate and facilitated the formation of α crystalline form. In addition no nucleation effect was observed during the crystallization process due to incorporation of nanoclay into the blends.     

Morphology and mechanical and viscoelastic properties of rubbery epoxy/organoclay montmorillonite nanocomposites

The morphology and mechanical and viscoelastic properties of rubbery epoxy/organoclay montmorillonite (MMT) nanocomposites were investigated with wide‐angle X‐ray scattering (WAXS), transmission electron microscopy (TEM), tensile testing, and dynamic mechanical thermal analysis. An ultrasonicator was used to apply external shearing forces to disperse the silicate clay layers in the epoxy matrix. The first step of the nanocomposite preparation consisted of swelling MMT in a curing agent, that is, an aliphatic diamine based on a polyoxypropylene backbone with a low viscosity for better diffusion into the intragalleries. Then, the epoxy prepolymer was added to the mixture. Better dispersion and intercalation of the nanoclay in the matrix were expected. The organic modification of MMT with octadecylammonium ions led to an increase in the initial d‐spacing (the [d₀₀₁] peak) from 14.4 to 28.5 Å, as determined by WAXS; this indicated the occurrence of an intercalation. The addition of 5 phr MMTC18 (MMT after the modification) to the epoxy matrix resulted in a finer dispersion, as evidenced by the disappearance of the diffraction peak in the WAXS pattern and TEM images. The mechanical and viscoelastic properties were improved for both MMT and MMTC18 nanocomposites, but they were more pronounced for the modified ones. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 103: 3547–3552, 2007     

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     

A Model for Molecular Weight Prediction in Acrylonitrile Polymerization

Poly ethylene terephthalate (PET)-based nanocomposites containing three differently modified clays were prepared by melt compounding. The influence of type of modified clay on surface properties of the resultant nanocomposite was investigated by various analytic techniques, namely, Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), contact angle measurement (CAM), scanning electron microscopy (SEM) and reflectance spectroscopy (RS). Any possible interaction between each nanoclay and PET at the surface was elucidated by Fourier transform infrared spectroscopy. Atomic force microscopy studies of the resultant nanocomposites showed increased in surface roughness compared to pure PET. Contact angle measurements on the resultant PET composites demonstrated that the wettability of such composites depends on hydrophilicity of the nanoclay particles. Scanning electron microscopy images illustrated poor interfacial interaction between PET and Na⁺ clay particles causing fracture type non-uniformity of PET/Na⁺ clay nanocomposite.     

Extraordinarily high plastic deformation in polyurethane/silica nanoparticle nanocomposites with low filler concentrations

We have synthesized segmented polyurethane (SPU)/silica nanoparticle (SiNP) nanocomposites with extraordinarily high tensile strength and strain-at-break using an in-situ polymerization method with low SiNP concentrations. A 20-fold increase in strain-at-break compared with the pristine polymer has been achieved for the 0.5 wt% SiNP nanocomposites. A suite of characterization tools including transmission electron microscopy, ultra-small angle X-ray scattering, X-ray diffraction, differential scanning calorimetry and thermogravimetric analysis has been used to correlate the phase morphology, crystallization, and mechanical properties. The location of SiNP in the phase separated SPU is believed to be the main reason for the mechanical property enhancement.     

Dispersion of nanoclay into polypropylene with carbon dioxide in the presence of maleated polypropylene

The effect of maleic anhydride grafted polypropylene (PP-g-MA) on the mechanical and rheological properties of polypropylene (PP)–clay nanocomposites prepared with nanoclay expanded with CO₂ and direct melt blending was studied. The results from the studies of the mechanical properties, rheological properties, and transmission electron microscopy show that when PP-g-MA was combined with the technique that used CO₂, greater enhancements in the mechanical properties and degree of dispersion of nanoclay in PP were observed. Furthermore, yieldlike behavior in the viscosity and a tail in the low-frequency behavior of the elastic modulus was attributed to the reaction of PP-g-MA with the nanoclay surface and not exfoliation. A fairly well-dispersed morphology was observed for concentrations as high 6.8 wt % clay when the clay was expanded and mixed with CO₂. At this concentration, mechanical properties such as yield strength and modulus increased by as much as 13 and 69%, respectively, relative to the pure PP. Furthermore, the modulus of the composite samples prepared with PP-g-MA and CO₂ was some 15% higher than that of samples prepared by direct melt compounding (without the use of CO₂). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology and chain mobility of reactive blend nanocomposites of PP‐EVA/Clay

Polypropylene (PP)‐ethylene vinyl acetate (EVA)/clay nanocomposites were prepared via reactive blending using dicumyl peroxide (DCP) as an initiator with the goal of enhancing the interaction between both phases and modified nanoclay. The effect of the reactive blending and clay incorporation strategies (direct and masterbatch) on the blend and nanostructure morphology, and chain mobility of nanocomposites were studied. The chemical analysis showed the chemical bonding of PP‐EVA, which helped to enhance the interaction in the nanocomposites. The nanocomposites obtained from the direct clay strategy presented a co‐continuous morphology of bordering intercalated and agglomerated nanoclay sheets, while the nanocomposites obtained from the masterbatch strategy showed that blend morphology change from droplet to co‐continuous with the increase of EVA concentration, with intercalated/exfoliated nanoclay sheets located in the EVA domains and at the interface. The dynamic mechanical and creep‐recovery results showed different behavior for the both strategies in terms of chain mobility and relaxation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40897.     

A processing-induced clay dispersion and its effect on the structure and properties of polyamide 6

The nanostructures and morphologies of polyamide 6 (PA6)/organoclay nanocomposites prepared by melt compounding have been studied by using X-ray diffraction (XRD) and transmission electron microscopy (TEM). A combination of XRD and TEM indicates that an exfoliated clay morphology dominates at low clay loadings (≤5 wt%) and a mixture of intercalated and exfoliated structures exists at high clay concentrations. It is worth noting, however, that optical microscopy (OM) even shows the presence of large clay agglomerates in samples with higher clay contents. OM images further present an overview of an uneven clay distribution due to the effect of injection molding. The crystalline structure of PA6 is greatly affected by this unevenness in the processing-induced clay dispersion, as evidenced by differential scanning calorimetry (DSC). The thermal dynamic and mechanical properties of PA6 and the nanocomposites have been investigated as a function of clay concentration. The tensile tests show that the degree of dispersion of the nanoclay within the polymer matrix plays a vital role in property improvement. Copyright © 2004 Society of Chemical Industry     

Effect of clay modification on the morphology and the mechanical/physical properties of ABS/PMMA blends

The effect of three types of organoclays on the morphology and mechanical properties of lower critical solution temperature‐type poly(acrylonitrile‐butadiene‐styrene)/poly(methyl methacrylate) (ABS/PMMA) blends was investigated. Polymers were melt‐compounded with 2 and 4 wt % of clays using a twin‐screw extruder. X‐ray scattering and transmission electron microscopy revealed that the intercalation of the nanoclay in the hybrid nanocomposite was more affected by the polarity of the organoclay. Although the morphology of the blends varied by PMMA content, scanning electron microscopy showed smaller PMMA domains for the hybrid systems containing clay particles. Although good dispersion of the nanoclay through the ABS matrix and at the blend interface led to enhancement of tensile strength, the increment of the stiffness was more noticeable for nanocomposites including less polar organoclay. Well‐dispersed clay platelets increased the glass transition temperature. In addition, nanoscratching analysis illustrated an improvement in scratch resistance of ABS because of the presence of PMMA and organoclay. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of clay‐dispersed poly(styrene‐co‐methyl methacrylate) nanocomposite via miniemulsion atom transfer radical polymerization: A reverse approach

Poly(styrene‐co‐methyl methacrylate) nanocomposites were synthesized using reverse atom transfer radical polymerization (RATRP) in miniemulsion. Cetyltrimethylammonium bromide (CTAB) as a cationic surfactant applicable at higher temperatures was used for miniemulsion stabilization. Successful RATRP was carried out by using 4,4′‐dinonyl‐2,2′‐bipyridine (dNbPy) as ligand. Monodispersed droplets and particles with sizes in the range of 200 nm were revealed by dynamic light scattering (DLS). Conversion and molecular weight study was carried out using gravimetry and size exclusion chromatography (SEC) respectively. By adding clay content, a decrease in the conversion and molecular weight and an increase in the PDI value of the nanocomposites are observed. Thermal stability of the nanocomposites in comparison with the neat copolymer is revealed by thermogravimetric analysis (TGA). Increased T_g values by adding clay content was also obtained using differential scanning calorimetry (DSC). Scanning electron microscopy (SEM) images of the nanoconposite with 1 wt % of nanoclay loading, display monodispersed spherical particles with sizes in the range of ～ 200 nm. SEM findings are more compiled with dynamic light scattering (DLS) results. Well‐dispersed exfoliated clay layers in the polymer matrix of the nanocomposite with 1 wt % nanoclay loading is confirmed by transmission electron microscopy (TEM) images and X‐ray diffraction (XRD) data. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012