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 Nanoclay on the Mechanical,Thermal, and Water Absorption Properties of an UP-toughened Epoxy Network

Unsaturated polyester (UP)-toughened epoxy nanocomposites were prepared, and their effective mechanical and thermal properties were studied. Two types of organo-modified montmorillonite (OMMT) clays were used to prepare the nanocomposites. X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis showed the formation of exfoliated silicate layers in the UP-toughened epoxy matrix. Mechanical tests revealed that nanocomposites (containing 1 wt% OMMT clay) showed an increase in tensile strength to 13.8%, flexural strength to 10%, and impact strength to 4% compared with an UP-toughened epoxy blend. The effect of different heating rates on the curing behavior of UP-toughened epoxy nanocomposites was investigated using non-isothermal differential scanning calorimetry. The data were interpreted using the Kissinger and Flynn–Wall–Ozawa models to find the curing reaction parameter. The water uptake behavior for nanocomposites increased with the addition of OMMTs. Scanning electron microscopy micrographs indicated morphological changes in the impact fractured samples of UP-toughened epoxy nanocomposites.     

Morphology,mechanical properties,and thermal stability of rigid PVC/clay nanocomposites

PVC/Poly(ε‐caprolactone) (PCL)/organophilic‐montmorillonite (OMMT) and PVC/Polylactide (PLA)/OMMT nanocomposites were prepared by a two‐step process. PCL/OMMT and PLA/OMMT master batches were prepared by melt blending using a two‐roller mill first, and then they were blended with PVC via extrusion. PVC/OMMT nanocomposites were also prepared using a two‐roller mill. Morphology, mechanical properties, and thermal stability were investigated. The formation of exfoliated or intercalated nanocomposites was confirmed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Only the PVC/PCL/OMMT nanocomposite showed both higher tensile strength and stiffness than unfilled PVC. Atomic force microscopy (AFM) indicated dependency of this behavior not only on the clay dispersion, but also on the adhesion between the OMMT and the polymer matrix. Furthermore, scanning electron microscopy (SEM) showed that the large plastic deformation of the PVC/PCL matrix also contributed to the strength increase of the PVC nanocomposites. The effect of PCL/OMMT on the improvement of the thermal stability of PVC was remarkable while the effect of PLA/OMMT was moderate. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers.     

Comprehensive high‐performance epoxy nanocomposites co‐reinforced by organo‐montmorillonite and nano‐SiO2

Comprehensive high‐performance epoxy nanocomposites were successfully prepared by co‐incorporating organo‐montmorillonite (o‐MMT) and nano‐SiO₂ into epoxy matrix. Because of the strong interaction between nanoscale particles, the MMT layers were highly exfoliated, and the exfoliated nanoscale MMT monoplatelets took an interlacing arrangement with the nano‐SiO₂ particles in the epoxy matrix, as evidenced by X‐ray diffraction measurement and transmission electron microscopy inspection. Mechanical tests and thermal analyses showed that the resulting epoxy/o‐MMT/nano‐SiO₂ nanocomposites improved substantially over pure epoxy and epoxy/o‐MMT nanocomposites in tensile modulus, tensile strength, flexural modulus, flexural strength, notch impact strength, glass transition temperature, and thermal decomposition temperature. This study suggests that co‐incorporating two properly selected nanoscale particles into polymer is one pathway to success in preparing comprehensive high‐performance polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Poly(methyl methacrylate)/montmorillonite nanocomposites prepared with a novel reactive phosphorus–nitrogen‐containing monomer of N‐(2‐(5,5‐dimethyl‐1,3,2‐dioxaphosphinyl‐2‐ylamino)ethyl)‐ acrylamide and its thermal and flame retardant properties

A novel reactive phosphorus–nitrogen‐containing monomer, N‐(2‐(5,5‐dimethyl‐1,3,2‐dioxaphosphinyl‐2‐ylamino)ethyl)‐acrylamide (DPEAA), was synthesize and characterized. Flame retardant poly(methyl methacrylate)/organic‐modified montmorillonite (PMMA‐DPEAA/OMMT) nanocomposites were prepared by in situ polymerization by incorporating methyl methacrylate, DPEAA, and OMMT. The results from X‐ray diffraction and transmission electron microscopy (TEM) showed that exfoliated PMMA‐DPEAA/OMMT nanocomposites were formed. Thermal stability and flammability properties were investigated by thermogravimetric analysis, cone calorimeter, and limiting oxygen index (LOI) tests. The synergistic effect of DPEAA and montmorillonite improved thermal stability and reduced significantly the flammability [including peak heat release rates (PHRR), total heat release, average mass loss rate, etc.]. The PHRR of PMMA‐DPEAA/OMMT was reduced by about 40% compared with pure PMMA. The LOI value of PMMA‐DPEAA/OMMT reached 27.3%. The morphology and composition of residues generated after cone calorimeter tests were investigated by scanning electronic microscopy (SEM), TEM, and energy dispersive X‐ray (EDX). The SEM and TEM images showed that a compact, dense, and uniform intumescent char was formed for PMMA‐DPEAA/OMMT nanocomposites after combustion. The results of EDX confirmed that the carbon content of the char for PMMA‐DPEAA/OMMT nanocomposites increased obviously by the synergistic effect of DPEAA and montmorillonite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Solid‐state graft polymerization of styrene in spherical polypropylene particles in the presence of montmorillonite

In this work, cetyltrimethyl ammonium bromide and methacryloyloxyethyhrimethyl ammonium chloride were used to prepare organophilic montmorillonite (O‐MMT). Then, polypropylene (PP)–clay nanocomposites were prepared by the in situ grafting polymerization of styrene (St)‐containing O‐MMT onto PP with tert‐butyl perbenzoate as an initiator in the solid state. Fourier transform infrared spectroscopy, gel permeation chromatography, transmission electron microscopy, and X‐ray diffraction were applied to study the structure of the layered silicate and modified PP. The surfaces of the composites and, thus, the distribution of the clay in the PP matrix were characterized by scanning electron microscopy. The rheology and mechanical properties were studied and are discussed. According to the characterization results, OMMT and St were already grafted onto the PP main chain. Also, the intercalated structure of montmorillonite could be stabilized, and a stable exfoliated structure could be attained. Namely, intercalated PP/OMMT nanocomposites were obtained. The rheological results clearly show that these PP/OMMT nanocomposites had long‐chain‐branched structures. The peroxide modification of PP had minor effects on the tensile and bending strengths of the modified PP; however, this modification resulted in a significant reduction in the impact strength. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of clay modification on the morphological,mechanical, and thermal properties of polyamide 6/polypropylene/montmorillonite nanocomposites

Polyamide 6/polypropylene (PA6/PP = 70/30 parts) blends containing 4 phr (parts per hundred resin) of organophilic montmorillonite (OMMT) were prepared by melt compounding. The sodium montmorillonite (Na‐MMT) was modified using three different types of alkyl ammonium salts, namely dodecylamine, 12‐aminolauric acid, and stearylamine. The effect of clay modification on the morphological and mechanical properties of PA6/PP nanocomposites was investigated using x‐ray diffraction (XRD), transmission electron microscopy (TEM), tensile, flexural, and impact tests. The thermal properties of PA6/PP nanocomposites were characterized using thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and heat distortion temperature (HDT). XRD and TEM results indicated the formation of exfoliated structure for the PA6/PP nanocomposites prepared using stearylamine modified montmorillonite. On the other hand, a mixture of intercalated and exfoliated structures was found for the PA6/PP nanocomposites prepared using 12‐aminolauric acid and dodecylamine modified montmorillonite. Incorporation of OMMT increased the stiffness but decreased the ductility and toughness of PA6/PP blend. The PA6/PP nanocomposite containing stearylamine modified montmorillonite showed the highest tensile, flexural, and thermal properties among all nanocomposites. This could be attributed to better exfoliated structure in the PA6/PP nanocomposite containing stearylamine modified montmorillonite. The storage modulus and HDT of PA6/PP blend were increased significantly with the incorporation of both Na‐MMT and OMMT. The highest value in both storage modulus and HDT was found in the PA6/PP nanocomposite containing stearylamine modified montmorillonite due to its better exfoliated structure. POLYM. COMPOS., 31:1156–1167, 2010. © 2009 Society of Plastics Engineers     

Epoxy-Modified Mesua ferrea L. Seed-Oil-Based Polyester/Clay Nanocomposites

The nanocomposites of epoxy-modified Mesua ferrea L. seed-oil-based polyester resin were designed with 0-5 wt% loadings of organophillic montmorrilonite (OMMT). X-ray diffraction, transmission electron microscopy, and scanning electron microscopy studies revealed very good dispersion of OMMT with exfoliated structure in the matrix. The effects of OMMT on the curing, thermal, mechanical, and rheological behaviors of the nanocomposites were also investigated. Two times’ improvement in tensile strength, 2 kg increment in scratch hardness, and 68°C enhancement in thermal degradation temperature were obtained for the nanocomposites with 5 wt% OMMT loading compared to pristine polyester.     

Ethylene vinyl acetate/ethylene propylene diene terpolymer‐blend‐layered double hydroxide nanocomposites

Ethylene vinyl acetate (EVA‐45)/ethylene propylene diene terpolymer (EPDM) blend‐layered double hydroxide (LDH) nanocomposites have been prepared by solution blending of 1:1 weight ratio of EVA and EPDM with varying amounts of organo LDH (DS‐LDH). X‐ray diffraction and transmission electron microscopy analysis suggest the formation of partially exfoliated EVA/EPDM/DS‐LDH nanocomposites. Measurement of mechanical properties of the nanocomposites (3 wt% DS‐LDH content) show that the improvement in tensile strength and elongation at break are 35 and 12% higher than neat EVA/EPDM blends. Dynamic mechanical thermal analysis also shows that the storage modulus of the nanocomposites at glass transition temperature is higher compared to the pure blend. Such improvements in mechanical properties have been correlated in terms of fracture behavior of the nanocomposites using scanning electron microscopy analysis. Thermal stability of the prepared nanocomposites is substantially higher compared to neat EVA/EPDM blend, confirming the formation of high‐performance polymer nanocomposites. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Microwave‐assisted preparation of polylactide/organomontmorillonite nanocomposites via in situ polymerization

Microwave technology was introduced to assist the synthesis of polylactide (PLA)/organomontmorillonite (OMMT) nanocomposites in bulk by the in situ ring‐opening polymerization of D,L ‐lactide. Factors that influenced the polymerizing effects, such as the microwave power, irradiation time, and dosages of the catalyst and OMMT, were studied in terms of tensile strength. The polymerization time was decreased dramatically to 10 min under 90 W of microwave irradiation, and the mechanical and thermal properties of the PLA/OMMT nanocomposites were significantly improved. The composite with the highest mechanical properties was obtained when the dosages of the OMMT and the catalyst were 1.0 and 0.6 wt % of the lactide, respectively. The initial decomposition temperature of the PLA/OMMT(1.0 wt % OMMT) nanocomposite was heightened 11.5°C compared with that of pure PLA. The results of scanning electron microscopy confirmed an improvement in the toughness with the addition of OMMT. The transmission electron microscopy and X‐ray diffraction results indicate that an exfoliated and intercalated nanocomposite was successfully prepared. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mesua ferrea L. seed oil based amido‐amine modified nanoclay/epoxy nanocomposites

Hydrophilic bentonite and organo‐montmorillonite (OMMT) have been modified by using a vegetable oil based amido‐amine compound. The modified nanoclays were characterized by using X‐ray diffraction (XRD) and FTIR techniques. Increase in the basal spacing after the modification was observed in both the cases. Further, Mesua ferrea L. seed oil based sulfonated epoxy resin nanocomposites have been prepared by using these modified nanoclays [3 (w/w) of clay in each case]. The XRD, TEM, SEM, FTIR, and rheological studies confirmed the formation of partially exfoliated nanocomposites. The study also confirmed that hydrophilic bentonite is not suitable nanofiller for the system, though modified bentonite slightly improves the performance characteristics of the pristine polymer. Modified OMMT based nanocomposite shows significant improvement in tensile strength (～ 1.7 times), scratch hardness (～ 2 times), gloss (14 units), and thermal stability (18°C) compared to the pristine system. This nanocomposite also exhibit better performance than OMMT based analogous nanocomposite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Free‐volume hole properties of two kinds thermoplastic nanocomposites based on polymer blends probed by positron annihilation lifetime spectroscopy

Two type of nanocomposites—an immiscible blend, high density polyethylene/polyamide 6 (HDPE/PA‐6) with organomodified clay, and a compatibilized blend, high density polyethylene grafted with acrylic acid/PA‐6 (PEAA/PA‐6) with organomodified clay—were prepared via melt compounding. X‐ray diffraction and transmission electron microscopy results revealed that the clay was intercalated and partially exfoliated. Positron annihilation lifetime spectroscopy has been utilized to investigate the free‐volume hole properties of two type of nanocomposites. The results show a negative deviation of free‐volume size in PEAA/PA‐6 blend, and a positive deviation in HDPE/PA‐6 blend, and I₃ has a greater negative deviation in compatibilized blend than in immiscible blend due to interaction between dissimilar chains. For nanocomposites based on polymer blends, in immiscible HDPE/PA‐6/organomodified clay system, the variation of free‐volume size with clay content is not obvious and the free‐volume concentration and fraction decreased. While in the case of compatibilized PEAA/PA‐6/organomodified clay nanocomposites, complicated variation of free‐volume properties due to interactions between two phases and organomodified clay was observed. And the interaction parameter β shows the interactions between polymers and organomodified clay. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2463–2469, 2006     

Natural rubber/poly(ethylene‐co‐vinyl acetate)‐blend‐based nanocomposites

Natural rubber (NR)/poly(ethylene‐co‐vinyl acetate) (EVA) blend–clay nanocomposites were prepared and characterized. The blend nanocomposites were prepared through the melt mixing of NR/EVA in a ratio of 40/60 with various amounts of organoclay with an internal mixer followed by compression molding. X‐ray diffraction patterns revealed that the nanocomposites formed were intercalated. The formation of the intercalated nanocomposites was also indicated by transmission electron microscopy. Scanning electron microscopy, used to study the fractured surface morphology, showed that the distribution of the organoclay in the polymer matrix was homogeneous. The tensile modulus of the nanocomposites increased with an increase in the organoclay content. However, an increase in the organoclay content up to 5 phr did not affect the tensile strength, but the organoclay reduced this property when it was increased further. This study also indicated that a low silicate content dispersed in the blend matrix was capable of increasing the storage modulus of the material. The addition of the organoclay also increased the decomposition temperature of the NR/EVA blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 353–362, 2006     

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     

The effect of organic modifier‐12‐aminolauric acid on morphology and thermal properties of polylactide nanocomposites

A novel organically modified montmorillonite (OMMT) based on a bifunctional organic modifier‐12‐aminolauric acid (ALA) was synthesized. Polylactide (PLA) nanocomposites with this new and traditional OMMT were prepared by solution casting method. The effects of the organic modifiers on structure, morphology and thermal properties of PLA nanocomposites have been investigated using Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The results indicate that ALA has distinct effects on the dispersion of MMT platelets into the PLA matrix, where partial exfoliated as well as intercalated structures have been obtained, when compared with ordinary modifier, cetyltrimethyl ammonium bromide (CTAB). TGA data verifies that PLA nanocomposites with ALA‐MMT organoclay display enhanced thermal stability. The optimal clay loading of ALA‐MMT occurs at 3%wt, leading to the best compromise between clay dispersion and thermal properties. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

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     

Preparation and characterization of anionically polymerized butadiene‐isoprene copolymer/clay nanocomposites

Butadiene‐isoprene copolymer/montmorillonite (BIR/MMT) nanocomposites were synthesized successfully via in situ anionic polymerization. The results of transmission electron microscopy and X‐ray diffractometer showed that the clay layers were exfoliated and high reaction temperature benefited the exfoliation of layers in BIR/MMT. The polymerization still exhibited “living” characteristics with the addition of organophilic montmorillonite (OMMT). However, the contents of 1,2‐polybutadiene and 3,4‐polyisoprene of the copolymer decreased with the addition of OMMT, because of its absorption effect on N,N,N′,N′‐tetramethylethanediamine as revealed by ¹H NMR. Moreover, it was observed that the glass‐transition temperature of the BIR/MMT nanocomposites also decreased when compared with the BIR copolymers. The thermal stability of the nanocomposites was improved, because of the barrier property of exfoliated clay layers. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 1167–1172, 2006     

Preparation and characterization of exfoliated organic montmorillonite/poly(3,4‐ethyldioxythiophene) nanocomposites

Montmorillonite, organically modified by octadecylammine salt, has been adopted to successfully fabricate the exfoliated organic montmorillonite/poly(3,4‐ethyldioxythiophene) (OMMT/PEDOT) nanocomposites by in situ polymerization in aqueous media. Hydrochloric acid, 1,5‐naphthalenedisulfonic acid, and sodium benzenesulphonate have been employed to activate the polymerization of 3,4‐ethyldioxythiophene by offering active sites on the layers of montmorillonite. The resulting exfoliated nanocomposites have been characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, thermogravimetric analysis, and electrical conductivity measurement and showed controllable conductivity in the range of 10^?7 to 10^?2 S/cm and improved thermal stability compared with pure PEDOT. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Mechanical,thermal, and morphological properties of injection molded poly(lactic acid)/SEBS‐g‐MAH/organo‐montmorillonite nanocomposites

Poly(lactic acid)/organo‐montmorillonite (PLA/OMMT) nanocomposites toughened with maleated styrene‐ethylene/butylene‐styrene (SEBS‐g‐MAH) were prepared by melt‐compounding using co‐rotating twin‐screw extruder followed by injection molding. The dispersibility and intercalation/exfoliation of OMMT in PLA was characterized using X‐ray diffraction and transmission electron microscopy (TEM). The mechanical properties of the PLA nanocomposites was investigated by tensile and Izod impact tests. Thermogravimetric analyzer and differential scanning calorimeter were used to study the thermal behaviors of the nanocomposite. The homogenous dispersion of the OMMT silicate layers and SEBS‐g‐MAH encapsulated OMMT layered silicate can be observed from TEM. Impact strength and elongation at break of the PLA nanocomposites was enhanced significantly by the addition of SEBS‐g‐MAH. Thermal stability of the PLA/OMMT nanocomposites was improved in the presence of SEBS‐g‐MAH. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Phase morphology evolution and compatibilization of immiscible polyamide 6/polystyrene blends using nano‐montmorillonite

Nanocomposites of organic nano‐montmorillonite (nano‐OMMT)‐filled immiscible polyamide 6 (PA6)/polystyrene (PS) blends were prepared by three different processing methods. Masterbatch M1 of OMMT/PA6 and masterbatch M2 of OMMT/PS were prepared as separate masterbatchs by melt mixing with PA6 or PS, and then either mixed together or each mixed individually with appropriate amounts of PS or PA6, respectively. The effects of nano‐OMMT content and processing method on the structure, phase morphology, and mechanical properties of the PA6/PS/OMMT nanocomposites were investigated by X‐ray diffraction, transmission electron microscopy, scanning electron microscopy, and mechanical properties tests. The results showed that the nano‐OMMT by M1 and M2 masterbatches dispersed primarily as exfoliated platelets in the PA6 matrix in the final composites regardless of the method of preparation. A drastic decrease of dispersed PS phase size and a very homogeneous size distribution were observed with the addition of nano‐OMMT. The PA6/PS/OMMT nanocomposites prepared from the M2 displayed the smallest dispersed PS phase size and best distribution of OMMT. The improvement of the mechanical properties of the PA6/PS/OMMT nanocomposites was attributed to the enhanced compatibilization of the immiscible PA6/PS blends by using nano‐OMMT. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers