Transparent copolyester/organoclay nanocomposites prepared by in situ intercalation polymerization: Synthesis,characterization, and properties

In this study, amorphous poly(ethylene terephthalate‐co‐1,3/1,4‐cyclohexylenedimethylene terephthalate) (PETG)/organoclay nanocomposites was synthesized by the in situ intercalation polymerization of terephthalic acid, ethylene glycol, 1,3/1,4‐cyclohexanedimethanol, and organoclay. The organoclay was obtained by modifying sodium montmorillonite (clay) with hexadecyl triphenylphosphonium bromide. The thermal, mechanical, optical, and gas barrier properties of these PETG nanocomposites with various organoclay contents (0–3 wt%) were discussed. The differential scanning calorimetry and X‐ray analyses revealed that all of the nanocomposites were amorphous. X‐ray diffraction and transmission electron micrographs showed that the organoclay was well dispersed in the polymer matrix, although some parts of the agglomerated layers remained on the scale of several hundreds of nanometers. The thermal stability and the mechanical property of the nanocomposites increased with organoclay content. The optical transmittances of nanocomposites that contained 0.5, 1, and 3 wt% of organoclay were 86.8%, 84.4%, and 77.4%, respectively. The oxygen transmission rate of the nanocomposite that contained 3 wt% of organoclay was about 50% of the PETG base polymer. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Synthesis and Characterization of Aromatic–Aliphatic Polyamide Nanocomposite Films Incorporating a Thermally Stable Organoclay

Nanocomposites were synthesized from reactive thermally stable montmorillonite and aromatic–aliphatic polyamide obtained from 4-aminophenyl sulfone and sebacoyl chloride. Carbonyl chloride terminal chain ends were generated using 1% extra sebacoyl chloride that could interact chemically with the organoclay. The distribution of clay in the nanocomposites was investigated by XRD, SEM, and TEM. Mechanical and thermal properties of these materials were monitored using tensile testing, TGA, and DSC. The results revealed delaminated and intercalated nanostructures leading to improved tensile strength and modulus up to 6 wt% addition of organoclay. The elongation at break and toughness of the nanocomposites decreased with increasing clay contents. The nanocomposites were thermally stable in the range 400–450 °C. The glass transition temperature increased relative to the neat polyamide due to the interfacial interactions between the two phases. Water uptake of the hybrids decreased upon the addition of organoclay depicting reduced permeability.     

Preparation of nanoclay‐dispersed polystyrene nanofibers via atom transfer radical polymerization and electrospinning

In this study, clay‐dispersed polystyrene (PS) nanocomposites were prepared with the in situ atom transfer radical polymerization method and were subsequently electrospun to form nanofibers 450–650 nm in diameter. The polymer chains extracted from the clay‐dispersed nanofibers exhibited a narrow range of molecular weight distribution. Thermogravimetric analysis (TGA) confirmed a higher thermal stability of the resulting nanocomposites compared to PS. The effect of the weight ratio of montmorillonite on the thermal properties of the nanocomposites was also studied by TGA. Differential scanning calorimetry revealed that the addition of the nanoclay increased the glass‐transition temperature. Moreover, degradation of the bromide chain‐end functionality took place at low temperatures. Scanning electron microscopy showed that the average diameter of the fibers was around 500 nm. The dispersion of clay layers was also evaluated by Al atoms in the PS matrix with the energy‐dispersive X‐ray detection technique. Transmission electron microscopy confirmed the exfoliation of the nanoclay within the matrix. However, the clay layers were oriented along the nanofiber axis. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterizations of poly(α‐naphthylamine)—Nanocomposites

Poly(α‐naphthylamine) (PNA)—natural clay nanocomposites were prepared by in situ polymerization method through oxidative initiation method. Effect of nanoclay on the rate of polymerization (R_p) of Naphthylamine (NA), thermal stability of PNA, and conductivity of PNA were tested. Effect of nanoclay on the morphology of PNA was also tested. The TGA results inferred that the % weight residue remain above 700°C was increased with the increase of amount of clay. XRD results confirmed the intercalation of PNA into the basal spacing of natural clay. TEM showed the presence of nanosized particle in the PNA‐natural clay nanocomposites. The conductivity value of polymer‐nanocomposite has increased with the increase of amount of natural clay. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Properties of high‐impact polystyrene/organoclay nanocomposites synthesized via in situ polymerization

High‐impact polystyrene (HIPS)/organically modified montmorillonite (organoclay) nanocomposites were synthesized via in situ polymerization. The effects of the organoclay on the morphology and material properties of HIPS/organoclay nanocomposites were investigated. X‐ray diffraction and transmission electron microscopy experiments revealed that intercalation of polymer chains into silicate layers was achieved, and the addition of nanoclay led to an increase in the size of the rubber domain in the composites. In comparison with neat HIPS, the HIPS/organoclay nanocomposites exhibited improved thermal stability as well as an increase in both the complex viscosity and storage modulus. The presence of intercalated organoclay drastically enhanced the gas‐barrier properties because of the increase in the tortuosity of the diffusive path for a penetrating gas molecule. Some mechanical properties, including the tensile modulus, were superior to those of conventional HIPS. Finally, the preparation of the nanocomposites with a minimal loss of impact properties was proposed through changes in the synthetic procedure. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Poly(amide‐imide)/organoclay nanocomposites using glycine as a natural amino acid: study on fire and thermal behavior

In the present study, new functional poly(amide‐imide)/organoclay nanocomposite films were successfully fabricated through the solution intercalation technique. New poly(amide‐imide) (PAI) containing glycine was synthesized via solution polycondensation of 1,1',3,3'‐tetraoxo(5,5'‐biisoindoline‐2,2'‐diyl)diacetic acid with 4,4′‐diaminodiphenylsulfone. The synthesized PAI was characterized by ¹H NMR, Fourier transform infrared (FTIR) spectroscopy, gel permeation chromatography, elemental analysis and inherent viscosity. Then, PAI/organoclay nanocomposite films containing 4 and 8 wt% of organoclay were prepared via solution intercalation through blending of organoclay 30B with the PAI solution. The nanostructures and properties of the PAI/organoclay were investigated using FTIR spectroscopy, XRD, transmission electron microscopy (TEM), TGA, DSC and microscale combustion calorimetry. XRD and TEM revealed the good dispersion of organoclay in the polymer matrix. TGA indicated that the addition of organoclay into the PAI matrix increases the thermal decomposition temperatures and char yields of the nanocomposites. Organoclay shows a positive effect in improving the flame retardancy of the PAI, reflecting the decrease in heat release rate, the total heat release and the heat release capacity of the PAI nanocomposites, while the thermal stability of the PAI nanocomposites only increased slightly compared with the neat polymer. © 2013 Society of Chemical Industry     

Polyamide- and polycarbonate-based nanocomposites prepared from thermally stable imidazolium organoclay

This paper explores the possible advantages of the more thermally stable imidazolium-based organoclay over a more conventional ammonium-based organoclay for facilitating exfoliation and minimizing polymer matrix degradation in melt blended polyamide 6 (PA-6) and polycarbonate (PC) nanocomposites. The thermal stability of the two organoclays was evaluated by TGA analyses. The extent of clay exfoliation was judged by analysis of the morphology and tensile modulus of these nanocomposites formed using a DSM Microcompounder, while the extent of color formation and molecular weight change were used to evaluate polymer matrix degradation. For PA-6 and PC nanocomposites, the use of the imidazolium organoclay only produced slight differences in both exfoliation and molecular weight change, although the imidazolium organoclay is remarkably more thermally stable than the ammonium organoclay.     

Encapsulation of organomodified montmorillonite with PMMA via in situ SR&;NI ATRP in miniemulsion

Encapsulation of organomodified montmorillonite within poly (methyl methacrylate) via in situ atom transfer radical polymerization with simultaneous reverse and normal initiation system (SR&NI ATRP) was successfully performed. Miniemulsion polymerization technique has been employed for its abundant advantages to encapsulate inorganic materials. Successful SR&NI ATRP was carried out using 4,4′-dinonyl-2,2′-bipyridine (dNbPy) as a hydrophobic ligand and cetyltrimethylammonium bromide (CTAB) as an effective cationic surfactant at high temperatures. Homogeneous distribution of droplets and particles with sizes in the range of around 170 nm was evaluated by dynamic light scattering (DLS) analysis. Final monomer conversion and molecular weight were determined by gravimetry and size exclusion chromatography (SEC) respectively. By increasing nanoclay content, conversion and molecular weight of nanocomposites decreased. Meanwhile, an increase in PDI values was also observed. X-ray diffraction (XRD) analysis results display organoclay layers disordered and delaminated in the polymer matrix. Thermal stability improvement of all the nanocomposites in comparison with the neat polymer was revealed by thermogravimetric analysis (TGA). Homogeneous distribution of spherical particles with sizes in the range of 170 nm was demonstrated by scanning electron microscopy (SEM) images. These results are complied with the DLS results. Transmission electron microscopy (TEM) image display a dispersion of partially exfoliated clay stacks in the matrix of PMNM 2.     

Synthesis and characterization of cationic gemini surfactant modified Na–bentonite and its applications for rubber nanocomposites

A cationic gemini surfactant (N‐isopropyl‐N , N‐dimethyldodecan 1‐aminium bromide) was synthesized by quaternization reaction. The synthesized surfactant was characterized by Fourier transform infrared (FTIR) and proton nuclear magnetic resonance (1H NMR) spectroscopy. Modified Na–bentonite (organoclay) was obtained by the intercalation of a gemini surfactant between the layers of sodium bentonite and characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), FTIR, thermogravimetry–differential thermal analysis (TGA–DTA) and differential scanning calorimetry (DSC) techniques. The results of XRD, TEM, FTIR, TGA, and corresponding DSC analysis indicate that gemini surfactant has been successfully intercalated into the clay layers. Rubber‐based nanocomposites have been prepared by incorporating various concentration of organically modified bentonite on to natural rubber/styrene–butadiene rubber (NR/SBR) rubber blend (75/25) using two roll mill. Effect of organoclay content on XRD, curing, mechanical, and scanning electron microscopy (SEM) properties of the nanocomposites are investigated. The morphological study showed the intercalation of nanoclay in NR/SBR blend chain. It was found that the organoclay decrease the optimum and scorch time of the curing reaction, increase maximum torque and the curing rate, which was attributed to the further intercalation during vulcanization process. Mechanical properties such as tensile strength, modulus and elongation at break have improved. POLYM. COMPOS., 38:396–403, 2017. © 2015 Society of Plastics Engineers     

Effect of organoclay loading level on mechanical properties,thermomechanical behavior,and heat build‐up of natural rubber/organoclay nanocomposites

Sodium‐montmorillonite nanoclay was modified with octadecylamine and compounded with natural rubber (NR) by dry mixing method. The effects of organoclay loading level on mechanical properties, thermal–mechanical behavior, and heat build‐up of NR/organoclay nanocomposites were investigated. Temperature scanning stress relaxation technique was used to characterize the thermal–mechanical behavior of the composites. The morphological properties were assessed by X‐ray diffraction and transmission electron microscopy. Loading levels of organoclay below 5 phr gave improved mechanical properties and heat build‐up, along with exfoliated clay structure in the nanocomposites. On the other hand, with loading levels above 7 phr the organoclay tended to agglomerate, and X‐ray diffraction revealed an intercalated structure. In these cases, the excess residual organoclay caused significantly increased stress relaxation and heat build‐up. Unmodified sodium‐montmorillonite as filler did not significantly affect the mechanical and heat build‐up properties of NR vulcanizates. POLYM. COMPOS., 37:1735–1743, 2016. © 2014 Society of Plastics Engineers     

Use of clay-anchored reactive modifier for the synthesis of poly (styrene-co-butyl acrylate)/clay nanocomposite via in situ AGET ATRP

Atom transfer radical polymerization using activators generated by electron transfer (AGET ATRP) was employed to synthesize well-defined poly (styrene-co-butyl acrylate)/clay nanocomposites. Dodecyltrimethylammonium bromide (DDTMAB) and Vinylbenzyltrimethylammonium chloride (VBTMAC) surfactants were used as clay modifier. The classical surfactant is used to expand the interlayer gallery of montmorillonite; however, double bond of reactive modifier participates in chain propagation process and forms clay-attached polymer chains. Subsequently synthesis of attached and free poly (styrene-co-butyl acrylate) chains and their composition was confirmed by Fourier-transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance spectroscopy (¹H NMR). Narrow distribution of nanocomposites molecular weight was confirmed by gel permeation chromatography (GPC). Partially exfoliated clay layers in the copolymer matrix were revealed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Thermal properties of the nanocomposites were evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Thermal decomposition of the nanocomposites was hindered in the presence of nanoclay. Dynamic mechanical thermal analysis (DMTA) results show that addition of nanoclay was also resulted in enhanced storage modulus (E′) in comparison with the neat copolymer. Lower glass transition temperature of nanocomposites was displayed by DSC.     

Synthesis of chain-extended organifier and properties of polyurethane/clay nanocomposites

Clay organifier with hydroxyl end-group and relatively high molecular weight was synthesized. The clay treated with the organifier was suspended in DMF and the dispersibility of organoclay in polyurethane matrix was enhanced by applying the sonication to the suspension of organoclay in DMF. The d-spacing of organoclay was found to be 2.29 nm compared to 1.18 nm of pristine montmorillonite. The polyurethane/clay nanocomposites formed an intercalated structure with some disorder and their d-spacings were about 2.6-2.7 nm. The barrier property, thermal stability and tensile properties significantly increased with increasing the dispersibility of organoclay. A 2.9-fold increase in tensile strength with 1 wt% of well-dispersed organoclay, a 41% decrease in oxygen permeability and a 1.7-fold increase in Young's modulus at 5 wt% of well-dispersed organoclay were achieved.     

Morphology,Thermal and Mechanical Properties of Biodegradable Poly(butylene succinate)/Poly(butylene adipate-co-terephthalate)/Clay Nanocomposites

Sodium montmorillonite (Na-MMT) was successfully modified by octadecylamine (ODA) through a cation exchange technique that showed by the increased of basal spacing of clay by XRD. The addition of the organoclay into the PBS/PBAT blends produced intercalated-type nanocomposites with improvements in tensile modulus and strength. The highest tensile strength of nanocomposite was observed at 1 wt% of organoclay incorporated. A TGA study showed that the thermal stability of the blend increased after the addition of the organoclay by 1 wt%. SEM micrographs of the fracture surfaces show that the morphology of the blend becomes smoother with presence of organoclay.     

Preparation and properties of natural rubber nanocomposites with solid‐state organomodified montmorillonite

A novel organomodified montmorillonite prepared by solid‐state method and its nanocomposites with natural rubber were studied. The nanocomposites were prepared by traditional rubber mixing and vulcanizing process. The properties of solid‐state organomodified montmorillonite were investigated by Fourier‐transform infrared spectroscopy (FITR) and thermogravimetric analysis (TGA). The dispersion of the layered silicate in rubber matrix was characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The results showed that the nanocomposites consisting of solid‐state organomodified montmorillonite and natural rubber are obtained. The solid‐state organomodified montmorillonite can not only accelerate the curing process, but also improve the mechanical and aging resistance properties of NR. The properties improvement caused by the fillers are attributed to partial intercalation of the organophilic clay by NR macromolecules. In addition, the dynamic mechanical analysis (DMA) results showed a decrease of tanδmax and increase of T_g when the organoclay is added to the rubber matrix, which is due to the confinement of the macromolecular segments into the organoclay nanolayers and the strong interaction between the filler and rubber matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Studies on thermal degradation and flame retardant behavior of the sisal fiber reinforced unsaturated polyester toughened epoxy nanocomposites

Unsaturated polyester (UP) toughened nanocomposites were prepared using both sisal fibers and montmorillonite clays. The effect of fibers and Cloisite 30B (C30B) nanoclays on the mechanical properties, thermal stability, flame retardant, and morphological behavior of the UP toughened epoxy (Epoxy/UP) were systematically studied. The chemical structures of Epoxy, UP, and Epoxy/UP systems were characterized using Proton Nuclear magnetic resonance (¹HNMR) and Fourier transform infrared (FTIR) spectra. The homogeneous dispersion of nanoclay within the polymer matrix was analyzed using transmission electron microscopy (TEM) and X‐ray diffraction (XRD) analysis. Incorporation of sisal fibers and C30B nanoclays within Epoxy/UP system resulted in an increase in the mechanical, thermal, and flame retardance properties. Thermogravimetric analysis (TGA) has been employed to evaluate the thermal degradation kinetic parameters of the composites using Kissinger and Flynn‐Wall‐Ozawa methods. Cone calorimeter, UL‐94, and LOI tests revealed a reduction in the burning rate of the matrix with the addition of fibers and nanoclays. The results showed that the treated fiber reinforced nanocomposites had higher thermal stability and better flame retardant properties than the treated fiber reinforced composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42068.     

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

Polyamide 6/polypropylene (PA6/PP=70/30 parts) blends containing 4 phr (parts per hundred resin) of organophilic modified montmorillonite (organoclay) were prepared using twin screw extruder followed by injection molding. Maleated polypropylene (MAH-g-PP) was used to compatibilize the blend system. The mechanical properties of PA6/PP nanocomposites were studied through tensile and flexural tests. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to assess the fracture surface morphology and the dispersion of the organoclay, respectively. X-ray diffraction (XRD) was used to characterize the formation of nanocomposites. The thermal properties were characterized by using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The dynamic mechanical properties of PA6/PP nanocomposites were analyzed by using dynamic mechanical thermal analyzer (DMTA). The strength and stiffness of PA6/PP nanocomposites were improved significantly in the presence of MAH-g-PP. This has been attributed to the synergistic effect of organoclay and MAH-g-PP. The MAH-g-PP compatibilized PA6/PP nanocomposites showed a homogeneous morphology supporting the compatibility improvement between PA6, PP and organoclay. TEM and XRD results revealed the formation of nanocomposites as the organoclay was intercalated and exfoliated. A possible chemical interaction between PA6, PP, organophilic modified montmorillonite and MAH-g-PP was proposed based on the experimental work.     

Microstructure and thermal properties of ethylene‐(vinyl acetate) copolymer/rectorite nanocomposites

Ethylene‐(vinyl acetate) copolymer (EVA)/rectorite nanocomposites were prepared by direct melt extrusion of EVA and organo‐rectorite. The microstructures and thermal properties of EVA nanocomposites were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), solid‐state nuclear magnetic spectroscopy, positron annihilation spectroscopy, thermal gravimetric analysis (TGA) and dynamic mechanical analysis techniques. XRD pattern and SEM images show that the intercalated structure is formed and rectorite is finely dispersed in EVA matrix. When organoclay content of the hybrid increases to 7.5 wt%, or pristine rectorite was used instead of organoclay, the crystallization behavior of EVA nanocomposite changes greatly and the ratio of the monoclinic to orthorhombic crystal increases significantly. The relative fractional free volume of the nanocomposite decreases with the increasing organo‐rectorite content, and the values of damping factor (tan δ) for all nanocomposites are lower than that of pure EVA. These facts illuminate that intercalated structure restricts the segment motion and mobilization of polymer chain. TGA results of EVA nanocomposites in air indicate that deacylation of EVA is accelerated because of the catalytic effect and the thermal degradation of the main chain is delayed owing to the barrier effect of silicate layers. Copyright © 2005 Society of Chemical Industry     

Comparative study of nanocomposites of polyolefin compatibilizers containing kaolinite and montmorillonite organoclays

This work studied the morphology and physical properties of nanocomposites of different ethylene copolymers and functionalized polyethylenes with two different types of organoclays, to assess the potential application of these fillers as reinforcing components in the design of polyethylene and other polyolefinic based nanocomposites with enhanced properties. A polyethylene‐grafted‐maleic anhydride (PEMA), a poly(ethylene‐co‐acrylic acid), a poly(ethylene‐co‐vinyl acetate), and an ionomer of poly(ethylene‐co‐methacrylic acid) containing a small fraction of polyamide 6 were used to prepare nanocomposites by melt compounding in internal mixer. Two different types of commercial clays were used to obtain nanocomposites with the same organoclay content (5 wt %), i.e., an organomodified montmorillonite and an organomodified kaolinite. The morphology was evaluated by wide angle X‐ray scattering, scanning electron microscopy, transmission electron microscopy, and optical microscopy. The thermal, mechanical and barrier properties were evaluated by differential scanning calorimetry and thermogravimetric analysis, tensile tests and oxygen transmission rate experiments, respectively. From the results, it was seen that PEMA and the ionomer are the best polymer matrices to disperse both organoclays under the conditions applied. Kaolinite and montmorillonite appeared to be dispersed in the nanorange, however, higher aspect ratio was observed for montmorillonite. The best improvements in thermal degradation and in mechanical reinforcement were shown for organomodified kaolinite nanocomposites. But the best improvements in thermo‐oxidative degradation and in oxygen barrier were seen for the nanocomposites with organomodified montmorillonite. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of polypropylene/solid‐state organomodified montmorillonite nanocomposites

A novel organomodified montmorillonite prepared by solid‐state method and its nanocomposites with polypropylene were studied. The interaction between modifying agent and montmorillonite was investigated by X‐ray diffraction (XRD) analysis, contact angle determination, and Fourier‐transform infrared spectroscopy. The results showed that the modifying agent behaves as an effective intercalating agent, enlarging the interlayer spacing of montmorillonite and making montmorillonite more hydrophobic. Polypropylene/solid‐state organomodified montmorillonite composites were prepared by melt‐mixing method. The dispersion of the silicates was investigated by XRD analysis and transmission electron microscopy. It was found that the nanocomposites are formed with solid‐state organomodified montmorillonite and polypropylene. The thermogravimetric analysis and differential scanning calorimetry results showed that the organoclay could enhance the thermal stability and decrease the relative crystallinity of polypropylene. Mechanical and rheological tests indicated that the organoclay improves the mechanical properties but has no obvious effect on rheological properties of polypropylene. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Lipid‐derived monomer and corresponding bio‐based nanocomposites

Fatty acid based monomer and corresponding hybrid polymer layered silicate nanocomposites have successfully been prepared by using in situ polymerizations. The hybrid materials were prepared by adding different ratios of nanoclay during free radical homopolymerization of 2‐(acryloyloxy)ethyl stearate (AOES) monomer and copolymerization of AOES with styrene. AOES monomer was synthesized by treating stearic acid with 2‐hydroxyethyl acrylate. The formation of AOES monomer, homopolymer and copolymer was confirmed by ¹H NMR spectroscopic analysis. Further analysis and characterization of the nanocomposites were carried out by XRD, transmission electron microscopy, AFM and attenuated total reflectance Fourier transform infrared spectroscopy. TGA of the polymer nanocomposites was also carried out to evaluate their thermal stability, while flammability tests were conducted to investigate the effect of layered silicate on flame retardancy. Nanofiller addition into the polymer matrix substantially improved the thermal properties and fire retardancy of the composites. © 2016 Society of Chemical Industry