The quantitative analysis of nano-clay dispersion in polymer nanocomposites by small angle X-ray scattering combined with electron microscopy

The main objective of this work is to propose a new approach for the quantitative analysis of the degree of dispersion of clay particles in the polymer matrix by small angle X-ray scattering (SAXS) combined with electron microscopy. Due to the low temperature processibility and good thermal stability, poly[(butylene succinate)-co-adipate] (PBSA) was chosen as a model polymer matrix for this study. The nanocomposites of PBSA with four different weight percentages of organically modified montmorillonite (OMMT) loadings were prepared via melt-blending method. The dispersed structure of the clay particles in the PBSA matrix was studied by SAXS. Results show that the clay particles are nicely dispersed in the case of all nanocomposites. However, with a systematic increase in clay loading, the dispersed clay structure of the nanocomposites changes from a highly delaminated to a flocculated and then to a stacked intercalated one. The probability of finding neighboring clay particles in the PBSA matrix as well as their thickness was calculated using the Generalized Indirect Fourier Transformation technique developed by Glatter and the modified Caillé theory proposed by Zhang. The morphology of the nanocomposites was also extensively studied by scanning transmission electron microscopy (STEM). In the case of all nanocomposites, SAXS results were in good agreement with STEM observations. Finally, a correlation between the predicted morphology of nanocomposites and their melt-state rheological properties is reported.     

Comparison of the clay minerals type on the properties of reinforced‐PVA nanocomposites

The aim of this study is to determine and compare the effect of the clay minerals in a clay–polymer nanocomposite concerning the mechanical and thermal properties. The effects of the different clay minerals on different polymers have been researched frequently, but the comparison of the clay minerals was never studied. Since clay minerals have different properties from each other such as surface area, crystal structure, and surface properties, the effect of the clay minerals on the nanocomposites would be different. In this study, montmorillonite (Mt), vermiculite (Verm), and sepiolite (Sep) clay minerals were used to prepare the nanocomposites for the comparison. A basic polymer, polyvinyl alcohol (PVA), was chosen as the polymer and the basic method, solution‐casting method, was used to prepare the nanocomposites. The structural and morphological characterizations were examined using X‐ray diffraction, transmission electron microscopy, and Fourier transform infrared techniques, and mechanical and thermal properties of the nanocomposites were determined by dynamical mechanical analysis, and differential scanning calorimetry methods. The results showed that the layered clay minerals Mt and Verm can be dispersed well in the polymer and improved the mechanical and thermal properties more than the fibrous Sep. The bigger surface area of Verm lead to higher values of the elastic modulus, while the more interaction between Mt and PVA lead to higher values of glass temperature. POLYM. COMPOS., 38:1698–1704, 2017. © 2015 Society of Plastics Engineers     

Effect of nanoclay type on dyeability of polyethylene terephthalate/clay nanocomposites

Polyethylene terephthalate (PET)-based nanocomposites containing three differently modified clays were prepared by melt compounding. The influence of type of clay on disperseability, thermal, and dyeing properties of the resultant nanocomposite was investigated by various analytic techniques, namely, X-ray diffraction, optical microscopy (OPM), differential scanning calorimetry, thermal gravimetric analysis, dynamical mechanical thermal analysis, contact angle measurement (CAM), reflectance spectroscopy, and light fastness. OPM images illustrated formation of large-sized spherulites in pure PET, while only small-sized crystals appeared in PET/clay nanocomposites. Decreased glass transition temperatures for all PET/clay nanocomposites indicate that the amorphous regions of such composites become mobile at lower temperatures than those in pure PET. CAMs on the resultant PET composites demonstrated that the wettability of such composites depends on hydrophilicity of the nanoclay particles. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of poly(butylene terephthalate) nanocomposites with various organoclays

Layered‐silicate‐based polymer–clay nanocomposite materials were prepared depending on the surface modification of montmorillonite (MMT). Nanocomposites consisting of poly(butylene terephthalate) (PBT) as a matrix and dispersed inorganic clay modified with cetyl pyridinium chloride (CPC), benzyl dimethyl N‐hexadecyl ammonium chloride, and hexadecyl trimethyl ammonium bromide by direct melt intercalation were studied. The organoclay loading was varied from 1 to 5 wt %. The organoclays were characterized with X‐ray diffraction (XRD) to compute the crystallographic spacing and with thermogravimetric analysis to study the thermal stability. Detailed investigations of the mechanical and thermal properties as well as a dispersion study by XRD of the PBT/clay nanocomposites were conducted. X‐ray scattering showed that the layers of organoclay were intercalated with intercalating agents. According to the results of a differential scanning calorimetry analysis, clay acted as a nucleating agent, affecting the crystallization. The PBT nanocomposites containing clay treated with CPC showed good mechanical properties because of intercalation into the polymer matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphology and properties of polymer/organoclay nanocomposites based on poly(ethylene terephthalate) and sulfopolyester blends

Poly(ethylene terephthalate) (PET) nanocomposite films containing two different organoclays, Cloisite 30B^® (C30B) and Nanomer I.28E^® (N28E), were prepared by melt blending. In order to increase the gallery spacing of the clay particles, a sulfopolyester (PET ionomer or PETi) was added to the nanocomposites via a master‐batch approach. The morphological, thermal and gas barrier characteristics of the nanocomposite films were studied using several characterization techniques such as scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, differential scanning calorimetry, dynamic mechanical analysis, rheometry and oxygen permeability. PET and PETi were found to form immiscible polymer blends and the nanoparticles were preferentially located in the PETi dispersed phase. A better dispersion of clay was obtained for nanocomposites containing N28E with PETi. On the contrary, for nanocomposites containing C30B and PETi, the number of tactoids increased and the clay distribution and dispersion became worse than for C30B alone. Overall, the best properties were obtained for the PET/C30B nanocomposite without PETi. Higher crystallinity was found for all nanocomposite films in comparison to that of neat PET. © 2012 Society of Chemical Industry     

Development and characterization of organoclay‐filled polyoxymethylene nanocomposites for high performance applications

The present work focuses on the preparation and characterization of organo‐modified fluorohectorite (OFH) clay filled polyoxymethylene (POM) nanocomposites by melt mixing method. The dispersion of OFH clay in the polymer matrix was confirmed by X‐ray diffraction (XRD), atomic force microscopy (AFM), and transmission electron microscopy (TEM) analysis. The surface properties of the nanocomposites, assessed by contact angle measurements, showed increase in hydrophobicity relative to the neat polymer. From the measured contact angle values, various surface parameters such as total surface free energy, interfacial free energy, work of adhesion, spreading coefficient, and Girifalco‐Good's interaction parameter were calculated. The thermal, mechanical, and dielectric properties of the nanocomposites were found to be improved by the incorporation of OFH clay into the POM matrix. The aging studies of the nanocomposites carried out by immersing the samples in various solvents showed an increase in the retention of mechanical property by the addition of OFH clay into the POM matrix. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Preparation of polystyrene–clay nanocomposites via dispersion polymerization using oligomeric styrene‐montmorillonite as stabilizer

This study describes the preparation of polystyrene–clay nanocomposite (PS‐nanocomposite) colloidal particles via free‐radical polymerization in dispersion. Montmorillonite clay (MMT) was pre‐modified using different concentrations of cationic styrene oligomeric (‘PS‐cationic’), and the subsequent modified PS‐MMT was used as stabilizer in the dispersion polymerization of styrene. The main objective of this study was to use the clay platelets as fillers to improve the thermal and mechanical properties of the final PS‐nanocomposites and as steric stabilizers in dispersion polymerization after modification with PS‐cationic. The correlation between the degree of clay modification and the morphology of the colloidal PS particles was investigated. The clay platelets were found to be encapsulated inside PS latex only when the clay surface was rendered highly hydrophobic, and stable polymer latex was obtained. The morphology of PS‐nanocomposite material (after film formation) was found to range from partially exfoliated to intercalated structure depending on the percentage of PS‐MMT loading. The impact of the modified clay loading on the monomer conversion, the polymer molecular weight, the thermal stability and the thermomechanical properties of the final PS‐nanocomposites was determined. Copyright © 2012 Society of Chemical Industry     

Phosphonium‐based layered silicate—Poly(ethylene terephthalate) nanocomposites: Stability,thermal and mechanical properties

PET‐clay nanocomposites were prepared using alkyl quaternary ammonium and phosphonium modified clays by melt‐mixing at 280°C using a micro twin screw extruder. The latter clays were prepared by synthesizing phosphonium surfactants using a simple one‐step method followed by a cation exchange reaction. The onset temperature of decomposition (T_onset) for phosphonium clays (>300°C) was found to be significantly higher than that of ammonium clays (around 240°C). The clay modified with a lower concentration (0.8 meq) of phosphonium surfactant showed a higher T_onset as compared to the clay modified with a higher concentration (1.5 meq) of surfactants. Nanocomposites prepared with octadecyltriphenyl phosphonium (C18P) modified clay showed a higher extent of polymer intercalation as compared with benzyltriphenylphosphonium (BTP) and dodecyltriphenylphosphonium (C12P) modified clays. The nanocomposites prepared with ammonium clays showed a significant decrease in the molecular weight of PET during processing due to thermal degradation of ammonium surfactants. This resulted in a substantial decrease in the mechanical properties. The molecular weight of PET was not considerably reduced during processing upon addition of phosphonium clay. The nanocomposites prepared using phosphonium clays showed an improvement in thermal properties as compared with ammonium clay‐based nanocomposites. T_onset increased significantly in the phosphonium clay‐based nanocomposites and was higher for nanocomposites which contained clay modified with lower amount of surfactant. The tensile strength decreased slightly; however, the modulus showed a significant improvement upon addition of phosphonium clays, as compared with PET. Elongation at break decreased sharply with clay. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The thermal,optical, flame retardant,and morphological consequence of embedding diacid‐capped ZnO into the recycled PET matrix

We extended our work to a fast and facile nanocomposites (NCs) manufacturing by incorporation of ZnO nanoparticles (NPs) on to a recycled poly(ethylene terephthalate) PET as a polymer matrix prepared by a dissolution/reprecipitation method. The surface of ZnO NPs was functionalized with synthesized optically active diacid containing alanine amino acid. Organo‐modified NPs which provided using solution blending technique through ultrasonic irradiation, were embedded into recycled PET. PET@ZnO/DA NCs containing different loadings of functionalized NPs (1, 3, 5 wt %) were investigated by thermal gravimetric analysis, field emission scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, Fourier transform infrared spectroscopy and UV–visible spectroscopy. Morphological studies revealed uniformly dispersed ZnO/DA NPs in the polymer matrix. The crystalline nature of PET slightly improved as a function of the NPs concentration. Char yield in TGA and LOI values indicated that the obtained NCs were capable of exhibiting flame retardant properties. The NCs were found to exhibit more absorbance in the UV and visible region in compare to the neat PET. The effect of ultrasonication in different solvent on the morphology of the recycled polymer particle was also studied. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43433.     

Synthesis and characterization of poly(ethylene terephthalate)/attapulgite nanocomposites

A kind of clay with fibrous morphology, attapulgite (AT), was used to prepare poly (ethylene terephthalate) (PET)/AT nanocomposites via in situ polymerization. Attapulgite was modified with Hexadecyltriphenylphosphonium bromide and silane coupling agent (3‐glycidoxypropltrimethoxysilane) to increase the dispersion of clay particles in polymer matrix and the interaction between clay particles and polymer matrix. FTIR and TGA test of the organic‐AT particles investigated the thermal stability and the loading quantity of organic reagents. XRD patterns and SEM micrographs showed that the organic modification was processed on the surface of rod‐like crystals and did not shift the crystal structure of silicate. For PET/AT nanocomposites, it was revealed in TEM that the fibrous clay can be well dispersed in polymer matrix with the rod‐like crystals in the range of nanometer scale. The diameter of rod‐like crystal is about 20 nm and the length is near to 500 nm. The addition of the clay particles can enhance the thermal stability and crystallization rate of PET. With the addition of AT in PET matrix, the flexural modulus of those composites was also increased markedly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1279–1286, 2007     

Effects of silane grafting on the morphology and thermal stability of poly(ethylene terephthalate)/clay nanocomposites

An alkylammonium intercalated montmorillonite (A‐MMT) was modified by edge grafting with 3‐glycidoxypropyltrimethoxysilane. In comparison with poly(ethylene terephthalate) (PET)/A‐MMT, the resultant grafted clay, S‐A‐MMT, exhibited improved miscibility with PET matrix and revealed better dispersion state in the melting compounded PET/S‐A‐MMT nanocomposites. As a result, the PET/S‐A‐MMT nanocomposite had slower degradation rate owing to the enhanced clay barrier effect. Meanwhile, the nanocomposite exhibited lower degradation onset temperature under nitrogen because of the clay catalysis effect, which can be explained by the decreasing degradation reaction energy calculated from Coats–Redfern method of degradation kinetics. In the other hand, nanocomposite with better clay dispersion state exhibited increasing thermal oxidative stability due to clay barrier effect of hindering oxygen to diffuse in, which accorded with the continuous and compact char surface formed during polymer degradation. The clay catalysis and barrier effect of silicate layers were presented directly in isothermal oxidative TGA experiment. Furthermore, the mechanical and crystallization properties of PET/clay nanocomposites were investigated as well. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Thermal aging and accelerated weathering of PVC/MMT nanocomposites: Structural and morphological studies

This work focuses on the influence of weathering factors—UV radiation, humidity, and temperature on the structure and morphology of poly(vinyl chloride)/montmorillonite (PVC/MMT) nanocomposites obtained by melt blending. It has been observed that organically modified MMT (OMMT) deteriorates the weathering resistance, the thermal behavior, as well as the long‐term stability of PVC. Decomposition of the organic modifier of MMT causes substantial color changes in the PVC nanocomposites as it facilitates the dehydrochlorination process of the polymer. However, the nonmodified MMT provides some stabilization during PVC weathering. The nanocomposites after annealing are characterized by higher glass transition temperature. The increase in heat capacity step (Δc_p) during glass transition suggests that in the PVC composites with nonmodified MMT stronger molecular interactions between the polymer and clay platelets occur than in PVC/OMMT nanocomposites. The scanning electron microscopy images on the surface and the cross section show that thermal aging and weathering proceed by different mechanisms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42090.     

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.     

Thermo‐oxidative stabilization of poly(lactic acid)‐based nanocomposites through the incorporation of clay with in‐built antioxidant activity

In this work, an innovative approach to overcome the issue of the poor thermo‐oxidative stability of polymer/clay nanocomposites is proposed. Specifically, biodegradable poly(lactic acid) (PLA)‐based nanocomposites, containing organo‐modified clay with in‐built antioxidant activity, were prepared. Through a two‐step chemical protocol, a hindered phenol antioxidant was chemically linked to the ammonium quaternary salt which was then intercalated between the clay platelets [(AO)OM‐Mt]. The nanocomposites were characterized and their thermo‐oxidative stability during melt processing and under long‐term thermal test conditions was investigated. PLA nanocomposites containing the (AO)OM‐Mt showed higher oxidative stability, along with better clay dispersion, compared to PLA‐nanocomposites containing commercial clay and a free hindered phenol antioxidant. Obtained results can be explained considering that (AO)OM‐Mt may act locally, at the interface, between the silicate layers and the polymer macromolecules, thus contributing to the observed improved stability of the polymer both during processing and under long‐term thermal‐oxidative conditions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44974.     

Synthesis and characterization of polyethylene‐octene elastomer/clay/biodegradable starch nanocomposites

The aim of this work is the production of new nanocomposites from metallocene polyethylene‐octene elastomer (POE), montmorillonite and biodegradable starch by means of a melt blending method. Characterizations of clay, modified clay, POE, POE‐g‐AA, and the hybrids produced from polymer, clay, and/or starch were performed by X‐ray diffraction (XRD) spectroscopy, Fourier transform infrared (FTIR) spectrophotometer, differential scanning calorimetry (DSC), thermogravimetry analyzer (TGA), scanning electron microscope (SEM), and Instron mechanical tester. As to the results, organophilic clay can be well dispersed into acrylic acid grafted polyethylene‐octene elastomer (POE‐g‐AA) in nanoscale sizes since cetyl pyridium chloride is partially compatible with POE‐g‐AA and allows POE‐g‐AA chains to intercalate into clay layers. Based on consideration of thermal and mechanical properties, it is also found that 12 wt % of clay content is optimal for preparation of POE‐g‐AA/clay nanocomposites. The new partly biodegradable POE‐g‐AA/clay/starch hybrid could obviously improve the elongation and the tensile strength at break of the POE‐g‐AA/starch hybrid since the former can give the smaller starch phase size and nanoscale dispersion of silicate layers in the polymer matrix. The nanocomposites produced from our laboratory can provide a stable tensile strength at break when the starch content is up to 40 wt %. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 397–404, 2005     

Influence of modified carbon nanotube on physical properties and crystallization behavior of poly(ethylene terephthalate) nanocomposite

Poly(ethylene terephthalate) (PET) nanocomposites reinforced with a very small quantity of modified carbon nanotube (CNT) were prepared by melt compounding using a twin‐screw extruder. The introduction of carboxylic acid groups on the surfaces of the nanotube leads to the enhanced interactions between the nanotube and the polymer matrix through hydrogen bonding formation. The thermal stability, mechanical, and rheological properties of the PET nanocomposites are strongly dependent on the interfacial interactions between the PET and the modified CNT as well as the dispersion of the modified CNT in the PET. The introduction of the nanotube can significantly influence the non‐isothermal crystallization behavior of the PET nanocomposites. This study demonstrates that a very small quantity of the modified CNT can substantially improve the thermal stability and mechanical properties of the PET nanocomposites, depending on the dispersion of the modified CNT and the interfacial interactions between the polymer matrix and the modified CNT. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Poly(ethylene terephthalate) nanocomposites by in situ interlayer polymerization: the thermo-mechanical properties and morphology of the hybrid fibers

Nanocomposites of poly(ethylene terephthalate) (PET) with C₁₂PPh-MMT as an organoclay were synthesized by using the in situ interlayer polymerization approach. The PET nanocomposites were melt-spun at different organoclay contents and different draw ratios to produce monofilaments. The thermo-mechanical properties and the morphologies of the PET nanocomposites were examined by using a differential scanning calorimeter, a thermogravimetric analyzer, a wide angle X-ray diffactometer, scanning and transmission electron microscopes, and a universal tensile machine. Some of the clay particles were well dispersed in the PET matrix, and some of them were agglomerated at a size level of greater than approximately 10 nm. The thermal stability and the tensile mechanical properties of the PET hybrid fibers increased with increasing clay content at a DR=1. However, the values of the ultimate tensile strength and the initial modulus of the hybrid fibers decreased markedly with increasing DR from 1 to 16.     

Characteristics of polystyrene/polyethylene/clay nanocomposites prepared by ultrasound‐assisted mixing process

In this study, polymer‐clay nanocomposites of various concentrations were prepared by ultrasonically assisted polymerization and melt‐mixing processes. A sonication process using power ultrasonic waves was employed to enhance nano‐scale dispersion during melt‐mixing of polymer blends and organically modified clay. We expected enhanced breakup of layered silicate bundles and further reduction in the size of the dispersed phase, with better homogeneity compared to the different immiscible blend pairs. X‐ray diffraction (XRD) and Transmission Electron Microscopy (TEM) were used to characterize the structures of the nanocomposites. The rheological behaviors of the obtained nanocomposites were measured with parallel plate rheometry. It was found that the ultrasound‐assisted process successfully generated exfoliated nanocomposites and promoted in‐situ compatibilization of the matrix comprising an immiscible pair of polymers in a blend. The resulting nanocomposite exhibited superior thermal stability and elastic modulus compared to the base polymer. Polym. Eng. Sci. 44:1198–1204, 2004. © 2004 Society of Plastics Engineers.     

Molecular interactions in intercalated organically modified clay and clay-polycaprolactam nanocomposites: Experiments and modeling

In this work we have evaluated molecular interactions in organically modified clay and polymer clay nanocomposite using a combination of experimental (photoacoustic FTIR, XRD) and computational (molecular dynamics (MD)) techniques. The FTIR data reveals hydrogen bond and ionic bond interaction between functional end groups of organic modifier and surface oxygen of interlayer clay sheet lying in the organically modified clay; and, the hydrogen bond formation between intercalated polymer and organic modifier and surface oxygen of clay sheet lying in the interlayer clay gallery in the polymer clay nanocomposite. In this work we report the nature of interactions between clay and polymer, clay and organic modifier in polymer-clay nanocomposites through experiments and molecular dynamics simulations.