Poly(ethylene oxide)/Laponite nanocomposites via melt-compounding: effect of clay modification and matrix molar mass

The present study focuses on the preparation of poly(ethylene oxide) (PEO) nanocomposites based on the synthetic Laponite clay. The clay was added both in its pure form as well as organically modified with low molar mass poly(ethylene glycol) (PEG) components in order to enhance the compatibility between Laponite and PEO. Several PEG's with different end groups were used. Almost all of them were found to intercalate in the clay intergallery spacing. An order of intercalation efficiency could be established. The modified clays displayed a good thermal stability at the nanocomposite processing temperature.The nanocomposites based on the pure Laponite clay as well as the modified clays display an intercalated structure with a modest intergallery spacing. The ion-dipole modification with the PEG's was ineffective in improving the compatibility between PEO and the Laponite silicate layers. Their respective mechanical properties were found to be increased a little, which can be attributed to the low effective aspect ratio of the silicate platelets present in the nanocomposites. This is caused by the low initial aspect ratio of Laponite (w/t=25) and the limited basal spacing increase. The addition of clay does not result in nucleation of the PEO crystallisation. In contrast, the crystallisation was inhibited, resulting in decreased heat of fusions, especially for the pure Laponite nanocomposites. The nanocomposites based on the modified Laponites display a good thermal stability.     

Melt-compounded salt-containing poly(ethylene oxide)/clay nanocomposites for polymer electrolyte membranes

The present study demonstrates the use of a simple and versatile melt-compounding route to prepare NaClO₄-containing poly(ethylene oxide) PEO/clay nanocomposites combining excellent mechanical properties with a competitive level of the ionic conductivity. The nanostructure and the resulting thermal, mechanical and conductive properties of the salt-containing PEO/clay nanocomposites were found to be highly sensitive to the clay type, i.e. aspect ratio of the clay, to the presence of an organic modifier in the intergallery spacing, and to the salt concentration. The highest increase of the shear storage modulus is obtained in the presence of single silicate layers, thus an exfoliated nanostructure, having a high aspect ratio. These structures are only obtained with an (polar) organically modified clay (Cloisite 30B), regardless of the presence of salt. The use of non-organically modified clays (Cloisite Na⁺ and Laponite) resulted in intercalated nanocomposites, with only a minor improvement in stiffness. A strong interaction between the Na⁺ from NaClO₄ and the Cloisite 30B silicate layers might be responsible for an increased PEO crystallinity and resultant additional increase in stiffness. A mechanism is proposed whereby the Na⁺ ions are drawn away from the PEO phase, to be complexed by the silicate layers, or even ion-exchanged with modifier cations. The addition of clay did not greatly affect the ion conductivity below the melt temperature of PEO. At higher temperatures, the nanocomposites displayed only slightly lower conductivities compared to the PEO/NaClO₄ complex, due to the presence of the clay platelets.     

Poly(ethylene oxide)/clay nanocomposites for solid polymer electrolyte applications

Poly(ethylene oxide) (PEO)/clay nanocomposites were prepared using a solution intercalation method. The organoclay (Nanocore I30E) used for nanocomposite synthesis was basically an octadecylammonium salt of montmorillonite clay prepared using an ion exchange method. Nanocomposite‐based solid polymer electrolytes were prepared using LiBF₄. The nanocomposite structures were characterised using wide‐angle X‐ray diffraction. The crystallisation behaviour and thermal properties were studied using differential scanning calorimetry. It was found that the crystallinity of the composite electrolytes decreases with increasing clay concentration up to 7.5 wt% and then increases with a further increase in clay concentration. The trend is different from that observed in PEO/clay nanocomposites without lithium salt where the crystallinity gradually decreases with increasing clay concentration. The solid polymer electrolyte samples were evaluated using an alternating current impedance analyser. A considerable increase in room temperature conductivity was observed at the optimum clay concentration. The conductivity decreases beyond the optimum clay concentration. Copyright © 2007 Society of Chemical Industry     

Rheological properties and crystal morphology of poly(ethylene oxide)/clay nanocomposites

Poly(ethylene oxide) (PEO)/organoclay nanocomposites were prepared by a solution intercalation method. The crystallization behavior of the nanocomposites was investigated by a cross‐polarized optical microscopy (CPOM) fitted with a hot‐stage facility. A decrease in size and regularity were observed as a result of incorporation of clay into the PEO matrix. The dynamic viscoelastic behavior of PEO/organoclay nanocomposites was assessed using a strain‐controlled parallel plate rheometer. The effects of clay concentration on the rheological properties of the nanocomposites were extensively studied. A significant increase in the viscosity and storage modulus of the nanocomposites was found with increasing clay content. The reinforcing effect of the organoclay was determined by using a dynamic mechanical analyzer (DMA) and compared with the theoretically calculated values. POLYM. COMPOS., © 2011 Society of Plastics Engineers.     

Interface structure of poly(ethylene terephthalate)/silica nanocomposites

The interface structure of the poly(ethylene terephthalate) (PET)/silica nanocomposites was characterized by Fourier transform infrared and solid-state nuclear magnetic resonance. Our study reveals that PET chains are grafted onto the surface of silica nanoparticles, and they form branched and lightly crosslinking structures during the polycondensation. Gel permeation chromatography measurements indicate that the grafted PET chains have a lower molecular weight and broader distribution. Furthermore, a model has been developed to elucidate the interaction of an entanglement network between silica and PET chains that lead to enhancements of G′, G″ and η* values of PET/2 wt% silica nanocomposites.     

Crystalline morphology and isothermal crystallization kinetics of poly(ethylene terephthalate)/clay nanocomposites

A poly(ethylene terephthalate) (PET)/montmorillonite clay nanocomposite was synthesized via in situ polymerization. Microscopic studies revealed that in an isothermal crystallization process, some crystallites in the nanocomposite initially were rod‐shaped and later exhibited three‐dimensional growth. The crystallites in the nanocomposite were irregularly shaped, rather than spherulitic, being interlocked together without clear boundaries, and they were much smaller than those of neat PET. With Avrami analysis, the isothermal crystallization kinetic parameters (the Avrami exponent and constant) were obtained. The rate constants for the nanocomposite demonstrated that clay could greatly increase the crystallization rate of PET. The results for the Avrami exponent were consistent with the observation of the rodlike crystallites in the PET/clay nanocomposite during the initial stage. Wide‐angle X‐ray scattering and Fourier transform infrared studies showed that, in comparison with neat PET, the crystal lattice parameters and crystallinity of the nanocomposite did not change significantly, whereas more defects may have been present in the crystalline regions of the nanocomposite because of the presence of the clay. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1381–1388, 2004     

Effect of clay on the morphology and properties of PMMA/poly(styrene-co-acrylonitrile)/clay nanocomposites prepared by melt mixing

Nanocomposites of blends of polymethylmethacrylate (PMMA) and poly(styrene-co-acrylonitrile) (SAN) with natural and organically modified montmorillonite clays (Cloisite^®25A and Cloisite^®15A) were prepared by melt mixing in a twin-screw extruder and the effect of clay on the phase separation morphology and physical properties of nanocomposites was investigated. Multi-pass samples were; those extruded once (one-pass), twice (two-pass) and three times (three-pass). Dispersion of clays in the matrix polymers was investigated using XRD and TEM. Interestingly enough, the clays were observed to be mainly located at the boundaries of PMMA and SAN for most of the nanocomposites. As the number of pass increased, the phase-separated domain size became larger for nanocomposites of PMMA/SAN containing PM, while nanocomposites with clay 25A or 15A showed less degree of growth in domain size in the TEM pictures. Viscosities of the continuous phase and separated domains, and the compatibilizing effect of clays were discussed as the probable explanations for these observations. These were supported by the rheological properties measurements, where the nanocomposites with clay 25A or 15A showed the higher complex viscosities than those of PM and also showed some shear thinning behavior. DSC and TGA analyses were also conducted.     

Preparation and properties of poly(ethylene terephthalate)/ATO nanocomposites

Antimony doped tin oxide (ATO) nanoparticles modified poly(ethylene terephthalate) (PET) composites used for manufacturing antistatic PET fiber were synthesized by in situ polymerization. The crystallization and multiple melting behavior of the nanocomposites were systemically investigated by means of Differential Scanning Calorimeter (DSC), Fourier Transform Infrared (FTIR), X‐ray Diffraction (XRD) techniques. The degree of crystallinity in nanocomposites increased with increasing ATO content. Smaller and more incomplete crystals are presented in the crystalline regions of the nanocomposites with increasing the content of ATO, which could be attributed to heterogeneous nucleation effects of ATO nanoparticles. Dynamic Mechanical Analysis (DMA) measurements showed that the storage moduli of the nanocomposites increased with increasing the content of ATO, due to formation of immobilized layer between polymer and filler. The interactions between ATO and PET molecules result in high tan δ for the PET/ATO nanocomposites. Percolation threshold of PET/ATO hybrid fibers prepared by the nanocomposites at room temperature was as low as 1.05 wt %, much lower than that of the composites filled with conventional conductive particles. Adding ATO nanoparticles obviously improves the conductivity of PET. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Rheology of poly(propylene)/clay nanocomposites

The linear and nonlinear shear rheological behaviors of poly(propylene) (PP)/clay (organophilic‐montmorillonite) nanocomposites (PP/org‐MMT) were investigated by an ARES rheometer. The materials were prepared by melt intercalation with maleic anhydride functionalized PP as a compatibilizer. The storage moduli (G′), loss moduli (G″), and dynamic viscosities of polymer/clay nanocomposites (PPCNs) increase monotonically with org‐MMT content. The presence of org‐MMT leads to pseudo‐solid‐like behaviors and slower relaxation behaviors of PPCN melts. For all samples, the dependence of G′ and G″ on ω shows nonterminal behaviors. At lower frequency, the steady shear viscosities of PPCNs increase with org‐MMT content. However, the PPCN melts show a greater shear thinning tendency than pure PP melt because of the preferential orientation of the MMT layers. Therefore, PPCNs have higher moduli but better processibility compared with pure PP.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2427–2434,2004     

Effect of preshearing on the structure and properties of poly(methyl methacrylate)/clay nanocomposite panels

The effect of preshearing resin mixtures prior to casting on the structure and properties of in situ polymerized poly(methyl methacrylate)/clay nanocomposite panels was investigated. The preshearing was performed with a mechanical stirrer and controlled by varying mixing time. The structure, thermomechanical, and optical properties of the panels prepared with different preshearing times were analyzed by XRD, TEM, DMA, and UV/visible spectrophotometer. The properties of the panels increased with preshearing time because of improved intercalation and exfoliation of the clay. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Crystal transformation and thermomechanical properties of poly(vinylidene fluoride)/clay nanocomposites

The crystal transformation and thermomechanical properties of melt‐intercalated poly(vinylidene fluoride) (PVDF)/clay nanocomposites are reported in this study. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were used to study the thermal properties of PVDF and its nanocomposites with various clay concentrations. The incorporation of clay in PVDF results in the formation of β‐form crystals of PVDF. DSC study of melting behavior suggested the presence of only α‐phase crystals in neat PVDF and both α‐ and β‐phase crystals in the nanocomposite. This conclusion was corroborated by findings from Fourier‐transform infrared (FTIR) spectroscopy and X‐ray diffraction (XRD). Dynamic mechanical analysis (DMA) indicated significant improvements in storage modulus over a temperature range of 20–150 °C. The coefficient of thermal expansion (CTE) decreases with increasing clay loading. Copyright © 2004 Society of Chemical Industry     

Non-toxic poly(ethylene terephthalate)/clay nanocomposites with enhanced barrier properties

Motivated by the technological need for poly(ethylene terephthalate) materials with improved barrier properties together with the requirement for sustainability this study focuses on an eco-friendly sulfonated polyester as clay compatibilizer to facilitate polymer mixing during melt compounding. We demonstrate that the nanocomposites based on sulfonated polyester are a reliable alternative to their imidazolium counterparts, exhibiting enhanced properties (water vapor and UV transmission), without sacrificing the excellent transparency, clarity and mechanical strength of the matrix.     

Preparation and characterization of poly(lactic acid)/poly(ethylene oxide) blend film: effects of poly(ethylene oxide) and poly(ethylene glycol) on the properties

Poly(lactic acid) (PLA) film plasticized with poly(ethylene oxide) (PEO) at various weight percentages (1–5 wt%) was prepared to improve the elongation, thus overcoming the inherent brittleness of the material. After optimization of the amount of PEO (4 wt%) through mechanical analysis, poly(ethylene glycol) (PEG), a well‐established plasticizer of PLA, was added (0.5–1.5 wt%) without hampering the transparency and tensile strength much, and again its amount was optimized (1 wt%). Neat PLA and PLA with the other components were solvent‐cast in the form of films using chloroform as a solvent. Improvement in elongation at break and reduction in tensile strength suggested a plasticizing effect of both PEO and PEG on PLA. Thermal and infrared data revealed that the addition of PEO induced β crystals in PLA. Scanning electron micrographs indicated a porous surface morphology of the blends. PEO alone in PLA exhibited the best optical clarity with higher percentage crystallinity, while PEG incorporation in PLA/PEO resulted in superior barrier properties. Also, the stability of the blends under a wide range of pH means prospective implementation of the films in packaging of food and non‐food‐grade products. © 2018 Society of Chemical Industry     

Mechanical properties and rheological behavior of poly(butylene terephthalate)/clay nanocomposites with different organoclays

Poly(butylene terephthalate)–clay nanocomposites with three different organically modified clays were prepared via melt blending in a twin‐screw extruder. Decyl triphenylphosphonium bromide, hexadecyl triphenylphosphonium bromide, and cetyl pyridinium chloride were used to modify the naturally occurring montmorillonite clay. The organically modified clays were characterized with X‐ray diffraction for the d₀₀₁‐spacing and with thermogravimetric analysis to determine the thermal stability. The prepared nanocomposites were injection‐molded and examined for the dispersion quality of the clay, the mechanical properties, and the rheological behavior. The tensile strength of the nanocomposites increased with a 1% addition of clay; however, more clay decreased the tensile strength. Nanocomposites with finely dispersed clay platelets and nanocomposites with poorly dispersed clay platelets showed very different rheological behaviors. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of clay on immiscible morphology of poly(butylene terephthalate)/polyethylene blend nanocomposites

Polymer blend nanocomposites containing poly(butylene terephthalate) (PBT), polyethylene (PE), and organoclay were prepared by direct melt compounding. Their immiscible morphologies weree investigated using electronmicroscopy, X‐ray diffraction, and parallel plate rheometry. The PE domain sizes were reduced when the polar PBT phase was continuous (PBT/PE = 60/40) because the clay tactoids effectively prevented the coalescence of the dispersed PE domains. However, when the PBT component presented domains dispersed in the rich PE matrix (PBT/PE = 40/60), the addition of clay (>2 wt %) changed the phase morphology into a novel cocontinuous one, which was further confirmed by rheological measurements. The existence of clay tactoids led to a sharp enhancement in the viscosity of the PBT phase, changing the viscosity ratio between the PBT and PE phases remarkably, which may have promoted the phase inversion. As a result, clay had significant effects on the morphology of the polymer blend. © 2006 Wiley Periodicals Inc. J Appl Polym Sci 102: 3628–3633, 2006     

Preparation and structure and mechanical properties of poly(styrene‐b‐butadiene)/clay nanocomposites

Star‐shaped and linear block thermoplastic poly(styrene‐b‐butadiene) copolymer (SBS)/organophilic montmorillonite clays (OMMT) were prepared by a solution approach. The intercalation spacing in the nanocomposites and the degree of dispersion of nanocomposites were investigated by X‐ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The mechanical properties, dynamic mechanical properties, and thermal stability of these nanocomposites were determined. Results showed that SBS chains were well intercalated into the clay galleries and an intercalated nanocomposite was obtained. The mechanical strength of nanocomposites with the star‐shaped SBS/OMMT were significantly increased. The addition of OMMT also gave an increase of the elongation, the dynamic storage modulus, the dynamic loss modulus, and the thermal stability of nanocomposites. The increase of the elongation of nanocomposites indicates that SBS has retained good elasticity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3430–3434, 2004     

Synthesis and characterization of exfoliated poly(styrene-co-methyl methacrylate)/clay nanocomposites via emulsion polymerization with AMPS

A method was described for synthesis of exfoliated poly(styrene-co-methyl methacrylate)/clay nanocomposites through an emulsion polymerization with reactive surfactant, 2-acrylamido-2-methyl-1-propane sulfonic (AMPS) which made the polymer end-tethered on pristine Na-MMT.AMPS widened the gap between clay layers and facilitates comonomers penetrate into clay. Silicate layers affect the composition of comonomers, for example A0.3M10S10T5 showed the elevated composition of MMA end tethered on silicate when compared to the feed ratio and polar methyl methacrylate (MMA) was considered to have the stronger interaction with clay layers than styrene.The exfoliated structure of extracted nanocomposite was confirmed by XRD and transmission electron microscopy. The onset of thermal decomposition for nanocomposites shifted to a higher temperature than that for neat copolymer. The dynamic moduli of nanocomposites increase with clay content. Dynamic storage modulus and complex viscosity increased as the clay content increased. In low frequency region all prepared nanocomposites exhibited apparent low-frequency plateaus in the linear storage modulus. Complex viscosity showed shear-thinning behavior as the clay content increases.     

New poly(phenylene oxide)/polystyrene blend nanocomposites with clay: Intercalation,thermal and mechanical properties

We present the first study and results on the preparation and characterization of montmorillonite clay filler based polymer blend nanocomposites of the miscible poly(phenylene oxide)/polystyrene blend. Intercalated nanocomposites, prepared by a melt‐processing method with 2–6 wt % commercially available organically modified sodium montmorillonite, have been characterized with wide‐angle X‐ray diffraction, transmission electron microscopy analysis, thermal analysis (thermogravimetric analysis and differential scanning calorimetry), and mechanical tensile tests. We show that nanocomposites can be successfully prepared in a batch mixer at temperatures much below the conditions conventionally used for this blend without organic degradation. Thermal stability is enhanced by nanoscale hybrid formation. The level of intercalation (change in the d‐spacing) does not change with the clay loading. Better dispersion of clay in the blend matrix has been observed at a low level of clay content. The nanocomposites show improved tensile modulus (by 31%) in comparison to the blend, whereas the tensile strength (stress at break) and elongation decrease in the presence of the filler with an increase in the clay loading. The Halpin–Tsai model is able to predict the modulus of the nanocomposites in very good agreement with the experimental data. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Suspension polymerization of poly(methyl methacrylate)/clay nanocomposites

Polymer/clay nanocomposites (PCNs) of poly(methyl methacrylate) and an organically modified clay, Cloisite 15a, were synthesized in situ with a suspension polymerization technique. The amount of clay present in the PCNs was varied to provide a better understanding of the effect of the clay on the properties of the polymer matrix. However, unexpectedly, we found that the concentration of clay had a dramatic impact on the molecular weight of the polymer matrix, and a relationship between the clay concentration and polymer molecular weight was determined. The PCNs were characterized with size exclusion chromatography (SEC), X‐ray diffraction, transmission electron microscopy, and oscillatory shear rheology. From oscillatory shear rheology, the full master curves for the PCNs were obtained by application of the time–temperature superposition principle. To enable the effect of the clay on the rheology to be quantified, the experimental data was compared to the time‐dependent diffusion model of des Cloizeaux for polydisperse polymer melts, which enabled the polydispersity to be incorporated through the use of the molecular weight distribution obtained via SEC. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009