Effect of tethering chemistry of cationic surfactants on clay exfoliation, electrospinning and diameter of PMMA/clay nanocomposite fibers

We examine the influence of tethering chemistry of cationic surfactants on exfoliation of montmorillonite (MMT) clay dispersed in methyl methacrylate (MMA) followed by in-situ polymerization to form poly(methyl methacrylate) (PMMA) nanocomposites, the effect of exfoliation and clay loading on the rheology of polymer/clay dispersions in dimethyl formamide, and the diameters of nanocomposite fibers formed from these dispersions by electrospinning. Incorporation of an additional reactive tethering group of methacryl functionality significantly improves the intercalation and exfoliation of clays in both in-situ polymerized PMMA nanocomposites and the corresponding electrospun fibers. The proper surfactant chemistry also increases the dispersion stability, extensional viscosity, extent of strain hardening and thus the electrospinnablity of the nanocomposite dispersions, especially at low nanocomposite concentrations. The degree of the enhancement in electrospinnability by clays with proper tethering chemistry is at least the same as or greater than that obtained with three times higher loading level of clay particles without proper tethering chemistry in the nanocomposites. These results suggest a new strategy to produce smaller diameter fibers from very dilute polymer solutions, which are otherwise not electrospinnable, by incorporating a small amount of well-exfoliated clays.     

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     

Effect of organic modifiers and silicate type on filler dispersion,thermal, and mechanical properties of ABS‐clay nanocomposites

Acrylonitrile–butadiene–styrene (ABS)–clay composite and intercalated nanocomposites were prepared by melt processing, using Na‐montmorillonite (MMT), several chemically different organically modified MMT (OMMT) and Na‐laponite clays. The polymer–clay hybrids were characterized by WAXD, TEM, DSC, TGA, tensile, and impact tests. Intercalated nanocomposites are formed with organoclays, a composite is obtained with unmodified MMT, and the nanocomposite based on synthetic laponite is almost exfoliated. An unintercalated nanocomposite is formed by one of the organically modified clays, with similar overall stack dispersion as compared to the intercalated nanocomposites. T_g of ABS is unaffected by incorporation of the silicate filler in its matrix upto 4 wt % loading for different aspect ratios and organic modifications. A significant improvement in the onset of thermal decomposition (40–44°C at 4 wt % organoclay) is seen. The Young's modulus shows improvement, the elongation‐at‐break shows reduction, and the tensile strength shows improvement. Notched and unnotched impact strength of the intercalated MMT nanocomposites is lower as compared to that of ABS matrix. However, laponite and overexchanged organomontmorillonite clay lead to improvement in ductility. For the MMT clays, the Young's modulus (E) correlates with the intercalation change in organoclay interlayer separation (Δd₀₀₁) as influenced by the chemistry of the modifier. Although ABS‐laponite composites are exfoliated, the intercalated OMMT‐based nanocomposites show greater improvement in modulus. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of organoclays on the thermal,mechanical, and oxygen barrier properties of poly(methylmethacrylate‐co‐acrylonitrile)/clay nanocomposites

The nanostructured hybrid materials of poly(methylmethacrylate‐co‐acrylonitrile) copolymer were synthesized with incorporation of two organically modified clays, Cloisite® 30B and 93A by in situ intercalative emulsifier‐free emulsion polymerization method. The synthesized products were characterized by Fourier transform infrared spectroscopy to get evidence of copolymerization and formation of copolymer‐clay nanocomposite. X‐ray diffraction study and transmission electron microscopy analysis revealed that the clays were successfully intercalated and exfoliated into the copolymer matrix. Thermal properties of the nanocomposites were studied as a function of clay content of different clay types by thermogravimetric analysis. The results showed significant effect of both the clays in enhancing thermal resistance of the materials. Mechanical properties of the composites were also found to be improved at optimum clay loading. Oxygen barrier property of these materials was measured and it was found that the oxygen permeability was reduced almost by half due to incorporation of clays at 3% loading. Further, it was observed that Cloisite® 93A was more effective for improvement in properties when compared with Cloisite® 30B in the hybrid materials. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

A flammability performance comparison between synthetic and natural clays in polystyrene nanocomposites

Polymer‐clay nanocomposites are a newer class of flame retardant materials of interest due to their balance of mechanical, thermal and flammability properties. Much more work has been done with natural clays than with synthetic clays for nanocomposite flammability applications. There are advantages and disadvantages to both natural and synthetic clay use in a nanocomposite, and some of these, both fundamental and practical, will be discussed in this paper. To compare natural and synthetic clays in regards to polymer flammability, two clays were used. The natural clay was a US mined and refined montmorillonite, while the synthetic clay was a fluorinated synthetic mica. These two clays were used as inorganic clays for control experiments in polystyrene, and then converted into an organoclay by ion exchange with an alkyl ammonium salt. The organoclays were used to synthesize polystyrene nanocomposites by melt compounding. Each of the formulations was analysed by X‐ray diffraction (XRD), thermogravimetric analysis (TGA) and transmission electron microscopy (TEM). Flammability performance was measured by cone calorimeter. The data from the experiments show that the synthetic clay does slightly better at reducing the heat release rate (HRR) than the natural clay. However, all the samples, including the inorganic clay polystyrene microcomposites, showed a decreased time to ignition, with the actual nanocomposites showing the most marked decrease. The reason for this is postulated to be related to the thermal instability of the organoclay (via the quaternary alkyl ammonium). An additional experiment using a more thermally stable organoclay showed a time to ignition identical to that of the base polymer. Finally, it was shown that while polymer‐clay nanocomposites (either synthetic or natural clay based) greatly reduce the HRR of a material, making it more fire safe, they do not provide ignition resistance by themselves, at least, at practical loadings. Specifically, the cone calorimeter HRR curve data appear to support that these nanocomposites continue to burn once ignited, rather than self‐extinguish. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis and characterization of epoxy based nanocomposites

Epoxy‐clay nanocomposites were synthesized to examine the effects of the content and type of different clays on the structure and mechanical properties of the nanocomposites. Diglycidyl ether of bisphenol‐A (epoxy) was reinforced by 0.5–11 wt % natural (Cloisite Na⁺) and organically modified (Cloisite 30B) types of montmorillonite. SEM results showed that as the clay content increased, larger agglomerates of clay were present. Nanocomposites with Cloisite 30B exhibited better dispersion and a lower degree of agglomeration than nanocomposites with Cloisite Na⁺. X‐ray results indicated that in nanocomposites with 3 wt % Cloisite 30B, d‐spacing expanded from 18.4 Å (the initial value of the pure clay) to 38.2 Å. The glass transition temperature increased from 73°C, in the unfilled epoxy resin, to 83.5°C in the nanocomposite with 9 wt % Cloisite 30B. The tensile strength exhibited a maximum at 1 wt % modified clay loading. Addition of 0.5 wt % organically modified clay improved the impact strength of the epoxy resin by 137%; in contrast, addition of 0.5 wt % unmodified clay improved the impact strength by 72%. Tensile modulus increased with increasing clay loading in both types of nanocomposites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1081–1086, 2005     

Enhanced electrical and electrochemical properties of PMMA-clay nanocomposite gel polymer electrolytes

In the present work, effect of organically modified montmorillonite (MMT) clays on PMMA-based electrolytes has been investigated. The nanocomposites have been prepared by solution intercalation technique with varying clay loading from 0 to 5 wt.%. The formation of partially exfoliated nanocomposites has been confirmed by XRD and TEM analyses. The obtained nanocomposites were soaked with 1 M LiClO₄ in 1:1 (v/v) solution of propylene carbonate (PC) and diethyl carbonate (DEC) to get the required gel electrolytes. Surface morphology and structural conformation of the nanocomposite electrolytes have been examined by SEM and FTIR analyses, respectively. It has been observed that the ionic conductivity of the nanocomposite gel polymer electrolytes increases with the increase in clay loading and attains a maximum value of 1.3 × 10⁻³ S/cm at room temperature as revealed by ac impedance spectroscopy. Improvement of electrochemical and interfacial stabilities has also been observed in the gel electrolytes containing MMT fillers.     

Synthesis of effective poly(4‐vinylpyridine) nanocomposites: in situ polymerization from edges/surfaces and interlayer galleries of clay

Poly(4‐vinylpyridine) (P4VP) nanocomposites have been prepared by using an in situ polymerization method in the presence of organically modified montmorillonite (MMT) clays with a quarternary salt of cocoamine containing a vinyl group, as well as trimethoxy vinyl silane. The nanocomposites were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The desired exfoliated nanocomposite structure was achieved when the MMT modification was conducted in the presence of both modifiers, whereas individual modifications all resulted in intercalated structures. This resultant exfoliated nanocomposite was found to have better thermal stability and dynamic mechanical performance when compared to the other nanocomposites, even with 2 % clay loading. Copyright © 2005 Society of Chemical Industry     

Enhancement of the thermal stability,mechanical properties and morphologies of recycled PVC/clay nanocomposites

Summary Recycled PVC/clay nanocomposites were prepared by melt mixing of recycled PVCs and modified clays. Characterization of the nanostructure of the nanocomposites was carried out using wide angle X-ray diffraction (WAXD) and transmission electron microscopy(TEM). In case of 10wt.%, the characteristic peak of modified clay was perfectly disappeared, because of aids of plasticizers as co-intercalator. Thermal stability was evaluated from the thermal decomposition behaviors and linear dimension changes by TGA and TMA system. Coefficients of thermal expansion of the nanocomposites were also observed from TMA analysis. Dynamic mechanical properties were evaluated using DMA system. The thermal and mechanical properties of the nanocomposites were improved simultaneously for varied clay loadings, 1,3,5,10wt.%, compared to recycled PVC. Especially, the storage modulus of the nanocomposites with 10wt.% clay loading was increased 11 times compared to that of recycled PVC.     

Crown ether‐modified clays and their polystyrene nanocomposites

Crown ether‐modified clays were obtained by the combination of sodium and potassium clays with crown ethers and cryptands. Polystyrene nanocomposites were prepared by bulk polymerization in the presence of these clays. The structures of nanocomposites were characterized by X‐ray diffraction and transmission electron microscopy. Their thermal stability and flame retardancy were measured by thermogravimetric analysis and cone calorimetry, respectively. Nanocomposites can be formed only from the potassium clays; apparently the sodium clays are not sufficiently organophilic to enable nanocomposite formation. The onset temperature of the degradation is higher for the nanocomposites compared to virgin polystyrene, and the peak heat release rate is decreased by 25% to 30%.     

Single-ion conducting polymer-silicate nanocomposite electrolytes for lithium battery applications

Solid-state polymer-silicate nanocomposite electrolytes based on an amorphous polymer poly[(oxyethylene)₈ methacrylate], POEM, and lithium montmorillonite clay were fabricated and characterized to investigate the feasibility of their use as ‘salt-free’ electrolytes in lithium polymer batteries. X-ray scattering and transmission electron microscopy studies indicate the formation of an intercalated morphology in the nanocomposites due to favorable interactions between the polymer matrix and the clay. The morphology of the nanocomposite is intricately linked to the amount of silicate in the system. At low clay contents, dynamic rheological testing verifies that silicate incorporation enhances the mechanical properties of POEM, while impedance spectroscopy shows an improvement in electrical properties. With clay content ≥15 wt.%, mechanical properties are further improved but the formation of an apparent superlattice structure correlates with a loss in the electrical properties of the nanocomposite. The use of suitably modified clays in nanocomposites with high clay contents eliminates this superstructure formation, yielding materials with enhanced performance.     

Effect of clay exfoliation and organic modification on morphological,dynamic mechanical,and thermal behavior of melt‐compounded polyamide‐6 nanocomposites

Polyamide‐6/clay nanocomposites were prepared employing melt bending or compounding technique followed by injection molding using different organically modified clays. X‐ray diffraction and transmission electron microscopy were used to determine the molecular dispersion of the modified clays within the matrix polymer. Mechanical tests revealed an increase in tensile and flexural properties of the matrix polymer with the increase in clay loading from 0 to 5%. C30B/polyamide‐6 nanocomposites exhibited optimum mechanical performance at 5% clay loading. Storage modulus of polyamide‐6 also increased in the nanocomposites, indicating an increase in the stiffness of the matrix polymer with the addition of nanoclays. Furthermore, water absorption studies confirmed comparatively lesser tendency of water uptake in these nanocomposites. HDT of the virgin matrix increased substantially with the addition of organically modified clays. DSC measurements revealed both γ and α transitions in the matrix polymer as well as in the nanocomposites. The crystallization temperature (T_c) exhibited an increase in case of C30B/polyamide‐6 nanocomposites. Thermal stability of virgin polyamide‐6 and the nanocomposites has been investigated employing thermogravimetric analysis. POLYM. COMPOS., 28:153–162, 2007. © 2007 Society of Plastics Engineers     

Effects of the nature and combinations of solvents in the intercalation of clay with block copolymers on the properties of polymer nanocomposites

Polystyrene (PS) nanocomposites were prepared by the free‐radical polymerization of styrene in the presence of organically modified montmorillonite (MMT) clays. MMT clay was modified with a low‐molecular‐weight and quarternized block copolymer of styrene and 4‐vinylpyridine [poly(styrene‐b‐4‐vinylpyridine) (SVP)] with 36.4 wt % PS and 63.6 wt % poly(4‐vinylpyridine) (P4VP). Special attention was paid to the modification, which was carried out in different compositions of a solvent mixture of tetrahydrofuran (THF) and water. The swelling behavior of the MMT clay was studied by an X‐ray diffraction technique. The diffraction peak shifted to lower 2θ angles for all of the modified clays, which indicated the intercalation of the quarternized SVP copolymer into the MMT layers in different degrees. Higher interlayer distances, which showed a high degree of block copolymer insertion, were obtained for solvent compositions with THF in water. The resultant nanocomposites were characterized by X‐ray diffraction, atomic force microscopy, scanning electron microscopy, thermogravimetric analysis, and dynamic mechanical analysis. The desired exfoliated nanocomposite structure was achieved when the MMT modification was conducted in 50 or 66 wt % THF, whereas the other modifications all resulted in intercalated structures. The resulting exfoliated nanocomposite was found to have better thermal stability and dynamic mechanical performance compared to the others, even with 2% clay loading. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Structure,permeability, and rheology of supercritical CO2 dispersed polystyrene-clay nanocomposites

Improvement in clay dispersion and clay-polymer interfacial interactions are keys to producing superior nanocomposites. A supercritical CO₂ (scCO₂) processing method was utilized to pre-disperse commercial organic clays, for further solvent mixing with polystyrene (PS) to form nanocomposites with significant dispersion and interfacial enhancement. The effect of scCO₂ processing on clay pre-dispersion, and clay dispersion and interfacial interaction in nanocomposites were investigated. SEM and WAXD of the clays indicated that after scCO₂ processing the clays lose their long region ordered layer structure appreciably, associated with reduction in particle size. WAXD and TEM of the PS/clay nanocomposites showed that the polymer penetrated into the pre-dispersed clay, leading to a disordered intercalated/exfoliated structure with improved interfacial interaction rather than a disordered intercalated structure as seen with as-received clays. Relationships between those structures, rheological and barrier properties were investigated. The scCO₂-processed nanocomposites showed a plateau in the low-frequency storage modules and increased complex viscosity, each associated with significant clay dispersion in the nanocomposite. With only 1.09% volume fraction of clay, significant reduction (∼49%) of oxygen permeation was achieved.     

Systematic study of interfacial interactions between clays and an ionomer

To study the interfacial interactions between an ionomer [poly(ethylene‐co‐acrylic acid) neutralized by zinc salts (PI)] and clays, PI–clay nanocomposites were prepared using a solution method. Two types of commercially available montmorillonite clays respectively K10 and KSF were used, and were modified with organic modifiers with chain lengths of 12–18 carbons. The interactions between the PI, clays, and modifiers were evaluated through study of the structure, morphology, and properties of the PI–clay nanocomposites. We found that the modifiers were successfully intercalated into the clay layers (Fourier transform infrared spectroscopy). The clay modified with a long‐chain agent showed an exfoliated nature in the nanocomposite. The thermal stability and storage modulus of PI were improved greatly by the addition of the clays, especially when the long‐chain modifier was used (thermogravimetric analysis and dynamic mechanical analysis). The differential scanning calorimetry results show that clay layers are inserted into the clusters because of solvent‐directed morphological evolution, so the transition of the ionic domains and the crystallinity of PI are changed. The interaction between PI, the modifier, and the silicate layer played an important role in the determination of the properties of the nanocomposites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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.     

High-Throughput Method for the Synthesis of High Performance Polystyrene Nanocomposites

A new approach toward the development and application of a high-throughput method for nanocomposites was proposed. Polystyrene clay nanocomposites were prepared, using different imidazolium modified montmorillonite clays as nanoadditives. The preparation was carried out utilizing the parallel synthesizer as a high-throughput technique. The effects of solvent, temperature, and type of compatibilizer on the final products were investigated. The final products were analyzed by means of thermogravimetric analysis (TGA), X-ray diffraction (XRD), and transmission electron microscopy (TEM). Polystyrene-dimethyl decylimidazolium-montmorillonite (PS/DMDIM-MMT) and polystyrene-dimethyl hexadecyl imidazolium-montmorillonite (PS/DMHDIM-MMT) nanocomposites were obtained, using chlorobenzene as a solvent at 150°C. The XRD and TEM data were employed to measure the degree of clay exfoliation in the fabricated samples. The results indicate that PS/DMDIM-MMT nanocomposite has an intercalated structure, whereas the PS/DMHDIM-MMT nanocomposite has an exfoliated structure.     

High performance Nylon12/clay nanocomposites for potential packaging applications

The barrier property enhancement of polymers is presently a matter of great concern for the manufacturing of food packaging and films with excellency in moisture and gas resistance. The objective of this work was to enhance the barrier performance of Nylon12/kaolin clay nanocomposites against water vapors and oxygen. Kaolin clays of different aspect ratios were utilized for nanocomposites manufacturing. Nanocomposites were prepared in twin screw extruder operating at 160–200°C, with an increment of 10°C, and at 110 rev/min. The loading of clay was varied from 1 to 5 wt%. Scanning electron microscopy and X-ray diffraction characterizations were used to investigate the morphological properties of nanocomposites. The transmission electron microscopy analysis was used to confirm the dispersion of clays in Nylon12 matrix. Enhancement in barrier performance of nanocomposite was noticed at 5 wt% clay loading. Oxygen barrier of nanocomposites was observed to be more prominent than water vapors owing to the presence of hydrogen bonding in Nylon12 structure which restricted oxygen passage. Experimental barrier values of nanocomposites were also fitted on barrier models namely Nielsen, Cussler model, and Gusev-Lutsi model.     

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 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