Synthesis and dielectric properties of polystyrene‐clay nanocomposite materials

Polystyrene‐clay nanocomposite (PsCN) materials were synthesized and their properties of crystallinity, thermal behavior, and dielectric characteristics were investigated. A polymerizable cationic surfactant, [2‐(dimethylamino)ethyl]triphenylphonium bromide, was used for the intercalation of montmorillonite (MMT). The organophilic MMT was prepared by Na⁺‐exchanged MMT and ammonium cations of a cationic surfactant in an aqueous medium. Organophilic styrene monomers were intercalated into the interlayer regions of organophilic clay hosts followed by a free‐radical polymerization. Exfoliation to 2 wt % MMT in the polystyrene (PS) matrix was achieved as revealed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Thermal properties by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were also studied. The dielectric properties of PsCNs in the form of film with clay loading from 1.0 to 5.0 wt % were measured under frequencies of 100 Hz–1 MHz at 25–70°C. A decreased dielectric constant and low dielectric loss were observed for PsCN materials. The dielectric response at low frequency that originated from dipole orientation was suppressed due to the intercalation of clay materials. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1368–1373, 2004     

Synthesis and properties of polystyrene–clay nanocomposites via in situ intercalative polymerization

Organophilic montmorillonite (MMT) was prepared by ion exchange between Na⁺ ions in the clay and twin benzyldimethyloctadecylammonium bromine cations in an aqueous medium. The organophilic MMT particles were easily dispersed and swollen in styrene monomer. Polystyrene–MMT nanocomposites were prepared by the free‐radical polymerization of styrene containing dispersed clay. The intercalation spacing in the nanocomposites and the degree of dispersion of these composites were investigated with X‐ray diffraction and transmission electron microscopy, respectively. The nanocomposites had higher weight‐average molecular weights, lower glass‐transition temperatures, and better thermal stability (the decomposition temperature was improved by ca. 70°C) than the virgin polystyrene. The rheological behavior of the polystyrene–MMT nanocomposites was also studied. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 201–207, 2005     

SEM study of a polystyrene/clay nanocomposite

We carried out a scanning electron microscopy study to investigate the morphology of a polystyrene (PS)/montmorillonite nanocomposite. Monodispersed spherical particles, about 200 nm in diameter, were observed when PS/montmorillonite powder was dispersed in water, whereas planar silicate sheets were found for cetyltrimethylammonium bromide‐exchange montmorillonite. The fracture surface of a PS/clay nanocomposite pellet sample showed a lot of fibrils rather than the smooth surface of a pure PS pellet. After the PS/clay nanocomposite pellet was chemically etched, flaky montmorillonite particles were homogeneously dispersed in the PS matrix. A film sample, prepared by the pressing of the PS/clay nanocomposite melt, revealed that the montmorillonite primary particles oriented parallel to the surface, and the corresponding X‐ray diffraction distribution map of silicon atoms confirmed that the dispersed particles were montmorillonite primary particles. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 66–69, 2002     

Significant decreased dielectric constant and loss of polystyrene–clay nanocomposite materials by using long‐chain intercalation agent

Polystyrene–clay nanocomposite (PsCN) materials have been prepared by a free radical polymerization process. Montmorillonite (MMT), modified by two different organics, was investigated: one contains a short chain and three benzyl groups on the ammonium ion (DAETPB), while the other contains a long chain (HTAC). The organic modification determines the extent of exfoliation or intercalation of the materials. Exfoliation is more likely to occur using HTAC, as then the gallery of clay has been opened more due to the long chain structure. Exfoliation of MMT in polystyrene (PS) matrix was revealed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were employed to confirm the increased thermal stability of these PsCN materials. Dielectric properties of polystyrene‐clay nanocomposites, in the form of film with clay loading from 1.0 to 5.0 wt %, were measured under frequencies of 100 Hz～1 MHz at 25～70°C. Decreased dielectric constant and low dielectric loss were observed for PsCN materials. Especially, the decrease of dielectric constant was found to be related to the extent of exfoliation of clay. It is recognized that the confinement effect of clay results in the suppression of the dielectric response of the nanocomposite materials at low frequency. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2402–2410, 2004     

Preparation and properties of (BATB–ODPA) polyimide–clay nanocomposite materials

A series of polymer–clay nanocomposite (PCN) materials consisting of 1,4‐bis(4‐aminophenoxy)‐2‐tert‐butylbenzene–4,4′‐oxydiphthalic anhydride (BATB–ODPA) polyimide (PI) and layered montmorillonite (MMT) clay were successfully prepared by an in situ polymerization reaction through thermal imidization up to 300°C. The synthesized PCN materials were subsequently characterized by Fourier‐Transform infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of material composition on thermal stability, mechanical strength, molecular permeability and optical clarity of bulk PI and PCN materials in the form of membranes were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), molecular permeability analysis (GPA) and ultraviolet‐visible (UV/VIS) transmission spectra, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1072–1079, 2004     

Preparation and characterization of polystyrene–clay nanocomposites by free‐radical polymerization

The polymerizable cationic surfactant, vinylbenzyldimethylethanolammouium chloride (VBDEAC), was synthesized to functionalize montmorillonite (MMT) clay and used to prepare exfoliated polystyrene–clay nanocomposites. The organophilic MMT was prepared by Na⁺ exchanged montmorillonite and ammonium cations of the VBDEAC in an aqueous medium. Polystyrene–clay nanocomposites were prepared by free‐radical polymerization of the styrene containing intercalated organophilic MMT. Dispersion of the intercalated montmorillonite in the polystyrene matrix determined by X‐ray diffraction reveals that the basal spacing is higher than 17.6 nm. These nanocomposites were characterized by differential scanning calorimetry (DSC), transmission electron micrograph (TEM), thermal gravimetric analysis (TGA), and mechanical properties. The exfoliated nanocomposites have higher thermal stability and better mechanical properties than the pure polystyrene. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1370–1377, 2002     

Synthesis and properties of polystyrene–montmorillonite nanocomposites by suspension polymerization

Organophilic montmorillonite was prepared using ion‐exchange method between sodium ions in clay layers and stearyltrimethyl ammonium chloride in the various solvents, including deionized water, ethanol, acetone, and toluene. The montmorillonite has the largest d₀₀₁ spacing, as determined by X‐ray diffraction in toluene, than the other solvents considered. Ethanol can completely wash out the overexchanged stearyltrimethyl ammonium chloride among layers of montmorillonite. However, deionized water is the preferred ion‐exchange solvent. The thermal stability of organophilic montmorillonite was investigated by high‐resolution thermogravimetric analysis (TGA). Polystyrene–montmorillonite nanocomposites were obtained by suspension free radical polymerization of styrene in the dispersed organophilic montmorillonite. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) revealed that montmorillonite had been exfoliated. 5.0 wt % of clay in the synthesized nanocomposite was found to be the optimum content that improved both thermal and mechanical properties over those of pure polystyrene under the experimental conditions applied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 101–109, 2004     

Polyacrylamide–clay nanocomposite materials prepared by photopolymerization with acrylamide as an intercalating agent

A series of nanocomposite materials consisting of water‐soluble polyacrylamide (PAA) and layered montmorillonite (MMT) clay platelets were prepared by the effective dispersion of the inorganic nanolayers of the MMT clay in the organic PAA matrix via in situ ultraviolet‐radiation polymerization. The acrylamide monomers functioned as both the intercalating agent and the reacting monomers. As a representative procedure for the preparation of the nanocomposites, organic acrylamide monomers were first intercalated into the interlayer regions of acrylamide‐treated organophilic clay hosts, and this was followed by one‐step ultraviolet‐radiation free‐radical polymerization with benzil as a photoinitiator. The as‐prepared polyacrylamide–clay nanocomposite (PCN) materials were subsequently characterized by Fourier transform infrared spectroscopy, wide‐angle powder X‐ray diffraction, and transmission electron microscopy. The effects of the material composition on the thermal stability, optical clarity, and gas‐barrier properties of pristine PAA and PCN materials, in the forms of fine powders and membranes, were also studied by differential scanning calorimetry, thermogravimetric analysis, ultraviolet–visible transmission spectroscopy, and gas permeability analysis. The molecular weights of PAA extracted from PCN materials and pristine PAA were determined by gel permeation chromatography with tetrahydrofuran as an eluant. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3489–3496, 2004     

Crystallization behavior of syndiotactic polystyrene nanocomposites for melt‐ and cold‐crystallizations

Analyses of the effects of montmorillonite (clay) on the crystallinity and crystallization behavior of syndiotactic polystyrene (s‐PS) were investigated by Fourier transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC). The dispersibility of the clay in s‐PS nanocomposites was studied by X‐ray and transmission electron microscopy (TEM). The clay was dispersed into the s‐PS matrix by melt blending on a scale of 1–2 nm or few tenths–100 nm, depending on the surfactant treatment. On adding clay, the crystallization behavior of the s‐PS tends to convert into the β‐crystal from the α‐crystal after being cold‐crystallized because the clay plays a vital role in facilitating the formation of the thermodynamically favored β‐form crystal when the s‐PS is cold‐ or melt‐crystallized. This phenomenon leads to a change in a conventional mechanism of molecular packing for the s‐PS. Evidently, the clay significantly affects the crystallinity and crystallization behavior of the s‐PS. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2492–2501, 2002     

Enhanced corrosion prevention effect of polysulfone–clay nanocomposite materials prepared by solution dispersion

A series of polymer–clay nanocomposite (PCN) materials containing polysulfone (PSF) and layered MMT clay were successfully prepared by effectively dispersing inorganic nanolayers of MMT clay in an organic PSF matrix via a solution dispersion technique. The synthesized PCN materials were subsequently investigated with a series of characterization techniques, including Fourier transform infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The prepared PCN coatings with low clay loading (1 wt %) on cold‐rolled steel (CRS) were found to be superior in corrosion prevention to those of bulk PSF, based on a series of electrochemical measurements of corrosion potential, polarization resistance, corrosion current and electrochemical impedance spectroscopy (EIS) in a 5 wt % aqueous NaCl electrolyte. The effects of material composition on the molecular barrier, mechanical strength and optical clarity of PSF and PCN materials, in the form of membranes, was also studied by molecular permeability analysis (GPA), dynamic mechanical analysis (DMA) and UV‐Visible transmission spectra, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 631–637, 2004     

Preparation and properties of heterocyclically conjugated poly(3‐hexylthiophene)–clay nanocomposite materials

A series of heterocyclically conjugated polymer–clay nanocomposite (PCN) materials that consisted of organic poly(3‐hexylthiophene) (P3HT) and inorganic montmorillonite (MMT) clay platelets were prepared by in situ oxidative polymerization with FeCl₃ as an oxidant. The as‐synthesized PCN materials were characterized by Fourier transform infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (WAXRD), and transmission electron microscopy (TEM). The effects of the material composition on the anticorrosion, gas barrier, thermal stability, flammability, mechanical strength, and electrical conductivity properties of the P3HT and PCN materials were studied by electrochemical corrosion measurements, gas‐permeability analysis (GPA), thermogrametric analysis (TGA), limiting oxygen index (LOI) measurements, dynamic mechanical analysis (DMA), and a four‐point probe technique, respectively. The molecular weights of extracted and bulk P3HT were determined by gel permeation chromatography (GPC) with THF as an eluant. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3438–3446, 2004     

Rubber–clay nanocomposite by solution blending

Ethylene vinyl acetate rubber (45% vinyl acetate content, EVA‐45) and organomodified clay (12Me‐MMT) composites were prepared by solution blending of the rubber and the clay. A combination of X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy studies showed that the composites obtained are on the nanometer scale. The measurements of the dynamic mechanical properties for different compositions over a temperature range (?100 to +100°C) showed that the storage moduli of these rubber–clay nanocomposites are higher above the glass to rubber transition temperature compared to the neat rubber. The tensile strength of the nanocomposites is about 1.6 times higher than that of the EVA‐45. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2216–2220, 2003     

Synthesis and dielectric properties of poly(methyl methacrylate)–clay nanocomposite materials

Poly(methyl methacrylate) (PMMA)–clay nanocomposite (PCN) materials were synthesized through in situ intercalative polymerization. A cationic surfactant, [2(dimethylamino)ethyl]triphenylphosphonium bromide, was used as an intercalating agent with pristine Na⁺‐montmorillonite (MMT). The synthesized PCN materials were subsequently investigated by a series of characterization techniques, including wide‐angle powder X‐ray diffraction, Fourier transform IR spectroscopy, transmission electron microscopy, thermogravimetric analysis, and differential scanning calorimetry. Compared to pure PMMA, the PCN materials exhibit higher thermal degradation temperatures and glass‐transition temperatures. The dielectric properties of PCN blending with a commercial PMMA material in film form with clay loading from 0.5 to 5.0 wt % were measured under frequencies of 100 Hz–1 MHz at 35–100°C. Significantly depressed dielectric constants and losses were observed for these PCN‐blending materials. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2175–2181, 2005     

Comparative studies of the properties of poly(methyl methacrylate)–clay nanocomposite materials prepared by in situ emulsion polymerization and solution dispersion

A series of polymer–clay nanocomposite (PCN) materials consisting of organic poly(methyl methacrylate) (PMMA) and inorganic montmorillonite (MMT) clay platelets were prepared successfully by the effective dispersion of nanolayers of the MMT clay in the PMMA framework through both in situ emulsion polymerization and solution dispersion. The as‐prepared PCN materials obtained with both approaches were subsequently characterized with wide‐angle powder X‐ray diffraction and transmission electron microscopy. For a comparison of the anticorrosion performance, a PCN material (e.g., 3 wt % clay loading) prepared by in situ emulsion polymerization, showing better dispersion of the clay platelets in the polymer matrix, exhibited better corrosion protection in the form of a coating on a cold‐rolled steel coupon than that prepared by solution dispersion, which showed a poor dispersion of the clay nanolayers according to a series of electrochemical corrosion measurements. Comparative studies of the optical clarity, molecular barrier properties, and thermal stability of samples prepared in both ways, as membranes and fine powders, were also performed with ultraviolet–visible transmission spectroscopy, molecular permeability analysis, thermogravimetric analysis, and differential scanning calorimetry. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1936–1946, 2004     

Preparation and characterization of polyethylene–clay nanocomposites by using chlorosilane‐modified clay

Clay was modified by trimethylchlorosilane; after modification, hydroxyl groups at the edge of layers were reacted and CEC value was drastically decreased. Polyethylene–clay composites were prepared by melt compounding. Wide angle X‐ray diffraction (WAXD) and transmission electron microscopy (TEM) showed that intercalated nanocomposites were formed using organoclay ion‐exchanged from chlorosilane‐modified clay, but conventional composites formed using organoclay directly ion‐exchanged from crude clay. Dynamic mechanical analysis (DMA) of PE and PE–clay composites was conducted; the results demonstrated that nanocomposites were more effective than conventional composites in reinforcement and addition of organoclay resulted in the increase of glass transition temperature (T_g), but crude clay had no effect on T_g of PE–clay composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 676–680, 2004     

Role of the cation‐exchange capacity in the formation of polystyrene–clay nanocomposites by in situ intercalative polymerization

An effect of the cation‐exchange capacity (CEC) on the formation of polystyrene–clay nanocomposites is reported. Two types of 2:1 layered silicates with different CECs, Wyoming (97 mequiv/100 g of clay) and bentonite H (BNH; 131 mequiv/100 g of clay) were investigated. The organoclay was prepared through the mixing of purified clay and octadecyldimethylammonium chloride (ODA) in an aqueous solution. The packing of the intercalated ODA surfactant depended on the CEC and the degree of solvent extraction. Two possible phases of the interlayer packing, solidlike and liquidlike, were detected for the extracted BNH because of the charge heterogeneity of the clay. The liquidlike phase showed a good affinity toward the styrene monomer, which promoted the formation of exfoliated nanocomposites. On the other hand, the solidlike phase showed a restricted dispersion in the styrene monomer. The organoclay interlayer showed limited expansion by the styrene monomer. This led to the formation of intercalated nanocomposites. An increase in the organoclay loading hindered the formation of the exfoliated nanocomposites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 785–789, 2005     

Polystyrene nanocomposite materials by in situ polymerization into montmorillonite–vinyl monomer interlayers

A different series of new polystyrene–clay nanocomposites have been prepared by grafting polymerization of styrene with vinyl‐montmorillonite (MMT) clay. The synthesis was achieved through two steps. The first step is the modification of clay with the vinyl monomers, such as N,N‐dimethyl‐n‐octadecyl‐4‐vinylbenzyl‐ammonium chloride, n‐octadecyl‐4‐vinylbenzyl‐ammonium chloride, triphenyl‐4‐vinylbenzyl‐phosphonium chloride, and tri‐n‐butyl‐4‐vinylbenzyl‐phosphonium chloride. The second step is the polymerization of styrene with different ratios of vinyl‐MMT clay. The materials produced were characterized by different physical and chemical methods: (1) IR spectra, confirming the intercalation of the vinyl‐cation within the clay interlayers; (2) thermogravimetric analysis (TGA), showing higher thermal stability for PS–nanocomposites than polystyrene (PS) and higher thermal stability of nanocomposites with of phosphonium moieties than nanocomposites with ammonium moieties; (3) swelling measurements in different organic solvents, showing that the swelling degree in hydrophobic solvents increases as the clay ratio decreases; (4) X‐ray diffraction (XRD), illustrating that the nanocomposites were exfoliated at up to a 25 wt % of organoclay content; and (5) scanning electron microscopy (SEM), showing a complete dispersion of PS into clay galleries. Also, transmission electron microscopy (TEM) showed nanosize spherical particles of ～ 150–400 nm appearing in the images. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3739–3750, 2007     

Preparation and properties of polyimide–clay nanocomposite materials for anticorrosion application

A series of polymer–clay nanocomposite (PCN) materials that consist of organosoluble polyimide and layered montmorillonite clay were prepared by the solution dispersion technique. The organosoluble polyimide containing non‐coplanar moiety in diamine monomer and flexible bridging linkages in dianhydride monomer was synthesized by chemical imidization. The as‐synthesized PCN materials were characterized by infrared spectroscopy, wide‐angle powder X‐ray diffraction, and transmission electron microscopy. The organosoluble polyimide showed better corrosion resistance compared to polyaniline, poly(o‐ethoxyaniline) and poly(methyl methacrylate) by using a series of standard electrochemical corrosion measurements of corrosion potential, polarization resistance, and corrosion current in 5 wt % aqueous NaCl electrolyte. Polyimide–clay nanocomposite materials incorporated with low loading of clay were found to further improve corrosion inhibition over pure polyimide. Effects of the material composition on the O₂/H₂O molecular permeability, optical clarity, and thermal properties of polyimide–clay nanocomposite materials were studied by molecular permeability analysis, UV–visible transmission spectra, thermogravimetric analysis, and differential scanning calorimetry, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3573–3582, 2004     

A comparative study of the preparation and physical properties of polystyrene–silica mesocomposite and nanocomposite materials

In this paper, a comparative study with regard to the preparation and physical properties of as‐prepared polystyrene–silica mesocomposite (PSM) and polystyrene‐silica nanocomposite (PSN) materials is presented. Vinyl‐modified mesoporous silica particles with a wormhole structure were first prepared by doping a sol‐gel metal oxide with an optically active non‐surfactant (dibenzoyl‐L ‐tartaric acid) as a template, followed by template removal through Soxhlet extraction. The as‐prepared silica particles with/without mesopores were subsequently characterized using the Brunauer–Emmett–Teller method and transmission electron microscopy (TEM) and Fourier transform infrared, ¹³C NMR and ²⁹Si NMR solid‐state spectroscopy. A specific feed amount of silica particles was subsequently reacted with styrene monomer by free radical polymerization to yield a series of PSM and corresponding PSN materials. Both as‐prepared composite systems were further characterized using TEM and scanning electron microscopy/energy‐dispersive X‐ray mapping studies. A systematic comparative study of the physical properties of both as‐prepared composite materials clearly illustrated that PSM had effectively enhanced thermal stability, optical clarity and dielectric properties compared to the corresponding PSN counterpart. Evaluation was carried out using thermogravimetric analysis, differential scanning calorimetry, UV‐visible transmission spectroscopy and dielectric constant measurements. Copyright © 2011 Society of Chemical Industry     

Thermal and surface characterization of polyurethane–urea clay nanocomposite coatings

This paper reports synthesis and characterization of polyurethane–urea (PU‐urea) and the nanocomposites derived from the PU‐urea with silicate clays. Organophilic montmorillonite cotreated by cetyl trimethyl ammonium bromide (CTAB) was synthesized and used to prepare PU‐urea/montmorillonite nanocomposites coatings. PU‐ureas were prepared from polyethylene glycol (PEG), polypropylene glycol (PPG), trimethylol propane (TMP), and 4,4′‐diphenylmethane diisocyanate (MDI) by reacting excess diisocyanate with polyether glycols. The excess isocyanate of the prepolymers was cured with atmospheric moisture. The synthesized moisture cured PU‐urea and nanocomposites were characterized by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetric (DSC), and angle resolved X‐ray photoelectron spectroscopy (AR‐XPS). The thermal stability of the PU‐urea nanocomposites was higher relative to the mother PU‐urea films. DSC results showed a slight enhancement in the soft segment glass transition temperature after 3 wt % clay loading. The surface properties showed an enrichment of the soft segment toward the surface. An enhancement in the hard segment composition in the nanocomposite coatings has resulted in enhancing the phase mixing process. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2393–2401, 2006