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

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

Fracture behavior of thermoplastic polyolefin/clay nanocomposites

A thermoplastic polyolefin (TPO) containing 70 wt % styrene–ethylene–butadiene‐styrene‐g‐maleic anhydride and 30 wt % polypropylene and its nanocomposites reinforced with 0.3–1.5 wt % organoclay were prepared by melt mixing followed by injection molding. The mechanical and fracture behaviors of the TPO/clay nanocomposites were investigated. The essential work of fracture (EWF) approach was used to evaluate the tensile fracture behavior of the nanocomposites toughened with elastomer. Tensile tests showed that the stiffness and tensile strength of TPO was enhanced by the addition of low loading levels of organically modified montmorillonite. EWF measurements revealed that the fracture toughness of the TPO/clay nanocomposites increased with increasing clay content. The organoclay toughened the TPO matrix of the nanocomposites effectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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

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

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

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

Nano/micro ternary composites based on PP,nanoclay, and CaCO3

Nano‐/microcomposites based on polypropylene/montmorillonite/calcium carbonate were prepared by melt mixing. Their structures and properties were characterized by small‐angle X‐ray diffraction, thermal analysis, and rheological measurements. The intercalation degree was found to be dependent on the compatibilizer content and the processing temperature. The addition of the organoclay slightly increased the melt crystallization temperature of polypropylene, acting as nucleating agents, and improved the degree of crystallinity. The rheological tests showed that nanocomposites increased the complex viscosity when compared with the microcomposites with the same filler content and exhibited a pronounced shear‐thinning behavior in the low frequency range. A Carreau‐Yasuda model was used to model the rheological behavior of these materials. The nano‐/microcomposites showed a significant improvement (about 50%) of the Young's modulus when compared with microcomposites with the same filler content due to the intercalation or exfoliation of the organoclay and the enhanced degree of crystallinity. Moreover, some formulations showed an enhancement of elongation at break and ultimate strength. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphology,thermal and mechanical behavior of polypropylene nanocomposites toughened with poly(ethylene‐co‐octene)

Rubber‐toughened polypropylene (PP) nanocomposites containing organophilic layered silicates were prepared by means of melt extrusion at 230 °C using a co‐rotating twin‐screw extruder in order to examine the influence of the organoclay and the addition of PP grafted with maleic anhydride (PPgMAH) as a compatibilizer on the morphological, mechanical and thermal properties. The mechanical properties of rubber‐toughened polypropylene nanocomposites (RTPPNCs) were studied through tensile, flexural and impact tests. Scanning electron microscopy (SEM) was used for investigation of the phase morphology and rubber particles size. X‐ray diffraction (XRD) was employed to characterize the formation of nanocomposites. The thermal properties were investigated by using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The dynamic mechanical properties were examined by using dynamic mechanical analysis (DMA). From the tensile and flexural tests, the optimum loading of organoclay in RTPP was found to be 6 wt%. The optimum loading of PPgMAH, based on the tensile and flexural properties, was also 6 wt%. The increase in the organoclay and PPgMAH content resulted in a severe embrittlement, manifested by a drop in the impact strength and tensile elongation at break. XRD studies revealed that intercalated RTPPNCs had been successfully prepared where the macromolecular PP segments were intercalated into the interlayer space of the organoclay. In addition, the organoclay was dispersed more evenly in the RTPPNC as the PPgMAH content increased. TGA results revealed that the thermal stability of the RTPPNC improved significantly with the addition of a small amount of organoclay. Copyright © 2006 Society of Chemical Industry     

New aramid‐based nanocomposites: Synthesis and characterization

New type of nanocomposites containing various proportions of montmorillonite in aromatic polyamide was prepared via solution intercalation method. Aramid chains were synthesized by reacting 4,4′‐oxydianiline with isophthaloyl chloride in N,N′‐dimethyl acetamide. Dodecylamine was used as swelling agent to change the hydrophilic nature of montmorillonite into organophilic. Appropriate amounts of organoclay were mixed in the polymer solution using high‐speed mixer for complete dispersion of the clay. Thin films cast from these materials after evaporating the solvent were characterized by XRD, TEM, mechanical, thermal, and water absorption measurements. The structure and morphology of the nanocomposites determined by XRD and TEM revealed the formation of exfoliated and intercalated clay platelets in the aramid matrix. Mechanical data indicated improvement in the tensile strength and modulus of the nanocomposites with clay loading up to 6 wt%. The glass transition temperature increased up to 12 wt% clay content and thermal stability amplified with increasing clay loading. The water absorption reduced gradually as a function of organoclay and approached to zero with 20 wt% organoclay in the aramid. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Synthesis and characterization of poly(ethylene terephthalate) nanocomposites with organoclay

Poly(ethylene terephthalate) (PET)/montmorillonite (MMT) nanocomposites were prepared by solution intercalation method. The clay was organo‐modified with the intercalation agent cetylpyridinium chloride (CPC). Wide‐angle X‐ray diffraction (XRD) showed that the layers of MMT were intercalated by CPC. Four nanocomposites with organoclay contents of 1, 5, 10, and 15 wt % were prepared by solution blending. XRD showed that the interlayer spacing of organoclay in the nanocomposites depends on the amount of organoclay present. According to the results of differential scanning calorimetry (DSC) analysis, clay behaves as a nucleating agent and enhances the crystallization rate of PET. The maximum enhancement of crystallization rate for the nanocomposites was observed in those containing about 10 wt % organoclay within the studied range of 1–15 wt %. From thermogravimetric analysis (TGA), we found that the thermal stability of the nanocomposites was enhanced by the addition of 1–15 wt % organoclay. These nanocomposites showed high levels of dispersion without agglomeration of particles at low organoclay content (5 wt %). An agglomerated structure did form in the PET matrix at 15 wt % organoclay. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 140–145, 2004     

Rheological behavior of polypropylene/layered silicate nanocomposites prepared by melt compounding in shear and elongational flows

Melt rheology and processability of exfoliated polypropylene (PP)/layered silicate nanocomposites were investigated. The nanocomposites were prepared by melt compounding process in the presence or absence of a PP‐based maleic anhydride compatibilizer. PP/layered silicate nanocomposites showed typical rheological properties of exfoliated nanocomposites such as nonterminal solid‐like plateau behavior at low frequency region in oscillatory shear flow, higher steady shear viscosity at low shear rate region, and outstanding strain hardening behavior in uniaxial elongational flow. The melt processability of exfoliated PP/layered silicate nanocomposites was significantly improved due to good dispersion of layered silicates and increased molecular interaction between the PP matrix and the layered silicate organoclay. Small‐angle X‐ray scattering and transmission electron microscopy results revealed that the layered silicate organoclay was exfoliated and good interaction between PP matrix and organoclay was achieved by using the PP‐g‐MAH compatibilizer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3506–3515, 2007     

The Nucleating Effect of Montmorillonite on Crystallization of PET/Montmorillonite Nanocomposite

Poly(ethylene terephthalate) (PET)/montmorillonite (MMT) nanocomposites were prepared by solution intercalation method. The clay was organo-modified with intercalation agent of cetyltrimetylammonium chloride (CMC). XRD showed that the layers of MMT were intercalated by CMC. Four nanocomposites with organoclay contents of 1, 5, 10, and 15 wt% were prepared by solution blending. XRD showed that the interlayer spacing of organoclay in the nanocomposites depends on the amount of organoclay. The nucleating effect of organoclay is investigated using differential scanning calorimetry (DSC) analysis. Clay behaves as a nucleating agent and enhances the crystallization rate of PET. Maximum enhancement in crystallization rate for the nanocomposites was observed in blends containing ca. 10 wt% of clay in the range of 1–15 wt%. According to transmission electron microscopy (TEM), the organoclay particle was highly dispersed in the PET matrix without a large agglomeration of particles for low organoclay content (5 wt%). Agglomerated structure did form in the PET matrix at 15 wt% organoclay content.     

Investigation of the influence of processing conditions on the thermal,rheological and mechanical behavior of polypropylene nanocomposites

The use of polypropylene (PP)‐layered silicate nanocomposite has attracted great interest in the polymer industry over the last years. On one hand, PP is widely used in many fields of applications because of good performance and cost. On the other hand, the major advantage of layered silicate nanofiller in the polymer matrix is the small amount of filler (<5 wt%) needed to enhance various properties such as Young's modulus. The most commonly used layered silicates are organomodified montmorillonite (MMT). In this study, a PP/organoclay nanocomposite, filled with layered silicate Nanofil SE3010 (1 and 5 wt%), provided by Rockwood Additives, USA, was used. The polymer nanocomposites were prepared via melt intercalation in a laboratory kneader. The compatibilizer (PP grafted with maleic acid anhydride) admixture content relative to the organoclay content (1 and 5 wt%) was chosen at a ratio of 1:1 (clay:compatibilizer). The influence of different processing conditions (rotation speed and residence time) on the thermal, rheological, and mechanical properties and the interlayer distance was investigated. It was the target to determine whether a short and intensive or a long and soft process performs better. Different properties prefer different states of dispersion of MMT in the polymer matrix. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Structure and properties of polypropylene/clay nanocomposites compatibilized by solid‐phase grafted polypropylene

Polypropylene/organic‐montmorillonite (PP/OMMT) nanocomposites were prepared via a solid‐phase PP graft (TMPP) with a higher grafting level as the compatibilizer. The effects of the compatibilizer on the structure and properties of PP/OMMT nanocomposites were investigated. The structure of the nanocomposites were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results showed that when the weight ratio of TMPP and OMMT is greater than 1:1, the OMMT can be dispersed in PP matrix uniformly at the nanoscale. The mechanical properties of the nanocomposites reached a maximum when the weight ratio of TMPP and OMMT is 1:1, although more uniform dispersion was achieved at a higher content of TMPP. The mechanical properties of the nanocomposites decrease with the content of TMPP. The crystallization behavior, dynamic rheological property, and thermal stability of the nanocomposites were investigated by differential scanning calorimetry (DSC), dynamic rheological analysis, and thermal gravimetric analysis (TGA), respectively. Due to the synergistic effects of TMPP and OMMT on the crystallization of PP, the crystallization peak temperature of the nanocomposites increased remarkably compared with that of the neat PP. TMPP shows β‐phase nucleating ability and OMMT promotes the development of β‐phase crystallite. The nanocomposites show restricted melt flow and enhanced temperature sensitivity compared with the neat PP. The thermal stability of the nanocomposites is obviously improved compared with that of the neat PP. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers.     

Mechanical and morphological properties of organic–inorganic,hybrid, clay‐filled,and cyanate ester/siloxane toughened epoxy nanocomposites

Organic–inorganic hybrids involving cyanate ester and hydroxyl‐terminated polydimethylsiloxane (HTPDMS) modified diglycidyl ether of bisphenol A (DGEBA; epoxy resin) filled with organomodified clay [montmorillonite (MMT)] nanocomposites were prepared via in situ polymerization and compared with unfilled‐clay macrocomposites. The epoxy‐organomodified MMT clay nanocomposites were prepared by the homogeneous dispersion of various percentages (1–5%), and the resulting homogeneous epoxy/clay hybrids were modified with 10% HTPDMS and γ‐aminopropyltriethoxysilane as a coupling agent in the presence of a tin catalyst. The siliconized epoxy/clay prepolymer was further modified separately with 10% of three different types of cyanate esters, namely, 4,4′‐dicyanato‐2,2′‐diphenylpropane, 1,1′‐bis(3‐methyl‐4‐cyanatophenyl) cyclohexane, and 1,3‐dicyanato benzene, and cured with diaminodiphenylmethane as a curing agent. The reactions during the curing process between the epoxy, siloxane, and cyanate were confirmed by Fourier transform infrared analysis. The results of dynamic mechanical analysis showed that the glass‐transition temperatures of the clay‐filled hybrid epoxy systems were lower than that of neat epoxy. The data obtained from mechanical studies implied that there was a significant improvement in the strength and modulus by the nanoscale reinforcement of organomodified MMT clay with the matrix resin. The morphologies of the siloxane‐containing, hybrid epoxy/clay systems showed heterogeneous character due to the partial incompatibility of HTPDMS. The exfoliation of the organoclay was ascertained from X‐ray diffraction patterns. The increase in the percentage of organomodified MMT clay up to 5 wt % led to a significant improvement in the mechanical properties and an insignificant decrease in the glass‐transition temperature versus the unfilled‐clay systems. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Extrusion of linear polypropylene–clay nanocomposite foams

This work presents new results on using organoclay with an appropriate polymeric compatibilizer as rheology‐modifying additives for extrusion foaming of a linear polypropylene (PP), which by itself does not display strain hardening in extensional flow of the melt. The uniaxial melt‐extensional viscosity behavior of several nanocomposites prepared with varying ratio of bound maleic anhydride to clay as well as varying compatibilizer molecular weight was investigated. A chemical‐blowing agent was used at a fixed concentration for foaming these nanocomposites in a single‐screw extruder. Among nanocomposites with similar levels of clay dispersion or intercalation, the ones that displayed significant strain hardening in the melt state along with slower crystallization led to extruded PP nanocomposite foams with smaller cell sizes and greater cell density by reducing cell coalescence. This was achieved with as little as 3 wt% organoclay and a high‐molecular weight PP‐g‐MA compatibilizer in linear PP. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Exfoliation and dispersion enhancement in polypropylene nanocomposites by in‐situ melt phase ultrasonication

A novel process using ultrasonics to enhance the exfoliation and dispersion of clay platelets in polypropylene‐based nanocomposites has been proposed and investigated. The materials studied were isotactic polypropylene of various molecular weights reinforced with organophilic montmorillonite clay (nanoclay) at 4–6 wt% loadings. X‐ray diffraction (XRD) and rheological measurements, on a model system of nanoclay in mineral oil, were first used to determine ultrasonic energy requirements. The effectiveness of the proposed ultrasonic processing technique on polypropylene nanocomposites was evaluated by XRD and transmission electron microscopy (TEM). The effects of added maleic anhydride–grafted polypropylene compatibilizer, polypropylene molecular weight, and pretreatment of the nanoclays on the nanocomposite exfoliation were also investigated. Results indicate that ultrasonic processing of polymer nanocomposites in the melt state is an effective method for improving exfoliation and dispersion of nanoclays. Issues regarding molecular weight degradation, optimization, mechanical properties, and continuous processing are beyond the scope of the present study and are currently being investigated in our laboratory. Polym. Eng. Sci. 44:1773–1782, 2004. © 2004 Society of Plastics Engineers.     

Organomodification of montmorillonite and its effects on the properties of poly(butylene succinate) nanocomposites

The pristine sodium montmorillonite (MMT) was organically modified with hexadecyltrimethylammonium bromide (HTAB) at different contents. The organoclay was characterized by X‐ray diffraction (XRD), Fourier transform infrared spectroscopy, energy dispersive X‐ray techniques, and thermogravimetric analysis. Then, poly(butylene succinate) (PBS) nanocomposites were prepared by melt‐mixing process using maleic anhydride‐grafted PBS (PBS‐g‐MA) as compatibilizer. It was found that the mechanical properties of PBS nanocomposites filled with organoclay were apparently higher than that of the nanocomposite filled with MMT. This is attributed to the better filler–matrix interactions between PBS and the organoclay and the better filler dispersion. This is verifiable through the XRD, scanning electron microscopy, and transmission electron microscopy. The addition of PBS‐g‐MA further improved the mechanical properties. It was also found that our laboratory synthesized organoclay modified with HTAB has provided a better reinforcing efficiency when compared with the commercial octadecylamine‐modified organoclay. Besides that the thermal properties of PBS nanocomposites were studied through differential scanning calorimetry. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Preparation and cure behavior of organoclay‐modified allyl‐functional benzoxazine resin and the properties of their nanocomposites

A new type of polybenzoxazine‐clay nanocomposites were prepared by the in‐situ polymerization of allyl‐functional benzoxazine monomer, bis(3‐allyl‐3,4‐dihydro‐2H‐1,3‐benzoxazinyl)isopropane (B‐ala), in the presence of two different types of organoclay, allyldimethylstearylammonium‐montmorillonite and propyldimethylstearylammonium‐montmorillonite. The organoclays were mixed with molten B‐ala, followed by pouring into glass mold and then gradual curing up to 250°C. DSC and IR were used to follow the cure behavior of B‐ala in the presence of organoclay, indicating that organoclays catalyzed the ring opening of cyclic benzoxazine structure. The XRD of the nanocomposites showed featureless patterns, suggesting the exfoliation of the organoclay into the matrix. The viscoelastic properties of the hybrids showed that the glass transition temperatures (T_g) of the nanocomposites shifted to lower temperature in the presence of small amount of organoclay, but T_g started to increase with the increase of the organoclay content. This result suggests that, in the presence of organoclay, the curing reaction of ally and benzoxazine occurred in a different way, resulting in a different network structure. However, the presence of dispersed layered silicates into the matrix enhanced the thermal stability over the neat thermoset resin. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Rheological properties of poly(lactic acid) based nanocomposites: Effects of different organoclay modifiers and compatibilizers

Poly(lactic acid) (PLA) nanocomposites containing five types of organically modified, layered silicates and two elastomeric compatibilizers, namely ethylene‐glycidyl methacrylate (E‐GMA) and ethylene‐butyl acrylate‐maleic anhydride (E‐BA‐MAH), were prepared using a twin screw extruder. The morphologies of the nanocomposites were determined by X‐ray diffraction (XRD) and transmission electron microscopy (TEM), and the rheological properties of the melts were measured using small‐amplitude oscillatory shear. XRD revealed that the addition of E‐GMA to the binary nanocomposites resulted in higher compatibility between the organoclay nanoplatelets and the polymer matrix. TEM showed that all of the nanocomposites contained mixed dispersed structures, involving tactoids of various sizes, as well as intercalated and exfoliated organoclay layers. Rheological properties were found to be affected by the differences in the compatibility between the organoclays and the polymer matrix, and by the addition of the compatibilizer. Organoclay types that resulted in high level of dispersion exhibited higher values of complex viscosity compared to that of neat PLA. The addition of E‐GMA introduced a solid‐like rheological behavior at low frequencies. All of the nanocomposites had similar rheological behavior at high frequencies. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42915.     

Nanocomposites of poly(trimethylene terephthalate) with organoclay

Two different kinds of clay were organomodified with cetylpyridinium chloride (CPC) as an intercalation agent. Poly(trimethylene terephthalate) (PTT)/organoclay nanocomposites were prepared by the solution intercalation method. Wide‐angle X‐ray diffraction (WAXD) indicated that the layers of clay were intercalated by CPC and the interlayer spacing was a function of the cationic exchange capacity (CEC) of the clay: the higher the CEC, the larger the interlayer spacing is. The WAXD studies showed that the interlayer spacing of organoclay in the nanocomposites depends on the amount of organoclay. From the results of differential scanning calorimetry analysis it was found that clay behaves as a nucleating agent and enhances the crystallization rate of PTT. The maximum enhancement of the crystallization rate for the nanocomposites was observed in nanocomposites containing about 5 wt % organoclay with a range of 1–15 wt %. The thermal stability of the nanocomposites was enhanced by the addition of 1–10 wt % organoclay as found from thermogravimetric analysis. The thermal stability of the PTT/organoclay nanocomposites was related to the organoclay content and the dispersion in the PTT matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3315–3322, 2003     

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