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     

Rubber‐toughened polypropylene nanocomposite: Effect of polyethylene octene copolymer on mechanical properties and phase morphology

Rubber‐toughened polypropylene (PP)/org‐Montmorillonite (org‐MMT) nanocomposite with polyethylene octene (POE) copolymer were compounded in a twin‐screw extruder at 230°C and injection‐molded. The POE used had 25 wt % 1‐octene content and the weight fraction of POE in the blend was varied in the range of 0–20 wt %. X‐ray diffraction analysis (XRD) revealed that an intercalation org‐MMT silicate layer structure was formed in rubber‐toughened polypropylene nanocomposites (RTPPNC). Izod impact measurements indicated that the addition of POE led to a significant improvement in the impact strength of the RTPPNC, from 6.2 kJ/m² in untoughened PP nanocomposites to 17.8 kJ/m² in RTPPNC containing 20 wt % POE. This shows that the POE elastomer was very effective in converting brittle PP nanocomposites into tough nanocomposites. However, the Young's modulus, tensile strength, flexural modulus, and flexural strength of the blends decreased with respect to the PP nanocomposites, as the weight fraction of POE was increased to 20 wt %. Scanning electron microscopy (SEM) was used for the investigation of the phase morphology and rubber particles size. SEM study revealed a two‐phase morphology where POE, as droplets was dispersed finely and uniformly in the PP matrix. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3441–3450, 2006     

Rectorite/thermoplastic polyurethane nanocomposites: Preparation,characterization, and properties

A newly developed kind of layered clay, rectorite (REC), has been used to yield intercalated or exfoliated thermoplastic polyurethane rubber (TPUR) nanocomposites by melt‐processing intercalation. Because of the swollen layered structure of REC, similar to that of montmorillonite, organic rectorites (OREC) can also be obtained through ion‐exchange reaction with two different quaternary ammonium salts (QAS1, QAS2) and benzidine (QAS3). The microstructure and dispersibility of OREC layers in TPUR matrix were examined by X‐ray diffraction and transmission electron microscopy, which revealed not only that the composites with lower amounts of clay are intercalation or part exfoliation nanocomposites, but also that the mechanical properties of the composites were substantially enhanced. The maximum ultimate tensile strength for TPUR/OREC nanocomposites appeared at 2 wt % OREC loading. With increasing OREC contents, the tear strength of the composites increased significantly. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 608–614, 2004     

TPO based nanocomposites. Part 1. Morphology and mechanical properties

The relationship between morphology and the mechanical properties of thermoplastic olefin (TPO) materials that are reinforced with organoclay fillers and prepared by melt processing is reported. Nanocomposites based on blends of polypropylene and elastomer and using an organoclay masterbatch were prepared in a twin-screw extruder. Transmission electron microscopy, atomic force microscopy and wide-angle X-ray scattering were employed to carry out a detailed particle analysis of the morphology of the dispersed clay and elastomer phases for these nanocomposites. The improvement in mechanical properties, e.g. stiffness enhancement as evaluated by stress-strain analysis and impact strength obtained from notched Izod impact tests, were successfully explained in terms of morphological changes induced by the presence of the clay and elastomer particles. Quantitative analyses of TEM micrographs and AFM images revealed a decrease in the aspect ratio of the clay particles and a reduction in the size of elastomer particles with increasing clay content. In addition, WAXD scans indicated a skin-core effect for the injection molded specimens in terms of both polypropylene crystal orientation and clay filler orientation. This information is essential for the understanding of the mechanism of mechanical property enhancement in nanocomposite materials.     

Preparation and properties of styrene–butadiene rubber based nanocomposites: The influence of the structural and processing parameters

Rubber‐based nanocomposites were prepared with octadecyl amine modified sodium montmorillonite clay and styrene–butadiene rubber with different styrene contents (15, 23, and 40%). The solvent used to prepare the nanocomposites, the cure conditions, and the cure system were also varied to determine their effect on the properties of the nanocomposites. All the composites were characterized with X‐ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and transmission electron microscopy (TEM). The XRD studies revealed exfoliation for the modified clay–rubber composites. The TEM photomicrographs showed a uniform distribution of the modified clay in the rubber matrix. The thickness of the particles in the exfoliated composites was around 10–15 nm. Although the FTIR study of the unmodified and modified clays showed extra peaks due to the intercalation of the amine chains into the gallery, the spectra for the rubber–clay nanocomposites were almost the same because of the presence of a very small amount of clay in the rubber matrix. All the modified clay–rubber nanocomposites displayed improved mechanical strength. The styrene content of the rubber had a pronounced effect on the properties of the nanocomposites. With increasing styrene content, the improvement in the properties was greater. Dicumyl peroxide and sulfur cure systems displayed similar strength, but higher elongation and slightly lower modulus values were obtained with the sulfur cure system. The curing of the samples at four different durations at 160°C showed that the cure time affected the properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 698–709, 2004     

Effects of mixing protocols on impact modified poly(lactic acid) layered silicate nanocomposites

Poly(lactic acid)/2 wt % organomodified montmorillonite (PLA/OMMT) was toughened by an ethylene‐methyl acrylate‐glycidyl methacrylate (E‐MA‐GMA) rubber. The ternary nanocomposites were prepared by melt compounding in a twin screw extruder using four different addition protocols of the components of the nanocomposite and varying the rubber content in the range of 5–20 wt %. It was found that both clay dispersion and morphology were influenced by the blending method as detected by X‐ray diffraction (XRD) and observed by TEM and scanning electron microscopy (SEM). The XRD results, which were also confirmed by TEM observations, demonstrated that the OMMT dispersed better in PLA than in E‐MA‐GMA. All formulations exhibited intercalated/partially exfoliated structure with the best clay dispersion achieved when the clay was first mixed with PLA before the rubber was added. According to SEM, the blends were immiscible and exhibited fine dispersion of the rubber in the PLA with differences in the mean particle sizes that depended on the addition order. Balanced stiffness‐toughness was observed at 10 wt % rubber content in the compounds without significant sacrifice of the strength. High impact toughness was attained when PLA was first mixed with the clay before the rubber was added, and the highest tensile toughness was obtained when PLA was first compounded with the rubber, and then clay was incorporated into the mixture. Thermal characterization by DSC confirmed the immiscibility of the blends, but in general, the thermal parameters and the degree of crystallinity of the PLA were not affected by the preparation procedure. Both the clay and the rubber decreased the crystallization temperature of the PLA by acting as nucleating agents. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41518.     

Ethylene–octene copolymer (engage)–clay nanocomposites: Preparation and characterization

In this work, preparation and properties of nanoclay modified by organic amine (octadecyl amine, a primary amine) and Engage (ethylene–octene copolymer)–clay nanocomposites are reported. The clay and rubber nanocomposites have been characterized with the help of Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and X‐ray diffraction (XRD). The X‐ray results suggest that the intergallery spacing of pristine clay increases with the incorporation of the amine. The XRD peak observed in the range of 3–10° for the modified clay also disappears in the rubber nanocomposites at low loading. TEM photographs show exfoliation of the clays in the range of 10–30 nm in Engage. In the FTIR spectra of the nanocomposite, there are common peaks for the virgin rubber as well as those for the clay. Excellent improvement in mechanical properties, like tensile strength, elongation at break, and modulus, is observed on incorporation of the nanoclay in Engage. The storage modulus increases, tan δ peak decreases, and the glass transition temperature is shifted to higher temperature. The results could be explained with the help of morphology, dispersion of the nanofiller, and its interaction with the rubber. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 603–610, 2006     

Preparation and properties of ethylene propylene rubber (EPR)–clay nanocomposites based on maleic anhydride‐modified EPR and organophilic clay

Ethylene propylene rubber–clay nanocomposites (EPR–CNs) were prepared by melt‐compounding maleic anhydride modified EPR (EPR‐MA) with organophilic clay, and their properties were examined. Silicate layers of organophilic clay were found to exfoliate and homogeneously disperse into the nanometer level in the nanocomposites by transmission electron microscopy observation. EPR–CNs exhibited higher tensile moduli compared to EPR‐MA and composites containing conventional fillers such as carbon black, talc. The storage moduli of EPR–CNs were also higher than those of EPR‐MA and the conventional composites. Creep resistances of EPR–CNs were much improved compared for EPR‐MA. Degree of swelling in hexadecane was remarkably restricted. Improvement of these properties is caused because dispersed silicate layers have much large interface with the EPR matrix and are thought to strongly restrain the EPR polymer chains. Nanocomposite technology using small amount of silicate layers is useful to improve properties of thermoplastic elastomer. Various kinds of thermoplastic elastomers are expected to be produced by loading of silicate layers with or without conventional fillers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 758–764, 2004     

Mechanical properties and failure surface morphology of amine‐cured epoxy/clay nanocomposites

The tensile and impact properties of amine‐cured diglycidyl ether of bisphenol A based nanocomposites reinforced by organomontmorillonite clay nanoplatelets are reported. The sonication processing scheme involved the sonication of the constituent materials in a solvent followed by solvent extraction to generate nanocomposites with homogeneous dispersions of the organoclay nanoplatelets. The microstructure of the clay nanoplatelets in the nanocomposites was observed with transmission electron microscopy, and the clay nanoplatelets were well dispersed and were intercalated and exfoliated. The tensile modulus of epoxy at room temperature, which was above the glass‐transition temperature of the nanocomposites, increased approximately 50% with the addition of 10 wt % (6.0 vol %) clay nanoplatelets. The reinforcing effect of the organoclay nanoplatelets was examined with respect to the Tandon–Weng and Halpin–Tsai models. The tensile strength was improved only when 2.5 wt % clay nanoplatelets were added. The Izod impact strength decreased with increasing clay content. The failure surfaces of the nanocomposites were observed with environmental scanning electron microscopy and confocal laser scanning microscopy. The roughness of the failure surface was correlated with the tensile strength. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 281–287, 2005     

Organic interfacial tailoring of styrene butadiene rubber–clay nanocomposites prepared by latex compounding method

The styrene butadiene rubber (SBR)–clay nanocompounds were prepared by the latex compounding method, and then hexadecyl trimethyl ammonium bromide (C16) and 3‐aminopropyl triethoxy silane (KH550) were added into these nanocompounds on a two‐roll mill to prepare nanocomposites with strong interfacial interaction. The structure and properties of SBR–clay nanocomposites were carefully studied by X‐ray diffraction (XRD) studies, transmission electron microscopy (TEM), Rubber Process Analyzer (RPA), and mechanical testing. Compared with unmodified nanocomposites, the dispersion structure of modified SBR–clay nanocomposites is better with part rubber‐intercalated or part modifier‐intercalated structure. The tensile strength and the modulus at 300% elongation of modified SBR–clay nanocomposites are higher than three times of those of unmodified nanocomposites, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1826–1833, 2007     

Polyamide 6/clay nanocomposites using a cointercalation organophilic clay via melt compounding

Polyamide 6/clay nanocomposites (PA6CN) were prepared via the melt compounding method by using a new kind of organophilic clay, which was obtained through cointercalation of epoxy resin and quaternary ammonium into Na‐montmorillonite. The dispersion effect of this kind of organophilic clay in the matrix was studied by means of X‐ray diffraction (XRD) and transmission electron microscopy (TEM); the silicate layers were dispersed homogeneously and nearly exfoliated in the matrix. This was probably the result of the strong interaction between epoxy groups and amide end groups of PA6. The mechanical properties and heat distortion temperature (HDT) of PA6CN increased dramatically. The notched Izod impact strength of PA6CN was 80% higher than that of PA6 when the clay loading was 5 wt %. Even at 10 wt % clay content, the impact strength was still higher than that of PA6. The finely dispersed silicate layers and the strong interaction between silicate layers and matrix decreased the water absorption. At 10 wt % clay content, PA6CN only absorbs half the amount of water compared with PA6. The dynamic mechanical properties of PA6CN were also studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 953–958, 2003     

Electrolytic admicellar polymerization of pyrrole on natural rubber/clay nanocomposites

Organic–inorganic composites consisting of natural rubber (NR), polypyrrole (PPy), and sodium montmorillonite (Na‐MMT) were synthesized via electrolytic admicellar polymerization. A constant potential of 9 volts was chosen for the synthesis. The PPy concentration was fixed at 100 mM, and the clay contents were varied from 1 to 7 parts per hundred of rubber (phr). The synthesized nanocomposites were characterized by Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), scanning electron microscopy, and transmission electron microscopy (TEM), together with thermal stability (TGA), mechanical properties, and electrical conductivity (σ_dc) studies. The FTIR spectra indicated the characteristic peaks of both PPy and MMT clay and also evidenced a slight interaction between the PPy chain and the clay layers, verifying the success of electrolytic admicellar polymerization. XRD and TEM results pointed out the good dispersion of clay platelets in the polymer matrix, suggesting an exfoliated structure. The morphology of the nanocomposites was greatly dependent on the amount of MMT clay, especially at a 7 phr loading. The initial modulus and tensile strength of the nanocomposites containing the 7 phr loading were about four and two times higher, compared with unfilled NR/PPy, respectively. Thermal stability studies revealed a slight improvement in the decomposition temperature for the PPy component by the clay layers, whereas the opposite trend was found for the NR component. More interestingly, the electrical conductivity of the admicelled rubber increased significantly (～ 19–32 times) with increasing clay contents from 1 to 7 phr, in comparison with unfilled NR/PPy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphology and properties of PVC/clay nanocomposites via in situ emulsion polymerization

PVC/Na⁺–montmorillonite (MMT) nanocomposites were prepared via a simple technique of emulsion polymerization at several different MMT clay concentrations. X‐ray diffraction and transmission electron microscopy studies revealed the formation of a mixture of intercalated and exfoliated nanostructure. Tensile testing results showed that the tensile modulus of the nanocomposites increased with the addition of clay, while the tensile strength decreased little. The notched impact strength of the nanocomposites was also improved. For systems containing clay in the range of 2.1 to 3.5 wt %, the impact strength was almost two times as large as that of pure PVC. However, those mechanical properties began to decrease with the continuously increasing amount of clay. The fracture surface of pure PVC and the nanocomposites was observed by scanning electron microscope. Thermal properties of the nanocomposites were found to increase as a result of clay incorporation. The glass transition temperatures of the PVC/clay nanocomposites were nearly identical to that of pure PVC. The Vicat softening points exhibited a progressively increasing trend with the clay content added. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 277–286, 2004     

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

Nanocomposites containing a thermoplastic blend and organophilic layered clay (organoclay) were produced by melt compounding. The blend composition was kept constant [polyamide 6 (PA6) 70 wt % + polypropylene (PP) 30 wt %], whereas the organoclay content was varied between 0 and 10 wt %. The mechanical properties of the nanocomposites were determined on injection‐molded specimens in both tensile and flexural loading. Highest strength values were observed at an organoclay content of 4 wt % for the blends. The flexural strength was superior to the tensile one, which was traced to the effect of the molding‐induced skin‐core structure. Increasing organoclay amount resulted in severe material embrittlement reflected in a drop of both strength and strain values. The morphology of the nanocomposites was studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy‐dispersion X‐ray analysis (EDX), and X‐ray diffraction (XRD). It was established that the organoclay is well dispersed (exfoliated) and preferentially embedded in the PA6 phase. Further, the exfoliation degree of the organoclay decreased with increasing organoclay content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 175–189, 2004     

Synthesis and characterization of elastomeric polyurethane and PU/clay nanocomposites based on an aliphatic diisocyanate

This investigation reports preparation of polyurethane and polyurethane/clay nanocomposites based on polyethylene glycol, isophorone diisocyanate (IPDI), an aliphatic diisocyanate and 1,4‐ Butanediol as chain extender by solution polymerization. In this case PU/clay nanocomposites were prepared via ex‐situ method using 1, 3, and 5 wt % of Cloisite 30B. Thermogravimetric analysis showed that the maximum decomposition temperature (T_max) of the PU/clay nanocomposite is much higher than the pristine PU. The tensile properties improved upon increasing the organoclay (Cloisite 30B) content upto 3 wt %, and then decreased to some extent upon further increasing the nanoparticle loading to 5 wt %. Optical properties of the nanocomposites were studied by UV‐vis spectrophotometer. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) were used to study the morphology of the nanocomposites. It was observed that with the incorporation of 3 wt % nanoclay the crystallinity in PU nanocomposite increases, then diminishes with further loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3328–3334, 2013     

Polyamide 66/Clay Nanocomposites via Melt Intercalation

Polyamide 66/clay nanocomposites (PA66CN) were prepared via a melt compounding method using a new kind of organophilic clay, which was obtained through co‐intercalation of epoxy resin and quaternary ammonium into Na‐montmorillonite. The dispersion effect of silicate layers in the matrix was studied by means of XRD and TEM. The silicate layers were dispersed homogeneously and nearly exfoliated in the matrix as a result of the strong interaction between epoxy groups and PA66. The mechanical properties and heat distortion temperature (HDT) of PA66CN increased dramatically. The notched Izod impact strength of PA66CN was 50% higher than that of PA66 when the clay loading was 5 wt.‐%. Even at 10 wt.‐% clay content, the impact strength was still higher than that of PA66. The finely dispersed silicate layers and the strong interaction between silicate layers and the matrix reduced the water absorption, at 10 wt.‐% clay content; PA66CN only absorbs 60% water compared with PA66. The addition of silicate layers changed the crystal structure in PA66CN.     

TPO based nanocomposites. Part 2. Thermal expansion behavior

The linear thermal expansion behavior of thermoplastic polyolefin, or TPO, nanocomposites based on a polypropylene/elastomer/masterbatch mixture was examined using a thermomechanical analyzer (TMA). For these experiments the masterbatch consisted of a mixture of organoclay and maleated polypropylene. The nanocomposites were prepared in a twin-screw extruder. The effects of both the elastomer domains and the filler particles on the thermal expansion behavior of the nanocomposites were investigated by means of transmission electron microscopy (TEM) and atomic force microscopy (AFM). The addition of elastomer tends to increase the linear coefficient of thermal expansion, CTE. On the other hand, the addition of clay significantly reduces the thermal expansion in both the flow (FD) and transverse directions (TD) of injection molded specimens; however, the extent of reduction of CTE in the FD is much greater than in the TD. The CTE in the normal direction (ND) increases when either the clay or elastomer content is increased. The trends in thermal expansion for the nanocomposites are discussed in terms of the morphology of both dispersed clay and elastomer phases based on TEM and AFM observations and subsequent particle analyses.     

Use of purified and modified bentonites in linear low‐density polyethylene/organoclay/compatibilizer nanocomposites

Polyethylene‐based ternary nanocomposites were prepared with different clay structures, obtained by the modification of purified Resadiye bentonite as the reinforcement, a random terpolymer of ethylene, butyl acrylate, and maleic anhydride with the trade name Lotader3210 as the compatibilizer, and linear low‐density polyethylene (LLDPE) as the polymer matrix in an intensive batch mixer. The quaternary ammonium/phosphonium salts used for the modification of bentonite were dimethyldioctadecyl ammonium (DMDA) chloride (Cl), tetrakisdecyl ammonium (TKA) bromide (Br), and tributylhexadecyl phosphonium (TBHP) Br. The effects of the physical properties and structure of the organoclay on the clay dispersion were studied at different clay contents (2 and 5 wt %) and at a compatibilizer/organoclay ratio of 2.5. The extent of organoclay dispersion was determined by X‐ray diffraction (XRD) and was verified by transmission electron microscopy (TEM), mechanical testing, and rheological analysis. XRD analysis showed that the nanocomposite with the organoclay DMDA contained intercalated silicate layers, as also verified by TEM. The TEM analysis of the nanocomposites with TBHP exhibited intercalated/partially exfoliated clay dispersion. TKA, with a crowded alkyl environment, sheltered and hindered the intercalation of polymer chains through the silicate layers. In comparison to pure LLDPE, nanocomposites with a 33–41% higher Young's modulus, 16–9% higher tensile strength, and 75–144% higher elongation at break were produced with DMDA and TBHP, respectively (at 5 wt % organoclay). The storage modulus increased by 807–1393%, and the dynamic viscosity increased by 196–339% with respect to pure LLDPE at low frequencies for the samples with DMDA and TBHP (at 5 wt % organoclay). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Bio‐based polymer nanocomposites based on layered silicates having a reactive and renewable intercalant

Soybean oil‐based polymer nanocomposites were synthesized from acrylated epoxidized soybean oil (AESO) combined with styrene monomer and montmorillonite (MMT) clay by using in situ free radical polymerization reaction. Special attention was paid to the modification of MMT clay, which was carried out by methacryl‐functionalized and quaternized derivative of methyl oleate intercalant. It was synthesized from olive oil triglyceride, as a renewable intercalant. The resultant nanocomposites were characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effect of increased nanofiller loading in thermal and mechanical properties of the nanocomposites was investigated by thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The nanocomposites exhibited improved thermal and dynamic mechanical properties compared with neat acrylated epoxidized soybean oil based polymer matrix. The desired exfoliated nanocomposite structure was achieved when the OrgMMT loading was 1 and 2 wt % whereas partially exfoliated nanocomposite was obtained in 3 wt % loading. It was found that about 400 and 500% increments in storage modulus at glass transition and rubbery regions, respectively were achieved at 2 wt % clay loading compared to neat polymer matrix while the lowest thermal degradation rate was gained by introducing 3 wt % clay loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2031–2041, 2013     

Phenolic resin‐crosslinked natural rubber/clay nanocomposites: Influence of clay loading and interfacial adhesion on strain‐induced crystallization behavior

Nanocomposites of natural rubber (NR) and pristine clay (clay) were prepared by latex mixing, then crosslinked with phenolic resin (PhOH). For comparative study, the PhOH‐crosslinked neat NR was also prepared. Influence of clay loading (i.e., 1, 3, 5, and 10 phr) on mechanical properties and structural change of PhOH‐crosslinked NR/clay nanocomposites was studied through X‐ray diffraction (XRD), transmission electron microscopic (TEM), wide‐angle X‐ray diffraction (WAXD), tensile property measurement, and Fourier transform infrared spectroscopy (FTIR). XRD and TEM showed that the clay was partly intercalated and aggregated, and that the dispersion state of clay was non‐uniform at higher clay loading (>5 phr). From tensile test measurement, it was found that the pronounced upturn of tensile stress was observed when the clay loading was increased and a maximum tensile strength of the PhOH‐crosslinked NR/clay nanocomposites was obtained at 5 phr clay. WAXD observations showed that an increased addition of clay induced more orientation and alignment of NR chains, thereby lowering onset strain of strain‐induced crystallization and promoting crystallinity of the NR matrix during tensile deformation. FTIR investigation indicated a strong interfacial adhesion between NR matrix and clay filler through a phenolic resin bridge. This suggested that the PhOH did not only act as curative agent for crosslinking of NR, but it also worked as coupling agent for promoting interfacial reaction between NR and clay. The presence of strong interfacial adhesion was found to play an important role in the crystallization process, leading to promotion of mechanical properties of the PhOH‐crosslinked NR/clay nanocomposites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43214.