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     

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     

Synthesis and characterization of cationic gemini surfactant modified Na–bentonite and its applications for rubber nanocomposites

A cationic gemini surfactant (N‐isopropyl‐N , N‐dimethyldodecan 1‐aminium bromide) was synthesized by quaternization reaction. The synthesized surfactant was characterized by Fourier transform infrared (FTIR) and proton nuclear magnetic resonance (1H NMR) spectroscopy. Modified Na–bentonite (organoclay) was obtained by the intercalation of a gemini surfactant between the layers of sodium bentonite and characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), FTIR, thermogravimetry–differential thermal analysis (TGA–DTA) and differential scanning calorimetry (DSC) techniques. The results of XRD, TEM, FTIR, TGA, and corresponding DSC analysis indicate that gemini surfactant has been successfully intercalated into the clay layers. Rubber‐based nanocomposites have been prepared by incorporating various concentration of organically modified bentonite on to natural rubber/styrene–butadiene rubber (NR/SBR) rubber blend (75/25) using two roll mill. Effect of organoclay content on XRD, curing, mechanical, and scanning electron microscopy (SEM) properties of the nanocomposites are investigated. The morphological study showed the intercalation of nanoclay in NR/SBR blend chain. It was found that the organoclay decrease the optimum and scorch time of the curing reaction, increase maximum torque and the curing rate, which was attributed to the further intercalation during vulcanization process. Mechanical properties such as tensile strength, modulus and elongation at break have improved. POLYM. COMPOS., 38:396–403, 2017. © 2015 Society of Plastics Engineers     

Preparation,structure and properties of nitrile–butadiene rubber–organoclay nanocomposites by reactive mixing intercalation method

The nanocomposites of nitrile–butadiene rubber (NBR) and organo‐montmorillonite modified by hexadecyltrimethyl ammonium bromide (HMMT) were prepared by the reactive mixing intercalation method in the presence of the resorcinol and hexamethylenetetramine complex (RH). The structure of the NBR–RH–HMMT nanocomposites was characterized by XRD, TEM, FTIR, determination of crosslinking density, and so on. The results showed that the d‐spacing of HMMT increased substantially with RH addition and the layers of HMMT were dispersed in rubber matrix on a nanometer scale. The mechanical properties of the NBR–RH–HMMT nanocomposites were far superior to those of NBR–HMMT composites, and the glass transition temperature of NBR–RH–HMMT nanocomposite was higher than that of NBR. The reactive mixing intercalation method by introducing RH could enhance the interface combination between the rubber and the organoclay through the interactions of RH with NBR and modified clay. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1905–1913, 2006     

Preparation and characterization of nanocomposites based on thermoplastic elastomers from rubber–plastic blends

In the present work, thermoplastic elastomer (TPE)–clay nanocomposites (TPN) based on different rubber–plastic blends from ethylene–octene copolymer [Engage]–Polypropylene and brominated poly(isobutylene‐co‐paramethyl styrene)–nylon 6 were prepared by melt blending. Hexadecyltrimethylammonium bromide and octadecyl amine‐modified sodium montmorillonite were used as organoclays. The nanocomposites were prepared by adding the nanoclay separately into the rubber and plastic phases. The TPNs were characterized with the help of transmission electron microscopy (TEM) and X‐ray diffraction. The X‐ray diffraction peaks observed in the range of 3–10° for the modified clays disappeared in the thermoplastic elastomeric nanocomposites. TEM photographs showed exfoliation and intercalation of the clays in the range of 20–30 nm in the particular phase where the clay was added. Excellent improvement in mechanical properties like tensile strength, elongation at break, and modulus was observed on incorporation of the nanoclays in the rubber phase of TPN. When the nanoclay was added to the plastic phase, the mechanical reinforcement is comparatively poorer due to partial destruction of the crystallinity. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1645–1656, 2006     

Effect of carbon black on properties of rubber nanocomposites

Polymer based nanocomposites were prepared using brominated poly(isobutylene‐co‐paramethylstyrene) (BIMS) rubber and octadecyl amine modified montmorillonite nanoclay. The effect of nature and loading of carbon black on these nanocomposites and the control BIMS was investigated thoroughly using X‐ray diffraction technique (XRD), Fourier transform infrared spectroscopy (FTIR), and mechanical properties. The addition of 4 parts of the modified nanoclay to 20 phr N550 carbon black filled samples increased the tensile strength by 53%. Out of the three different grades of carbon black (N330, N550, and N660), N550 showed the best effect of nanoclay. Optimum results were obtained with the 20 phr filler loading. For comparison, china clay and silica at the same loading were used. Fifty‐six and 46% improvements in tensile strength were achieved with 4 parts of nanoclay added to the silica and the china clay filled samples, respectively. N330 carbon black (20 parts) filled styrene butadiene rubber (SBR) based nanocomposite registered 20% higher tensile strength with 4 parts of the modified nanoclay. In all the above carbon black filled nanocomposites, the modulus was improved in the range of 30 to 125%. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 443–451, 2005     

Radiation induced modification of NBR and SBR montmorillonite nanocomposites

Nanocomposites of two different kinds of rubber (acrylonitrile-butadiene rubber NBR and styrene butadiene rubber SBR)/organo-montmorillonite nanocomposites modified by hexadecyltrimethyl ammonium bromide were prepared by the reactive mixing intercalation method in the presence of trimethylolpropane trimethylmethacrylate (TMPTMA). The influence of gamma irradiation on the morphology and properties of the rubber nanocomposites was investigated. Intercalated polar or unsaturated matrices (e.g., NBR and SBR)/OMMT nanocomposites can be obtained, which was confirmed by X-ray diffraction (XRD). The clay layers could be uniformly dispersed in the rubber matrix on the nanometer level. Mechanical tests showed that the nanocomposites had good mechanical properties as compared to the neat composites. The results also showed that the irradiated NBR/OMMT nanocomposites had higher thermal stabilities than irradiated SBR/OMMT nanocomposites.     

Morphology and mechanical properties of clay/styrene‐butadiene rubber nanocomposites

Based on the character of a clay that could be separated into many 1‐nm thickness monolayers, clay styrene‐butadiene rubber (SBR) nanocomposites were acquired by mixing the SBR latex with a clay/water dispersion and coagulating the mixture. The structure of the dispersion of clay in the SBR was studied through TEM. The mechanical properties of clay/SBR nanocomposites with different filling amounts of clay were studied. The results showed that the main structure of the dispersion of clay in the SBR was a layer bundle whose thickness was 4–10 nm and its aggregation formed by several or many layer bundles. Compared with the other filler, some mechanical properties of clay/SBR nanocomposites exceeded those of carbon black/SBR composites and they were higher than those of clay/SBR composites produced by directly mixing clay with SBR through regular rubber processing means. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1873–1878, 2000     

Morphology and mechanical properties of layered silicate reinforced natural and polyurethane rubber blends produced by latex compounding

Natural rubber (NR), polyurethane rubber (PUR), and NR/PUR‐based nanocomposites were produced from the related latices by adding a pristine synthetic layered silicate (LS; sodium fluorohectorite) in 10 parts per hundred parts rubber (phr). The dispersion of the LS latices in the composite was studied by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Further information on the rubber/LS interaction was received from Fourier transform infrared spectroscopy (FTIR) and dynamic mechanical thermal analysis (DMTA). Tensile and tear tests were used to characterize the performance of the rubber nanocomposites. It was found that LS is more compatible and thus better intercalated by PUR than by NR. Further, LS was preferably located in the PUR phase in the blends, which exhibited excellent mechanical properties despite the incompatibility between NR and PUR. Nano‐reinforcement was best reflected in stiffness‐ and strength‐related properties of the rubber composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 543–551, 2004     

Synthesis and characterization of styrene butadiene rubber—Bentonite clay nanocomposites

In the present study, naturally occurring unfractionated bentonite clay was used to prepare styrene butadiene rubber/bentonite clay nanocomposite by latex stage blending. The bentonite clay was organo‐modified by in situ resol formation by the reaction of resorcinol and formaldehyde. The latex clay mixture was co‐coagulated with acid. The resulting clay masterbatch was compounded and evaluated by Fourier Transform Infrared spectroscopy, X‐ray diffraction (XRD), Transmission Electron Microscopy (TEM), Energy Dispersive X‐ray spectroscopy (EDS), Scanning Electron Microscopy, Thermogravimetric analysis, and Differential Scanning Calorimetry. XRD showed that the interplanar distance of the in situ resol‐modified bentonite clay increased from 1.23 to 1.41 nm for the unmodified bentonite. TEM analysis indicated partial exfoliation and/or intercalation. EDS (Si and Al mapping) of the clay revealed the nature of the dispersion in the nanocomposites vis‐à‐vis the conventional styrene‐butadiene rubber (SBR)/bentonite clay composite. Thermogravimetric analysis was used to compare the decomposition trends of the SBR/clay nanocomposites with the SBR/clay composite. The glass transition temperature of SBR/clay nanocomposites increased as compared with that of neat SBR. Substantial improvement in most of the other mechanical properties was also observed in case of the nanocomposites. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

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     

Effect of PEgMA/amine silane compatibilizer on clay dispersion of polyethylene-clay nanocomposites

The compatibilization effects provided by an amine silane modified polyethylene (PEgAS) versus those by a maleated polyethylene (PEgMA), for forming PE–clay based nanocomposites, were studied. PEgAS was prepared by condensation reaction between PEgMA and g-(aminopropyl) triethoxy silane (APTS). It had the triethoxy-silane functionality on one end and was solution mixed with an organomodified clay (Cloisite 20A) to promote the reaction of the silane groups with the hydroxyl groups on the surface of the clay. The obtained masterbatches were then compounded with PE to obtain PE–clay nanocomposites by melt blending in a twin screw extruder, using different compatibilizers and clay contents. FTIR, XRD, STEM, and Instron were used to characterize the structural, morphological, and mechanical properties of the nanocomposites. Results showed that the PEgAS formed more exfoliated–intercalated morphology and better mechanical properties, especially in modulus and tensile strength as compared with PEgMA composites and neat PE. The Young modulus was 35% higher, and the tensile strength was 18% higher with PEgAS composites.     

Thermoplastic elastomeric nanocomposites from poly[styrene–(ethylene‐co‐butylene)–styrene] triblock copolymer and clay: Preparation and characterization

Thermoplastic elastomer (TPE)–clay nanocomposites based on poly[styrene–(ethylene‐co‐butylene)–styrene] triblock copolymer (SEBS) were prepared. Natural sodium montmorillonite (MMT) clay was organically modified by octadecyl amine to produce an amine‐modified hydrophobic nanoclay (OC). Commercially available Cloisite 20A (CL20) and Cloisite 10A, tallow ammine modified nanoclays, were also used. The intergallery spacing of MMT increased on amine modification as suggested by the shifting of the X‐ray diffraction (XRD) peak from 7.6 to 4.5 and 3.8° in the cases of OC and CL20, respectively. The latter demonstrated no XRD peak when it was used at 2 and 4 parts phr in the SEBS system. Transmission electron microscopy studies showed the intercalation–exfoliation morphology in SEBS containing 4 parts of CL20₄–SEBS, agglomeration in SEBS having 4 parts of MMT, and mixed morphology in SEBS with 4 parts of OC systems. Locations of the clay particles were indicated by the atomic force micrographs. Mechanical and dynamic mechanical thermal analysis studies confirmed the best properties with the CL20₄–SEBS nanocomposites. Significant improvements in mechanical properties such as tensile strength, modulus, work to break, and elongation at break were achieved with the CL20₄–SEBS in polymer‐layered silicate nanocomposites. Dynamic mechanical studies further showed the affinity of the organoclays toward both segments of the TPE and a compatibilization effect with CL20 at a 4‐phr loading. Atomic force microscopy showed distinctly different morphologies in nanocomposites prepared through solution and melt processing. Comparisons of the mechanical, dynamic mechanical, and morphological properties of the nanocomposites prepared by melt and solution intercalation processes were done. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2040–2052, 2006     

Preparation and properties of polyethylene–clay nanocomposites by an in situ graft method

The polyethylene–clay nanocomposites were prepared by the in situ graft copolymerization of styrene containing twin‐benzyldimethyldioctadecylammonium bromine modified montmorillonite (TBDO‐MMT) in polyethylene with dicumyl peroxide (DCP) as an initiator in molten state. XRD and TEM analysis indicated that intercalated polyethylene/MMT nanocomposites are obtained. The mechanics performance, crystal behavior, thermal properties, and the effect of MMT contents on PE/MMT nanocomposite were also studied. As comparison, polyethylene/montmorillonite composites prepared by a simply melt compounding without styrene were studied as well. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4921–4927, 2006     

Preparation and characterization of rubber–clay nanocomposites

Rubber–clay nanocomposites were prepared by two different methods and characterized with TEM and XRD. The TEM showed clay had been dispersed to one or several layers. The XRD showed that the basal spacing in the clay was increased. It was evident that some macromolecules intercalated to the clay layer galleries. The clay layer could be uniformly dispersed in the rubber matrix on the nanometer level. The mechanical tests showed that the nanocomposites had good mechanical properties. Some properties exceeded those of rubber reinforced with carbon black, so the clay layers could be used as an important reinforcing agent as the carbon black was. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1879–1883, 2000     

Mechanical and thermal behavior of styrene butadiene rubber composites reinforced with silane-treated peanut shell powder

Biocomposites of styrene butadiene rubber (SBR) reinforced with silane-treated peanut shell powder (SPSP) of different filler loadings and particle sizes were prepared by two roll mixing mills with sulfur as a vulcanizing agent. The cure characteristics of composites were studied, and they vulcanized at 160 °C. Test samples were prepared by compression moulding, and their physicomechanical properties, such as tensile strength tear strength, modulus, hardness, and abrasion resistance of SBR vulcanizates, were studied with filler loading 0, 5, 10, 15, and 20 parts per hundred rubber (phr). Composites with 10 phr filler having small particle size exhibited better properties. The interfacial adhesion between filler and matrix has a major role in the properties of composites. Surface modification of PSP was done by silane coupling agent to improve the interfacial adhesion and it characterised by FTIR, XRD, TGA, UV, and SEM. Better properties are shown by the composites with SPSP. Thermal stability of the composites was also determined using thermogravimetric analysis.     

Preparation,characterization, and application of NR/SBR/Organoclay nanocomposites in the tire industry

The natural rubber/styrene butadiene rubber/organoclay (NR/SBR/organoclay) nanocomposites were successfully prepared with different types of organoclay by direct compounding. The optimal type of organoclay was selected by the mechanical properties characterization of the NR/SBR/organoclay composites. The series of NR/SBR/organoclay (the optimal organoclay) nanocomposites were prepared with various organoclay contents loading from 1.0 to 7.0 parts per hundreds of rubber (phr). The nearly completely exfoliated organoclay nanocomposites with uniform dispersion were confirmed by transmission electron microscopy (TEM) and X‐ray diffraction (XRD). The results of mechanical properties measurement showed that the tensile strength, tensile modulus, and tear strength were improved significantly when the organoclay content was less than 5.0 phr. The tensile strength and the tear strength of the nanocomposite with only 3.0 phr organoclay were improved by 92.8% and 63.4%, respectively. It showed organoclay has excellent reinforcement effect with low content. The reduction of the score and cure times of the composites indicated that the organoclay acted as accelerator in the process of vulcanization. The incorporation of a small amount of organoclay greatly improved the swelling behavior and thermal stability, which was attributed to the good barrier properties of the dispersed organoclay layers. The outstanding performance of co‐reinforcement system with organoclay in the tire formulation showed that the organoclay had a good application prospect in the tire industry, especially for the improvement of abrasion resistance and the reduction of production cost. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of organoclay reinforcement on the curing characteristics and technological properties of styrene–butadiene rubber

Rubber nanocomposites based on styrene–butadiene rubber (SBR) and organophilic layered silicate were prepared. Clay structures based on dodecyl benzene sulfonic acid (DBSA), nonyl phenol ethoxylate (NPE), and DBSA/NPE (50/50%) were prepared and characterized. The results indicate the intercalation of the used surfactants within the clay layers. Varying amount of organoclay, 2, 4, 6, 8, and 10 (phr), was added to the SBR matrix. X‐ray diffraction revealed exfoliated structure for the modified clay–SBR composites. No new component in the rubber was found by fourier transform infrared measurements (FTIR). Scanning electron microscopy showed a uniform distribution of the modified clay with mixed DBSA/NPE (6 phr) in the matrix. The rheometric characteristics and physicomechanical properties of the SBR compounds were analyzed. The effect of DBSA/NPE clay loading on aging resistance of SBR nanocomposites at 90 ± 1°C for 4 and 7 days was also investigated. Rubber nanocomposites displayed an increase in the minimum and maximum torques, acceleration of the vulcanization process, and improved mechanical properties, with organoclay content up to 6 phr. This effect was more noticeable in the presence of the treated clay with DBSA/NPE. Also incorporation of DBSA/NPE‐clay (6 phr) resulted in significant improvement of the degradation profile of the nanocomposites at 90 ± 1°C for 4 days. POLYM. COMPOS., 36:1293–1302, 2015. © 2014 Society of Plastics Engineers     

Tough hyperbranched epoxy/poly(amido‐amine) modified bentonite thermosetting nanocomposites

A tough and highly flexible hyperbranched epoxy and poly(amido‐amine) modified bentonite based thermosetting nanocomposite was demonstrated. The FTIR, XRD, and TGA analyses confirmed the modification of bentonite. The formation of partially exfoliated structure of the nanocomposite with good physicochemical interactions among the hyperbranched epoxy, poly(amido‐amine) hardener and modified clay was investigated by the FTIR, XRD, SEM, and TEM analyses. Significant improvements of 750% toughness, 300% elongation at break, 50% tensile strength, 300% modulus, and 250% adhesive strength of the pristine epoxy were achieved by the formation of nanocomposites with 3 wt % of modified clay. The experimental modulus values of the nanocomposites were compared with three theoretical models to account the interactions between filler and matrix. Thus, the studied epoxy nanocomposite has great potential to be used as an advanced epoxy thermoset. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40327.     

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

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