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.     

熔体法制备有机黏土/橡胶纳米复合材料的结构及性能

将有机黏土(OC)分别加入到天然橡胶(NR)、丁苯橡胶(SBR)、丁基橡胶(IIR)和三元乙丙橡胶(EPDM)中,通过熔体法制备了纳米复合材料。探讨了橡胶黏度及其分子结构对OC在复合材料中分散状况的影响,研究了复合材料的力学性能。结果表明,在以NR为基体的复合材料中。OC片层分散均匀,且剥离程度较高;在SBR,IIR,EPDM中,OC以插层结构为主,且插层效果从大到小的顺序依次为SBR,IIR,EPDM。与相应的纯胶相比,OC／NR纳米复合材料的定伸应力提高,拉伸强度和扯断伸长率有所下降;OC／SBR,OC／IIR,OC／EPDM纳米复合材料的定伸应力变化不大,拉伸强度和扯断伸长率明显提高,且OC／SBR和OC／EPDM复合材料的撕裂强度提高。     

Preparation and properties of nanocomposites based on different polarities of nitrile–butadiene rubber with clay

Nanocomposites were prepared with different grades of nitrile–butadiene rubber (NBR) [with nitrile (CN) contents of 26, 35, and 42%] with organoclay (OC) by a melt‐compounding process. The rubber/clay nanocomposites were examined by transmission electron microscopy (TEM) and X‐ray diffraction (XRD). An increase in the polarity of NBR affected the XRD results significantly. The dispersion level of the nanofiller in the nanocomposites was determined by a function of the polarity of the rubber, the structure of the clay, and their mutual interaction. The intercalated structure and unintercalated structure coexisted in the lower polar of NBR. In addition, a relatively uniformly dispersed state corresponded to a more intercalated structure, which existed in the higher polar of NBR matrix. Furthermore, high‐pressure vulcanization changed the extent of intercalation. The mechanical properties and gas barrier properties were studied for all of the compositions. As a result, an improvement in the mechanical properties was observed along with the higher polarity of NBR. This improvement was attributed to a strong interaction of hydrogen bonding between the CN of NBR and the OH of the clay. Changes in the gas barrier properties, together with changes in the polarity of the rubbers, were explained with the help of the XRD and TEM results. The higher the CN content of the rubber was, the more easily the OC approached to the nanoscale, and the higher the gas barrier properties were. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Study on the morphology,static and dynamic mechanical properties of (styrene butadiene rubber/ethylene propylene diene monomer/organoclay) nanocomposites vulcanized by the gamma radiation

Blends of styrene‐butadiene rubber/ethylene–propylene‐diene monomer (SBR/EPDM) with and without organoclay (OC) were prepared by melt mixing method. Then the samples were vulcanized by gamma radiation in comparison to conventional sulfur curing system. Characterization by X‐ray diffraction analysis, atomic force microscopy, and Field emission scanning electron microscopy revealed the intercalation structure and good dispersion of the OC in prepared nanocomposites. In addition to this, by increasing the absorbed dose of radiation and using OC, reduction in solvent uptake, increase in crosslink density and improvement of mechanical and dynamic–mechanical properties were observed. Comparison of the tensile strength of irradiated nanocomposite with the sulfur cured one's displayed the synergistic effect of the OC and gamma radiation on tensile properties of SBR/EPDM blend. Mooney–Rivlin plot confirmed the increase in crosslink density and interaction between rubbers due to presence of OC and increasing absorbed dose. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43581.     

Effects of Characteristics of Rubber,Mixing and Vulcanization on the Structure and Properties of Rubber/Clay Nanocomposites by Melt Blending

Summary: Three rubber‐based nanocomposites, natural rubber (NR), styrene‐butadiene rubber (SBR), and ethylene‐propylene‐diene rubber (EPDM) matrixes, were prepared with octadecylamine modified fluorohectorite (OC) by melt blending. X‐ray diffraction (XRD) revealed that the SBR/OC and EPDM/OC nanocomposites exhibited a well‐ordered intercalated structure and a disordered intercalated structure, respectively. In the case of the NR/OC nanocomposite, it exhibited an intermediate intercalated and even exfoliated structure. These results were in good agreement with transmission electron microscopy (TEM) observations. Furthermore, in the NR/OC and SBR/OC systems, the mixing process played a predominant role in the formation of nanometer‐scale dispersion structure, whereas the intercalated structure of EPDM/OC formed mainly during the vulcanization process. The tensile strength of SBR/OC and EPDM/OC nanocomposites loading 10 phr OC was 4–5 times higher than the value obtained for the corresponding pure rubber vulcanizate, which could be ascribed to the slippage of the rubber molecules and the orientation of the intercalated OC. For the strain‐induced crystallization NR, the exfoliated OC efficiently improved the modulus of the NR/OC nanocomposite relative to the pure NR. However, its hindrance on NR crystallization during the tensile process may be the main reason for the decrease in tensile strength of NR/OC.

XRD diffraction patterns of three nanocomposites containing 10 phr organoclay.     

Structure and properties of nitrile rubber (NBR)–clay nanocomposites by co‐coagulating NBR latex and clay aqueous suspension

Nitrile rubber (NBR)–clay nanocomposites were prepared by co‐coagulating the NBR latex and clay aqueous suspension. Transmission electron microscopy showed that the silicate layers of clay were dispersed in the NBR matrix at the nano level and had a planar orientation. X‐ray diffraction indicated that there were some nonexfoliated silicate layers in the NBR–clay nanocomposites. Stress–strain curves showed that the silicate layers generated evident reinforcement, modulus, and tensile strength of the NBR–clay nanocomposites, which were significantly improved with an increase in the amount of clay, and strain‐at‐break was higher than that of the gum NBR vulcanizate when the amount of clay was more than 5 phr. The NBR–clay nanocomposites exhibited an excellent gas barrier property; the reduction in gas permeability in the NBR–clay nanocomposites can be described by Nielsen's model. Compared with gum NBR vulcanizate, the oxygen index of the NBR–clay nanocomposites increased slightly. The feasibility of controlling rubber flammability via the nanocomposite approach needs to be evaluated further. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3855–3858, 2003     

Nitrile rubber/organomontmorillonite nanocomposites produced by solution and melt compounding: Effect of the polarity of the quaternary ammonium intercalants

A comparative study of the development of nitrile rubber (NBR) based nanocomposites was performed; two organomontmorillonites (Cloisite 15A and Cloisite 30B) and two procedures for clay dispersion (melt blending and solution intercalation) were used. The nanocomposites were cured with a system based on dicumyl peroxide in the presence of m‐phenylenebismaleimide as a coagent for curing. The dispersion of the organoclay inside the NBR matrix was investigated with transmission electron microscopy and X‐ray diffraction. All the cured systems displayed a combination of intercalated, partially exfoliated clay platelets and confined, deintercalated clay; the degree of dispersion depended on the amount of clay, the type of intercalant, and the intercalation procedure. The highest amount of intercalated/exfoliated clay was obtained with a previous dispersion of the clay (Cloisite 30B) in an NBR solution. All the nanocomposites presented outstanding tensile strength and creep response, and this indicated a reinforcing effect of the layered silicates. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Improvement of properties of silica‐filled styrene–butadiene rubber compounds using acrylonitrile–butadiene rubber

Since silica has strong filler–filler interactions and adsorbs polar materials, a silica‐filled rubber compound has a poor dispersion of the filler and poor cure characteristics. Improvement of the properties of silica‐filled styrene–butadiene rubber (SBR) compounds was studied using acrylonitrile–butadiene rubber (NBR). Viscosities and bound rubber contents of the compounds became lower by adding NBR to the compound. Cure characteristics of the compounds were improved by adding NBR. Physical properties such as modulus, tensile strength, heat buildup, abrasion, and crack resistance were also improved by adding NBR. Both wet traction and rolling resistance of the vulcanizates containing NBR were better than were those of the vulcanizate without NBR. The NBR effects in the silica‐filled SBR compounds were compared with the carbon black‐filled compounds. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1127–1133, 2001     

Molecular simulations of gas transport in nitrile rubber and styrene butadiene rubber

Nitrile rubber (NBR, 39:61 wt% of acrylonitrile:butadiene) and styrene butadiene rubber (SBR, 50:50 wt% of styrene:butadiene) matrices have been equilibrated by molecular dynamics (MD) simulations. Transition-state approach is used to calculate the diffusion and solubility coefficients of small penetrants in these matrices, indicating quite low values in NBR and reasonable agreement with experimental results. MD simulations have been performed to analyze water diffusion in these matrices. Aggregation of water molecules is observed in the hydrophobic matrix SBR. MD simulations with fictitious nonpolar water molecules inhibit aggregation and lead to enhanced diffusion in SBR. In NBR there is a slight increase in diffusion for fictitious water molecules. The lower diffusion constants in NBR result from slower local relaxation of the matrix due to tighter intermolecular packing and higher cohesive energy density. The free volume distribution that affects solubility coefficients is not a major determining factor for the diffusion coefficients in these matrices.     

Acrylonitrile butadiene nanocomposites containing different clays by latex compounding method

Considering elastomers nanocomposites, most of the works are focused on natural rubber, styrene butadiene rubber and rubber blends, while few of them deal with nitrile butadiene rubber (NBR). This article presents the reinforcing effect of two raw sodic montmorillonites (Mts) and one organoclay on NBR matrix prepared by the latex compounding method. Raw Mts increase the mechanical properties of neat matrices. A pseudoplastic behavior is observed with the incorporation of clays into the NBR latex, indicating interactions between polymer chains and clay sheets, in agreement with the results of zeta potential analysis. X‐ray diffraction evaluates changes in the interlayer distance of the clay, indicating the NBR intercalation phenomenon in all cases. Matrices with different clay proportions present variations in the mechanical properties, depending if the aggregation phenomenon is promoted. Morphological analysis of clays and nanocomposites as well as thermal analysis were performed. The variation in mechanical properties after an aging process was studied, evaluating the effects on the tensile strength, ultimate strain and 300% modulus. POLYM. ENG. SCI., 59:736–744, 2019. © 2018 Society of Plastics Engineers     

Preparation and characteristics of nitrile rubber (NBR) nanocomposites based on organophilic layered clay

The effect of clay modification on organo‐montmorillonite/NBR nanocomposites has been studied. Organo‐montmorillonite/NBR nanocomposites were prepared through a melt intercalation process. NBR nanocomposites were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), dynamic mechanical thermal analysis (DMTA) and a universal testing machine (UTM). XRD showed that the basal spacing in the clay increased, which means that the NBR matrix was intercalated in the clay layer galleries. On TEM images, organo‐montmorillonite (MMT) particles were clearly observed, having been exfoliated into nanoscale layers of about 10–20 nm thickness from their original 40 µm particle size. These layers were uniformly dispersed in the NBR matrix. The DMTA test showed that for these nanocomposites the plateau modulus and glass transition temperature (T_g) increased with respect to the corresponding values of pure NBR (without clay). UTM test showed that the nanocomposites had superior mechanical properties, ie strength and modulus. These improved properties are due to the nanoscale effects and strong interactions between the NBR matrix and the clay interface. Copyright © 2003 Society of Chemical Industry     

Nitrile butadiene rubber/hindered phenol nanocomposites with improved strength and high damping performance

A hindered phenol (AO-80) was studied to prepare rubber nanocomposites with nitrile butadiene rubber (NBR). The NBR/AO-80 rubber nanocomposites were successfully developed by applying the adopted preparation procedure/conditions, especially by introducing mechanical kneading of the NBR/AO-80 composites at a temperature higher than the melting point of AO-80, followed by the crosslinking of NBR molecules during the subsequent hot-pressing/vulcanization process. The nanocomposites consisted of two phases: (1) the AO-80 enriched phase (nanoparticles with the average size of approximately 20 nm) and (2) the NBR enriched phase (matrix). The generation and uniform distribution of the nanoparticles were attributed to the high temperature mechanical kneading process, the strong intermolecular interactions between AO-80 and NBR molecules, and the formation of a three-dimensional NBR network. The morphological, structural and mechanical properties of the composites were systematically investigated in each preparation step using SEM, TEM, DSC, XRD, FT-IR, DMTA and a tensile tester. The results indicated that the prepared NBR/AO-80 rubber nanocomposites had single relaxation transitions, improved tensile strengths, high dynamic mechanical loss values, and reasonably good stabilities. The NBR/AO-80 rubber nanocomposites are expected to have important applications as a high performance damping material.     

Compatibility studies on some polymer blend systems by electrical and mechanical techniques

Systematic electrical and mechanical studies were carried out on natural rubber (NR) blended with different types of synthetic rubber such as styrene‐butadiene rubber (SBR), polybutadiene rubber (BR), and ethylene‐propylene‐diene monomer (EPDM) as nonpolar rubbers and nitrile‐butadiene rubber (NBR) and chloroprene rubber (CR) as polar rubbers. The NR/SBR, NR/BR, NR/EPDM, NR/NBR, and NR/CR blends were prepared with different ratios (100/0, 75/25, 50/50, 25/75, and 0/100). The permittivity (ε′) and dielectric loss (ε″) of these blends were measured over a wide range of frequencies (100 Hz–100 kHz) and at room temperature (∼ 27°C). The compatibility results obtained from the dielectric measurements were comparable with those obtained from the calculation of the heat of mixing. These results were confirmed by scanning electron microscopy and showed that NR/SBR and NR/BR blends were compatible while NR/EPDM, NR/NBR, and NR/CR blends were incompatible. To overcome the problem of phase separation (incompatibility) between NR and EPDM, NBR, or CR, a third component such as SBR or poly(vinyl chloride) (PVC) was added as a compatibilizing agent to these blends. The experimental data of dielectric and mechanical measurements showed that the addition of either SBR or PVC could improve the compatibility of such blends to some extent. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 60–71, 2001     

NR/SBR/organoclay nanocomposites: Effects of molecular interactions upon the clay microstructure and mechano‐dynamic properties

Nanocomposites based on (70/30) blends of natural rubber (NR), styrene‐butadiene rubber (SBR), and organoclay (OC) have been prepared successfully via melt‐mixing process. Effects of the extent of polymers/clay interactions upon the developed microstructure, fatigue life, and dynamic energy loss by the nanocomposites have been investigated. Maleated EPDM (EPDM‐g‐MAH) and epoxidized NR (ENR50) were employed as compatibilizer. Nanocomposites were characterized by means of X‐ray diffractometer (XRD), transmission electron microscope (TEM), scanning electron microscope, atomic force microscopy, root mean square, and dynamic mechanical thermal analysis. EPDM‐g‐MAH showed more potential in enhancing dispersion of the clay nanolayers and their interaction with rubber phases. More potential for separating and dispersing the clay nanoplatelets with better interface enhancement was exhibited by EPDM‐g‐MAH as compatibilizer. This was consistent with higher resistance towards large strain cyclic deformations along with more heat build‐up characteristics showed by EPDM‐g‐MAH based nanocomposites especially at compatibilizer/organoclay ratio of 3. Pronounced non‐terminal behavior within low frequency region was also observed for melt storage modulus of this nanocomposite, indicating higher extent of intercalation/exfoliation microstructure with reinforced interfaces than the nanocomposite generated by ENR50. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

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     

Mechanical and physicochemical properties of electron beam irradiated rubber/clay nanocomposites

Effect of electron beam irradiation on the mechanical and physicochemical properties of both styrene butadiene rubber (SBR)/clay and ethylene propylene diene monomer (EPDM)/clay nanocomposites containing clay contents from 3 to 10 phr prepared by melt blending method has been investigated. The prepared composites were subjected to electron beam irradiation doses of up to 150 kGy to induce radiation curing, whereas the mechanical properties in terms of tensile strength (TS), tear strength (Ts), and elongation at break (E_b) were studied as a function of irradiation dose and clay content. TS and Ts increased with increasing irradiation dose up to 100 kGy, they were decreased with further increase in dose. An increase in TS and Ts for SBR and EPDM nanocomposites containing various organomodified montmorillonite (OMMT) contents (3–5 phr) was noticed, whereas a decrement behavior was observed at higher OMMT content. The elongation at break decreased continuously with both irradiation dose and OMMT content. The crosslink density for either EPDM or SBR samples increases with increasing irradiation dose up to 150 kGy and by increasing clay content up to 5 phr, whereas it decreases at higher clay content (7–10 phr). At 5 phr OMMT and 100 kGy irradiation, SBR nanocomposites showed higher TS and Ts than EPDM nanocomposites, while the crosslink density of SBR is lower. POLYM. COMPOS., 34:1600–1610, 2013. © 2013 Society of Plastics Engineers     

Effect of silane coupling agent on the structure and mechanical properties of nano‐dispersed clay filled styrene butadiene rubber

In rubber nanocomposites containing inorganic clay, the reinforcement effect has always been relatively insignificant due to the poor interfacial interaction between the rubber matrix and clay fillers. In this work, the silane coupling agent bis[3‐(triethoxysilyl)propyl]tetrasulfide (Si‐69) was employed through mechanically blending with styrene butadiene rubber (SBR)/clay (100/30) nanocompound that was prepared by combined latex compounding and spray‐drying technique, to serve as the molecular bridge between SBR matrix and clay filler and strengthen the interfacial interaction. TEM and XRD characterization indicated that Si‐69 significantly improved the dispersion of the silicate layers in the SBR matrix. The RPA analysis and the mechanical property study of the SBR/clay nanocomposites revealed that the filler network interaction was weakened while the filler–rubber interaction was strengthened upon the addition of Si‐69. POLYM. COMPOS., 37:890–896, 2016. © 2014 Society of Plastics Engineers     

丁腈橡胶/乙丙橡胶并用胶性能的研究

研究丁腈橡胶(NBR)/三元乙丙橡胶(EPDM)并用比对力学性能、老化性能和耐油性能的影响以及增容剂对共混胶性能的影响.结果表明,在NBR/EPDM共混胶中随EPDM用量的增加,硫化胶的硬度、拉伸强度、撕裂强度和定伸应力呈现下降趋势、拉断伸长率及耐低温性能有所改善,降低了NBR的耐汽油性能,但提高了耐含乙醇汽油性能.随着增容剂CM用量的增加,硫化胶拉伸强度、撕裂强度、100％定伸应力及硬度都呈增大趋势,采用扫描电镜可以清晰的看到添加CM改性后NBR/EPDM共混胶相容性得到显著改善.     

Characteristics of ethylene propylene diene monomer rubber/organoclay nanocomposites resulting from different processing conditions and formulations

Several parameters which affect the nanocomposite formation in a sulfur‐cured ethylene propylene diene rubber (EPDM) containing 10 phr organoclay (montmorillonite modified with octadecylamine; MMT–ODA), were investigated. The parameters varied were linked to processing (mixer type, temperature) and rubber recipe (compatibilizer, accelerator). Increasing temperature and high shear mixing (internal mixer instead of open mill) improved the mechanical performance of the rubber nanocomposites. A more pronounced effect was achieved by using polar EPDM rubbers (maleic anhydride and glycidyl methacrylate grafted version) as compatibilizer. Among the accelerators, zinc diethyldithiocarbamate proved to be most suitable. The microstructure of the rubber/organoclay systems was studied by X‐ray diffraction, transmission electron microscopy and scanning electron microscopy. Organoclay intercalation/exfoliation was accompanied by its more or less severe confinement (reaggregation, deintercalation). This was traced to a partial or full removal of the ODA intercalant from the clay galleries via the formation of a zinc complex in which amine groups of the ODA and sulfur participated. Copyright © 2004 Society of Chemical Industry