Studies of reinforcement behavior of unique elastomer‐based nanocomposite gels

Unique nanocomposite (NC) gels were prepared by blending water swollen unmodified montmorillonite clay suspension with natural rubber (NR) and styrene‐butadiene rubber (SBR) latices followed by prevulcanization. These were extensively characterized by dynamic light scattering, solvent swelling, tensile, and dynamic mechanical measurements. Reinforcement behavior of NC gels was investigated by adding NC gels into virgin NR and SBR matrices at various loadings. The distribution and morphology of NC gels in the elastomer matrices was studied by X‐ray dot mapping and high‐resolution transmission electron microscopy. Experimental results indicated tremendous improvement of tensile strength (TS) and modulus of the NC gel‐filled matrices along with noticeable changes in dynamic mechanical and rheological properties. Compared with virgin NR, the TS of 16 phr NC gel‐filled NR system increased by 117%. Similar level of enhancement of TS was also registered for the NC gel‐filled SBR systems. NC gel‐filled systems showed higher shear viscosities and lower die‐swell values compared with their virgin counterparts. Contemporary particulate composite and nanofiller reinforcement models were used to understand the reinforcing behavior of these NC gels. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Magadiite/styrene‐butadiene rubber composites for tire tread applications: Effects of varying layer spacing and alternate inorganic fillers

Magadiite (MGD), a synthetic layered silicate (Na₂Si₁₄O₂₉·9H₂O) with surface chemistry similar to precipitated silica, was cation‐exchanged with three different organic cations to explore the effect of varying MGD layer spacing on the mechanical properties of MGD‐based styrene‐butadiene rubber (SBR) composites. This work also compares the mechanical properties of MGD/SBR composites with those formulated with montmorillonite (MMT) and precipitated silica. Dodecylpyridinium (DP⁺) produces greater expansion of MGD layers than cetyltrimethylammonium (CTA⁺); the resulting DP‐MGD/SBR composites have greater yield strain, toughness, and rubbery storage modulus than comparable CTA‐MGD/SBR composites. MGD treated with hexadecylammonium (HDA⁺) has the greatest layer spacing, but the HDA‐MGD layers collapse upon melt‐blending with SBR. CTA‐treated MMT (CMMT) exfoliates in aqueous suspension, but the platelets re‐stack upon drying and during melt‐blending with SBR. The presence of exfoliated and/or disordered platelet stacks in CMMT/SBR probably accounts for its higher tensile and dynamic moduli compared to MGD‐ and silica‐based SBR composites. Dynamic mechanical properties are used to predict tire tread performance metrics for these composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44764.     

Synthesis of Na+‐montmorillonite/amphiphilic polyurethane nanocomposite via bulk and coalescence emulsion polymerization

Polyurethane/clay nanocomposites have been synthesized using Na⁺‐montmorillonite (Na⁺‐MMT)/amphiphilic urethane precursor (APU) chains that have hydrophilic polyethylene oxide (PEO) chains and hydrophobic segments at the same molecules. Nanocomposites were synthesized through two different crosslinking polymerization methods. One is UV curing of melt mixed APU/Na⁺‐MMT mixtures; the other is coalescence polymerization of APU/Na⁺‐MMT emulsions. These two kinds of composites had intercalated silicate layers of Na⁺‐montmorillonite by insertion of PEO chains in APU chains, which was confirmed by X‐ray diffraction measurement and transmission electron microscopy. These composite films also showed improved mechanical properties compared to pristine APU films. Although the two kinds of nanocomposites exhibited the same degree of intercalation and were synthesized based on the same precursor chains, these nanocomposite films had the different mechanical properties. Nanocomposites synthesized using APU/Na⁺‐MMT emulsions, having microphase‐separated structure, had greater tensile strength than those prepared with melt‐mixed APU/Na⁺‐MMT mixtures. Location of intercalated Na⁺‐MMT by PEO chains at the oil–water interface also could be confirmed by rheological behavior of the APU/Na⁺‐MMT/water mixture. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3130–3136, 2003     

Preparation and characterization of transparent poly(methyl methacrylate)/Na+‐MMT nanocomposite films by solution casting

Films of poly(methyl methacrylate) (PMMA)/sodium montmorillonite (Na⁺‐MMT) nanocomposites have been successfully prepared utilizing Na⁺‐MMT by N,N‐dimethylformamide solution casting. The nanocomposite films show high transparency, enhanced thermal resistance, and mechanical properties in comparison with the neat polymer film. The transparency of the films was investigated by UV‐vis spectra. The exfoliated dispersion of Na⁺‐MMT platelets in nanocomposites were investigated by X‐ray diffraction and transmission electron microscopy. The enhanced thermal resistance and mechanical properties of PMMA were studied by thermal gravimetric analysis and dynamic mechanical analysis, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of quasi‐nanogel particles on the rheological and mechanical properties of natural rubber: A new insight

The influence of sulfur‐crosslinked, quasi‐nanosized gels on the rheological and mechanical properties of raw natural rubber (NR) was investigated. Latex gels with different crosslink densities were prepared through the variation of the sulfur‐to‐accelerator ratio. These gels were characterized by dynamic light scattering, solvent swelling, and mechanical properties. The gels were mixed with raw NR latex at concentrations of 2, 4, 8, and 16 phr, and their effect on the rheological properties of NR was studied by Monsanto processability tester. The presence of gel in raw NR reduced the apparent shear viscosity and die swell considerably. Initially, the viscosity decreased up to a 8 phr gel loading and then increased with an increase in the gel loading. However, the change in the viscosity was related to the crosslink density of the gels. A new empirical equation relating the viscosity, volume fraction of the gels, and crosslink density was proposed. The die swell of gel‐filled raw NR was at least 10% lower than that of unfilled raw NR and decreased with an increase in the gel loading. The effect of the gels on the die swell properties was explained through the calculation of the principal normal stress difference of gel‐filled NR systems. Scanning electron photomicrographs of the extrudates revealed much better surface smoothness for the gel‐filled virgin rubber systems than for the unfilled rubber. The addition of the gels to raw NR increased the modulus and tensile strength, whereas the elongation at break decreased. The effect of the gels on the dynamic mechanical properties of NR was also investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

有机蒙脱土对天然橡胶/丁苯橡胶的补强及增容作用

采用机械混炼法制备了天然橡胶(NR)/丁苯橡胶(SBR)/有机蒙脱土(OMMT)纳米复合材料,采用TEM和XRD对复合材料的亚微观结构进行了表征,并对复合材料的表观交联密度、静态力学性能、动态力学性能和硫化热效应进行了研究。结果表明,复合材料为剥离型纳米复合材料;OMMT能够明显提高纳米复合材料的交联密度和静态力学性能;OMMT导致NR/SBR共混胶动态损耗因子降低,并且能够促使NR和SBR玻璃化转变温度更为接近,起到了增容作用;OMMT实现了NR和SBR两相的同步硫化。     

Effect of potassium persulfate on graft copolymerization and mechanical properties of cassava starch/natural rubber foams

The aim of this study was to improve the mechanical properties of thermoplastic starch foams prepared from cassava starch blended with natural rubber latex by reactive blending. Potassium persulfate was used as an initiator for graft copolymerization between the starch and natural rubber during baking. The starch–natural rubber graft copolymer (starch‐g‐NR copolymer) was successfully produced during both suspension and melt blending based on ¹H‐NMR and FTIR characterization. Natural rubber increased the flexural modulus of starch/natural rubber foams without potassium persulfate, thus indicating the compatibility of the blends. The starch‐g‐NR copolymer, acting as a compatibilizing agent, enhanced the impact strength of foams, but it did not improve the flexural modulus. This may be due to the potassium persulfate decreasing the molecular weight of the natural rubber. Relative humidity also played an important role on the mechanical properties. Foams became more ductile at higher relative humidities. Since foam density increased with an increasing natural rubber content, the specific impact strength was also considered. A soil burial test showed that the cassava starch foams and foams containing 15 pph of natural rubber were fully biodegraded within 8 and 18 weeks, respectively. The starch‐g‐NR copolymer delayed biodegradation of foams and foams containing high natural rubber content, i.e., 35 pph, showed a low ability to be biodegraded. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of the interaction of hardness,resilience, and fatigue properties on the abrasion properties of rubber blends

The establishment of prediction model for abrasion properties of vulcanizates, based on their simple physio‐mechanical properties, is a hot research field in tribology. The hardness (H), resilience (R), and dynamic fatigue fracture parameters (m) of rubber vulcanizates were combined together in this article, named as hardness–resilience product (H^mR), and its relationships with the abrasion loss for various vulcanizates [natural rubber (NR), styrene–butadiene rubber (SBR), butadiene rubber (BR), and their blends] was investigated by using Akron and DIN abrader. The results showed that, for NR/SBR blends with different SBR content, compared with log(H⁴R), the abrasion loss had much better linear relationship with log(H^mR) for both Akron and DIN abrasion. This good linear relationship, for both Akron and DIN abrasion, also appeared in the SBR/BR blends with different BR content. Furthermore, for both blending systems (NR/SBR and SBR/BR), when all the data above were put together, the abrasion loss also had good linear relationships with its log(H^mR) no matter for Akron or DIN abrasion, which indicated that this linear relationship had some universality. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1212‐1219, 2013     

Synergism Effect of Montmorillonite and Cellulose Whiskers on the Mechanical and Barrier Properties of Natural Rubber Composites

A series of nanocomposite films based on natural rubber (NR), Na⁺‐montmorillonite (MMT), and cellulose whiskers (W) was prepared, keeping a total filler content equal to 5 wt.‐%. In the binary NR/MMT system, small stacks of intercalated montmorillonites were homogeneously dispersed within the polymer matrix whereas they were clearly lying in the vicinity of cellulose whiskers in the ternary NR/MMT/W blends. The effects of MMT and W on mechanical and gas barrier properties of the nanocomposite films were investigated. A significant increase of the rubbery modulus was obtained upon filler addition. The reinforcing effect was particularly important for the nanocomposite film reinforced with 1 wt.‐% MMT and 4 wt.‐% W. The improvement of the gas barrier properties observed upon filler addition was explained by a tortuosity effect. The calculated tortuosity values indicated that the simultaneous use of MMT and W could greatly slow down the gas diffusion rate in NR. Formation of MMT‐W subassembly should be responsible for this synergism effect.

     

Nanoclay distribution and its influence on the mechanical properties of rubber blends

The distribution of modified and unmodified nanoclays inside the rubber phases of immiscible rubber–rubber blends composed of nonpolar–polar natural rubber (NR)/epoxidized natural rubber (ENR) and nonpolar–nonpolar NR/polybutadiene rubber (BR) was investigated for the first time. The distribution of clays at various loadings in the blends was calculated from the viscoelastic properties of the blends. For example, in the 50 : 50 NR/ENR blend, 42% Cloisite 30B migrated to the NR phase, and 58% went to the ENR phase. However, in the same blend, only 7% Cloisite Na⁺ was found in the NR phase, and 93% was found in the ENR phase. Again, in the 50 : 50 NR/BR blends, the NR phase contained 85% Cloisite 30B, whereas 55% Cloisite Na⁺ migrated to the NR phase. All these observations were explained with the help of viscosity, X‐ray diffraction, and morphology analyses. The effect of the distribution of the clay on the mechanical properties was also discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Harmless hydrogels based on PVA/Na+‐MMT nanocomposites for biomedical applications: Fabrication and characterization

A series of nanocomposite hydrogels were prepared by a freeze‐thaw process, using polyvinyl alcohol (PVA) as polymer matrix and 0–10 wt% of hydrophilic natural Na‐montmorillonite (Na⁺‐MMT), free from any modification, as composite aggregates. The effect of nanoclay content and the sonication process on the nanocomposite microstructure and morphology as well as its properties (physical, mechanical, and thermal) were investigated. The microstructure and morphology were investigated by Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, atomic force microscopy, and X‐ray diffraction technique. The thermal stability and mechanical properties of nanocomposite hydrogels were examined using thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis; moreover hardness and water vapor transmission rate measurements. It was concluded that the microstructure, morphology, physical (thermal) and mechanical properties of nanocomposite hydrogels have been modified followed by addition of nanoclay aggregates. The results showed that Na⁺‐MMT may act as a co‐crosslinker. Based on the results obtained, the nanocomposite hydrogel PVA/Na⁺‐MMT synthesized by a freeze‐thaw process, appeared to be a good candidate for biomedical applications. POLYM. COMPOS., 38:1135–1143, 2017. © 2015 Society of Plastics Engineers     

Studies on polymer blends: Blending methods for natural rubber and styrene-butadiene rubber

The relations between the properties and the blend ratios of natural rubber (NR) and styrene-butadiene rubber (SBR) blends were studied in comparison with four blending methods. The relations between the properties of unvulcanized and vulcanized blends and the blend ratios of blends prepared by means of solution blending, latex blending, roll blending, and Banbury mixer blending were studied. In practice, such rubber blending methods as roll blending are more effective for obtaining uniform blends than Banbury mixer blending the latter. In roll blending, it is more effective to blend NR and SBR by way of a master-batch in which the ingredients are compounded beforehand than to blend raw rubber. In solution and latex blending, very uniform blends are easily obtained. It was found, however, that the properties of NR/SBR blends prepared carefully showed a direct relation to their blend ratios, regardless of blending method used.     

Rheological behavior of gel‐filled raw natural rubber and styrene‐butadiene rubber with reference to gel‐matrix intermixing

Natural rubber (NR) and styrene‐butadiene rubber (SBR) latex gels were prepared by sulfur prevulcanization technique with varying amounts of curing agent and accelerator systems to generate gradient in crosslink density. These gels were characterized by solvent swelling, dynamic light scattering, atomic force microscopy, and mechanical properties. Crosslinked NR gels were intermixed with neat SBR matrix and vice versa. Rheological behavior of chemically crosslinked gel‐filled NR and SBR was studied by capillary rheometry. Intermixing of crosslinked gels in the rubber matrices resulted in a considerable reduction in apparent shear viscosity and die swell values. This behavior was found to be dependent on several factors like gel concentration in the matrix, crosslink density of the gels, their size, and distribution. The effect of temperature on viscosity was studied extensively following the Arrhenious‐Eyring model. A shear rate‐temperature superposition mastercurve was constructed to predict the melt viscosities of the systems as a function of temperature. The change in die swell values was related to the change in first normal stress difference. The scanning electron photomicrographs of the extrudates revealed that presence of gels markedly improved the surface roughness of the raw rubbers. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Chitosan/clay nanocomposite film preparation and characterization

Nanocomposites of chitosan and nanoclays (MMT‐Na⁺ and Cloisite 30B) were prepared by solvent casting. The structural properties, thermal behaviors, and mechanical properties were characterized using X‐ray diffraction (XRD), transmission electron microscopy (TEM), atomic force microscopy, differential scanning calorimetry, thermogravimetry analyses, and an Instron universal testing machine. XRD and TEM results indicated that an exfoliated structure was formed with addition of small amounts of MMT‐Na⁺ to the chitosan matrix. Intercalation along with some exfoliation occurred with up to 5 wt % MMT‐Na⁺. Micro‐scale composite (tactoids) formed when Cloisite 30B was added to the chitosan matrix. Surface roughness increased with addition of a small amount of clay. Tensile strength of a chitosan film was enhanced and elongation‐at‐break decreased with addition of clay into the chitosan matrix. Melt behavior and thermal stability did not change significantly with addition of clays. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1684–1691, 2006     

Study on flammability of montmorillonite/styrene‐butadiene rubber (SBR) nanocomposites

The flammability of montmorillonite (MMT)/SBR nanocomposites, prepared by the technique of cocoagulating rubber latex and clay aqueous suspension, was investigated. Flammability studies, performed on the cone calorimeter, showed that the maximum heat release rate (HRR) of SBR decreased from 1987 to 1442 kw/m² with the introduction of nanoclay (20 phr). This nanocomposite had the lowest mass loss rate and the largest amount of char upon combustion compared with conventional SBR composites with the same clay loading and pure SBR. The permeability properties of MMT/SBR composites were also measured. It was deduced that the lowered permeability was responsible for the reduced mass loss rate and hence the lower HRR. Unfortunately, the oxygen index (OI) of the nanocomposites was not as high as expected. Combination of Mg(OH)₂ and clay was effective for the improvement of both mechanical properties and OI. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 844–849, 2005     

Preparation,structure, and properties of montmorillonite/cellulose II/natural rubber nanocomposites

In this work, sodium montmorillonite clay was added, as filler, to nanocomposites of natural rubber (NR) and cellulose II (regenerated cellulose) in amounts varying from 0 to 5 phr (per hundred resin). Natural rubber (NR)/cellulose II/montmorillonite nanocomposites were prepared by co‐coagulating NR latex, montmorillonite aqueous suspension and cellulose xanthate. The clay was previously exfoliated in water, and the resulting suspension was then added to the mixture of NR latex with cellulose xanthate. Morphological, rheometric, mechanical, and dynamic mechanical properties were evaluated, and an increase in these properties was observed upon the addition of cellulose and clay nanomaterials to the rubber matrix. The results show the advantage in using cellulose as a nanopolymer as well as MMT as nanofiller. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of hyperbranched polymer modified montmorillonite/chlorinated butyl rubber damping composites

In this work, Na⁺‐montmorillonite (MMT) was modified by hyperbranched polymer (HBP) and grafted with hindered phenol to improve the damping and other properties of the chlorinated butyl rubber (CIIR) composites. The hyperbranched polymer‐modified montmorillonite (HBP‐OMMT) was prepared by organic montmorillonite (OMMT) that was obtained from the cation exchange reaction between MMT and silane quaternary ammonium salt. The main characterization methods were Fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance, X‐ray diffraction, scanning electron microscopy, energy dispersive spectrometer, and thermogravimetric (TG) analysis. The basal spacings of MMT, OMMT, and HBP‐OMMT were 1.47, 2.94, and 4.09 nm, respectively. The onset and center temperatures of decomposition (T_?5% and T_max) of HBP‐OMMT were improved from 301 and 369 °C to 332 and 398 °C, respectively. The CIIR damping composites were prepared by mechanical blending of HBP‐OMMT with pure CIIR. The tensile strength and elongation at break of the composites were improved from 5.4 MPa and 890% to 7.6 MPa and 1066%. From TG curves, T_?5% and T_max were increased from 297.4 and 406.0 °C to 323.3 and 410.5 °C, respectively. The dynamic mechanical analysis results showed that tan δ rose from the original 1.20 to 1.44 with the addition of HBP‐OMMT. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43645.     

Preparation and Properties of Biodegradable Thermoplastic Starch/Clay Hybrids

Biodegradable thermoplastic starch (TPS)/clay hybrids were prepared by melt intercalation. Three organically modified montmorillonite (MMT) with different ammonium cations and one unmodified Na⁺ MMT (Cloisite Na⁺) were used. Cloisite Na⁺ showed the best dispersion in the TPS matrix. It was observed that the TPS/Cloisite Na⁺ hybrid showed an intercalation of TPS in the silicate layer due to the matching of the surface polarity and interactions of the Cloisite Na⁺ and the TPS, which gives higher tensile strength and better barrier properties to water vapor as compared to the other TPS/organoclay hybrids as well as the pristine TPS. It was found that the dynamic mechanical properties of the TPS/clay hybrids were also affected by the polar interactions.     

Effects of acid neutralization on the morphology and properties of organoclay nanocomposites formed from K+ and Na+ poly(ethylene-co-methacrylic acid) ionomers

Nanocomposites were prepared by melt blending various sodium (Na⁺) and potassium (K⁺) ionomers formed from poly(ethylene-co-methacrylic acid) and the M₂(HT)₂ organoclay formed from montmorillonite (MMT). The effects of the neutralization level of the acid groups and the precursor melt index on the morphology and properties of the nanocomposites were evaluated using stress-strain analysis, wide angle X-ray scattering (WAXS), and transmission electron microscopy (TEM) coupled with particle analysis. The aspect ratio generally increases as the neutralization level increases, except for Na⁺ ionomer nanocomposites with neutralization levels >50%. It appears from both WAXS and TEM analyses that Na⁺ ionomer nanocomposites have higher levels of MMT exfoliation and particle orientation in the flow direction than K⁺ ionomer nanocomposites. DSC results indicate that the level of crystallinity in the Na⁺ ionomers generally increases slightly with MMT addition, while the crystallinity in the K⁺ ionomers decreases slightly with MMT addition. The relative modulus of K⁺ ionomer nanocomposites increases as the degree of neutralization increases. The relative moduli of Na⁺ ionomer nanocomposites are higher than the relative modulus of K⁺ ionomer nanocomposites, likely due to the increased crystallinity of the Na⁺ ionomers and the decreased crystallinity of the K⁺ ionomers upon addition of MMT, the higher exfoliation levels measured by the aspect ratios and the particle densities, and the higher particle orientation indicated by TEM and WAXS. The relative modulus generally increases as the aspect ratio increases. The elongation at break generally decreases as the MMT content increases and as the neutralization level increases for both ionomer types. The fracture energy of most of the ionomers increases with the addition of MMT, reaches a maximum between 2.5 and 5 wt% MMT, and then decreases upon further MMT addition.     

Mechanical reinforcement in magadiite/styrene‐butadiene rubber composites

This work investigates mechanical properties of styrene‐butadiene rubber (SBR) composites incorporating magadiite (MGD), a synthetic layered silicate (Na₂Si₁₄O₂₉·9H₂O) with surface chemistry similar to precipitated silica used in tire tread formulations. Treatment with cetyltrimethylammonium (CTA⁺) expands the MGD layers and makes the interlayer face surfaces accessible to sulfur‐functional silane TESPT (Si69) and SBR, primarily during batch mixing. DMA and tensile testing of cured CMGD/SBR composites show that CTA‐treated MGD (CMGD) provides substantially higher levels of mechanical reinforcement than equivalent amounts of silica. However, CMGD/SBR composites exhibit larger loss tangent values above T_g, probably due to lower SBR‐SBR crosslink density resulting from interlayer trapping of sulfur released by Si69 during vulcanization. DMA and tensile testing also demonstrate Si69′s critical role in forming MGD‐SBR graft sites essential to mechanical reinforcement. Replacing silica with CMGD reduces composite weight without sacrificing tensile modulus, suggesting that use of CMGD in tire rubber formulations could improve vehicle energy efficiency. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44763.