Effects of palm ash loading and maleated natural rubber as a coupling agent on the properties of palm‐ash‐filled natural rubber composites

Natural rubber composites were prepared by the incorporation of palm ash at different loadings into a natural rubber matrix with a laboratory‐size two‐roll mill (160 × 320 mm²) maintained at 70 ± 5°C in accordance with the method described by ASTM D 3184–89. A coupling agent, maleated natural rubber (MANR), was used to improve the mechanical properties of the natural rubber composites. The results indicated that the scorch time and cure time decreased with increasing filler loading, whereas the maximum torque exhibited an increasing trend. Increasing the palm ash loading increased the tensile modulus, but the tensile strength, fatigue life, and elongation at break decreased. The rubber–filler interactions of the composites decreased with increasing filler loading. Scanning electron microscopy of the tensile fracture surfaces of the composites and rubber–filler interaction studies showed that the presence of MANR enhanced the interfacial interaction of the palm ash filler and natural rubber matrix. The presence of MANR also enhanced the tensile properties and fatigue life of palm‐ash‐filled natural rubber composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Physical properties of natural rubber/organoclay nanocomposites compatibilized with epoxidized natural rubber

Onium ion‐modified montmorillonite (organoclay) was melt compounded with natural rubber (NR) in an internal mixer and cured by using a conventional sulfuric system. Epoxidized natural rubber with 50 mol % epoxidation (ENR 50) was used in 10 parts per hundred rubber (phr) as a compatibilizer. The effect of organoclay with different filler loading up to 10 phr was studied. Cure characteristics were determined by a Monsanto MDR2000 rheometer, whereas the tensile, compression, and tear properties of the nanocomposites were measured according to the related ASTM standards. While the torque maximum and torque minimum increased slightly, both scorch time and cure time reduced with the incorporation of organoclay. The tensile strength, elongation at break, and tear properties went through a maximum (at about 2 phr) as a function of the organoclay content. As expected, the hardness, moduli at 100% (M100) and 300% elongations (M300) increased continuously with increasing organoclay loading. The compression set decreased with incorporation of organoclay. The dispersion of the organoclay in the NR stocks was investigated by X‐ray diffraction and transmission electron microscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1083–1092, 2006     

A novel grafting‐modified waste rubber powder as filler in natural rubber vulcanizates

Polycardanol was synthesized from cardanol, paraformaldehyde, p‐toluenesulfonic acid, phosphoric acid (H₃PO₄), and phosphorus pentoxide (P₂O₅) via a two‐step process. Results indicated that polycardanol is an acid with high molecular weight and can be self‐crosslinked at high temperature. A modified WRP (MWRP) grafted by long chain can be obtained from the reaction between WRP and polycardanol. The sulfur content of MWRP is 0.27%, which is lower than that of WRP by 0.47%. The oxygen content of MWRP is higher by 13% than that of WRP. The phosphorus content of MWRP reaches 5.25%. The water contact angle of MWRP is 91.5°, whereas that of WRP is 123.7°. The properties of the WRP/NR and MWRP/NR composites were also investigated. MWRP/NR possesses higher tensile strength than WRP/NR because of the enhanced interfacial interaction between MWRP and the NR matrix. Post‐treatment is also conducive for MWRP/NR to improve its tensile strength at high MWRP content. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42993.     

Synthesis and characterization of magnetic nanocomposites of fullerene‐containing polyurethane films for microwave applications

Novel nanocomposites of barium hexaferrite‐ and fullerene‐containing polyurethane were synthesized and characterized by scanning electron microscopy, transmission electron microscopy, X‐ray diffractometry, and energy‐dispersive X‐ray diffraction. The nanoparticles showed good dispersion in the polyurethane matrix. Their thermal, mechanical, and electromagnetic absorbance properties were studied. The complex permeability and permittivity were measured in the frequency range of 8.2–12.4 GHz. The maximum reflection loss of the nanocomposites was found to increase with increasing the ferrite content from 1% to 5%, with maximum value of −7.5 dB at only 5% composition. The incorporation of nanofiller not only imparts mechanical strength to the nanocomposite but also shows good radar‐absorbing properties at only 5% filler concentration. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Properties of silica‐filled styrene‐butadiene rubber compounds containing acrylonitrile‐butadiene rubber: The influence of the acrylonitrile‐butadiene rubber type

Because silica has strong filler‐filler interactions and adsorbs polar materials, a silica‐filled rubber compound exhibits poor dispersion of the filler and poor cure characteristics in comparison with those of a carbon black‐filled rubber compound. Acrylonitrile‐butadiene rubber (NBR) improves filler dispersion in silica‐filled styrene‐butadiene rubber (SBR) compounds. The influence of the NBR type on the properties of silica‐filled SBR compounds containing NBR was studied with NBRs of various acrylonitrile contents. The composition of the bound rubber was different from that of the compounded rubber. The NBR content of the bound rubber was higher than that of the compounded rubber; this became clearer for NBR with a higher acrylonitrile content. The Mooney scorch time and cure rate became faster as the acrylonitrile content in NBR increased. The modulus increased with an increase in the acrylonitrile content of NBR because the crosslink density increased. The experimental results could be explained by interactions of the nitrile group of NBR with silica. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 385–393, 2002     

Properties of a new synthetic rubber: High‐trans 1,4‐poly(butadiene‐co‐isoprene) rubber

A high‐trans 1,4‐butadiene/isoprene copolymer (TBIP) was synthesized in a 5‐L autoclave with hydrogen as an effective molecular weight modifier. The effects of hydrogen on the catalyst efficiency and molecular weight of the copolymers were investigated. The processability and physicomechanical properties of TBIP and their relationship to the composition, composition distribution, and molecular weight of TBIP were examined in detail. Increasing the H₂ pressure effectively reduced the molecular weight of TBIP. The optimum Mooney viscosity of TBIP and the 1,4‐butadiene molar content in the feed were 30–50 and 5–25%, respectively. No cis–trans isomerization was observed during the roll processing procedure for TBIP. The vulcanization characteristics of TBIP were similar to those of general rubbers, and no reverse vulcanization was observed for TBIP. A high green strength was the typical characteristic of TBIP. Vulcanized TBIP (TBIR) with an optimum composition and molecular weight presented outstanding antifatigue properties and low heat buildup in comparison with general rubbers. Compared with general sidewall stock [natural rubber (NR)/butadiene rubber (BR) = 50/50], TBIR exhibited a greater than 15‐fold increase in its crack‐initiation resistance. The other mechanical properties of TBIR were similar to those of 50/50 NR/BR. The heat‐aging mechanism of TBIR was crosslinking aging. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2941‐2948, 2004     

Development and characterization of graphitic carbon nitride as nonblack filler in natural rubber composites

A new type of elastomeric composite containing natural rubber (NR) and graphitic carbon nitride (g-C₃N₄) has been successfully prepared with the reinforced property. The reinforcing effect of g-C₃N₄ in NR composites was examined by cure, mechanical, morphological, and swelling studies. Besides, epoxidized NR with 50-mol % epoxy level (ENR-50) was used as a compatibilizer to enhance the hydrophilic g-C₃N₄ filler capacity for hydrophobic NR composites. At the same filler load level, the mechanical properties of NR/g-C₃N₄ composites, such as tensile strength and tensile modulus, were consistently increased with increased ENR-50 content. To note, the ENR compatibilized composites have shown better-reinforced performance, which has been attributed to the hydrogen bonding interactions between the uncondensed amine groups in g-C₃N₄ and the polar groups in ENR. We believe that these newly prepared NR composites based on g-C₃N₄ as nonblack filler and ENR-50 as compatibilizer can find potential applications in modern day rubber research. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48136.     

Effect of silane coupling agent on the fatigue crack propagation of silica‐filled natural rubber

Based on the real‐time crack tip morphology monitoring, the influence of silane coupling agent (SCA) on the crack‐growth behavior of silica‐filled natural rubber (NR) was analyzed. By using SCA, silica particles can be well dispersed and a filler–matrix network can be formed, which leads to lower crack‐growth rate. Results indicate that a dosage of 5 wt % (with respect to silica loading) is the optimal content. The real‐time observation and scanning electron microscopy (SEM) analysis proved that thin ligaments and dimples with homogeneous distribution appear on the crack tip. These crack tip morphologies reflect the low crack‐growth rate. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41980.     

Properties of silica/clay filled heavy‐duty truck tire thread formulation

A tire thread formulation for heavy‐duty trucks containing SBR/BR rubber blend and varying proportions of silica/clay fillers including a silane‐coupling agent have been investigated. The various mixes were compounded in a Banbury ‘O’ mixer and vulcanized using the EV‐system. Silica/clay (80/0) served as the control mix. The oscillating disc rheometer (ODR) was used in determination of cure characteristics. Substitution of silica (80 phr) with china clay up to 40 phr increased the cure rate of the rubber blend mixes as well as their maximum torque level (T_max). T_max was observed to be highest at a filler blend ratio of 40/40 phr. Synergism between silica and clay at this filler blend mixture is suggested to be responsible for the observation. The heat buildup was reduced from 43 to 20°C as the clay content increased. Results also showed that the rubber blend compound containing silica/clay (60/20) filler blend in the stated ratio exhibited the best balance of properties in the critical parameters such as the absolute torque level (69.5 dNm), heat buildup (39°C), and abrasion resistance (0.574 mg.loss/1,000 rev). The rate of depreciation of abrasion resistance of rubber blend compound as the clay content increased was found to be 0.035 mg loss/1,000 rev as silica is substituted with one part of china clay phr. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1024–1028, 2004     

Preparation and graft‐copolymerization of hydrogenated natural rubber in latex stage

Preparation and graft‐copolymerization of hydrogenated natural rubber are performed in latex stage after removal of proteins from the rubber with urea and surfactant. Hydrogenation of deproteinized natural rubber (DPNR) latex is carried out with palladium catalyst under hydrogen atmosphere. The hydrogenated DPNR (HDPNR) is crosslinked with a peroxide followed by graft‐copolymerization of styrene (Sty) and acrylonitrile (AN) in latex stage in order to prepare a graft‐copolymer of crosslinked HDPNR with poly(Sty‐co‐AN) (HDPNR‐graft‐PSAN). Characterization of the products is performed by nuclear magnetic resonance spectroscopy. The conversion of hydrogenation is investigated with respect to the catalyst feed, acidity (pH), and dry rubber content. In the resulting HDPNR‐graft‐PSAN, mole fraction of AN and Sty is 1.4 and 5.8 mol %, respectively. The graft‐copolymer is used to improve properties of PSAN as an impact modifier. The Charpy impact strength of crosslinked HDPNR‐graft‐PSAN/PSAN is about eight times as high as that of PSAN. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42435.     

Possible use of ultra‐fine acrylonitrile butadiene rubber powder as filler in natural rubber vulcanizates

Possible use of ultra‐fine acrylonitrile butadiene rubber powder (UFNBRP) as a filler for natural rubber (NR) was investigated. The UFNBRP was added into NR at various concentrations, and the compound properties were determined. It is found that, with increasing UFNBRP loading, the compound viscosity is increased, whereas both scorch time and optimum curing time are significantly reduced. The results also reveal that UFNBRP has negative effect not only on crosslink density but also on most mechanical properties of the vulcanizate, such as tensile strength, tear strength, compression set, and abrasion resistance. The deterioration of these mechanical properties is thought to arise mainly from the combined effect of large phase size of the dispersed UFNBRP and low interfacial adhesion taking place from the polarity difference between UFNBRP and NR. Interestingly, it is found that, after aging, UFNBRP could promote postcuring phenomenon leading to increases of both relative 100% modulus and relative tensile strength. Oil resistance is also found to improve considerably with increasing UFNBRP loading. This improvement is mainly attributed to the dilution effect, i.e., the higher the UFNBRP loading, the lower the NR portion and, thus, the greater the oil resistance of the vulcanizate. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Investigation of allyl‐capped carbosilane dendrimers used as crosslinker for silicone rubber

High‐temperature vulcanized silicone rubber was prepared by using allyl‐capped carbosilane dendrimers, in which the core molecules were Si(CH₂CH?CH₂)₄ and Ph₂Si(CH₂CH?CH₂)₂ as crosslinker and nanoscale reinforcing filler, respectively. Allyl‐capped carbosilane dendrimers improved the mechanical properties of silicone rubber. The optimum tensile strength and tear strength were 9.6 MPa and 31.0 kN/m, respectively, when using SiG_n(allyl)m as the crosslinker and 10.1 MPa and 32.0 kN/m, respectively, when using Ph₂SiG_n(allyl)m as the crosslinker. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1772–1775, 2006     

Experimental analysis of viscoelastic properties in carbon black‐filled natural rubber compounds

Processability and viscoelastic properties of natural rubber (NR) compounds filled with different carbon black loadings and types were investigated with the use of a steady shear rheometer, namely, the Mooney viscometer, and an oscillatory rheometer, namely, the Rubber Process Analyser (RPA2000). It was found that the type and amount of carbon black strongly influence the viscoelastic properties of rubber compounds. Both the dilution effect and filler transient network are responsible for the viscoelastic properties, depending on the vulcanization state. In the case of uncured compounds, the damping factor of the uncured NR decreases with increasing black loading. This is attributed to the reduction of mobilized rubber content in the compound (or the dilution effect). However, in the case of the cured NR vulcanizates, the filler transient network is the dominant factor governing the damping factor of the vulcanizate. With increasing black loading, the damping factor of the vulcanizate clearly increases. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2197–2203, 2005     

Processability characteristics and physico‐mechanical properties of natural rubber modified with rubber seed oil and epoxidized rubber seed oil

The processability characteristics and physico‐mechanical properties of natural rubber (NR) modified with raw rubber seed oil and epoxidized rubber seed oil have been studied. The modified mixes showed higher scorch time and lower cure rate, crosslink density, and ultimate state of cure compared to an unmodified mix. The thermal stability of the vulcanizates was practically unaffected by the modification. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1413–1418, 2000     

Morphology and dynamic mechanical properties of natural rubber/nitrile rubber blends containing trans‐polyoctylene rubber as a compatibilizer

The use of trans‐polyoctylene rubber (TOR) as a compatibilizer for blends of natural rubber (NR) and acrylonitrile‐butadiene rubber (NBR) was investigated using atomic force microscopy (AFM) and dynamic mechanical analysis (DMA). The NR/NBR blends containing varying proportions of TOR were prepared in an internal mixer. AFM micrographs of NR/NBR blend at 50/50 (w/w) composition showed heterogeneous phase morphology with NR as a matrix and NBR as a dispersed phase. Inclusion of TOR in the NR/NBR blend altered the phase morphology by reducing the size of the NBR phase. DMA of NR/NBR/TOR showed reduction in tan δ peak height of NBR and an increase in storage modulus E′ in the rubbery region for the NR/NBR blends. A comparison of the E′ obtained from experimental data with that from theoretical models was made to deduce the location of TOR in the blend. Based on the fittings of calculated and experimental values of E′, it was inferred that TOR was incorporated into the NR phase at lower proportion as well as at the interfacial region at higher proportion. The Cole–Cole plot illustrated the compatibilizing effect of TOR. Copyright © 2004 Society of Chemical Industry     

Viscoelastic properties of fly ash‐filled natural rubber compounds: Effect of fly ash loading

Fly ash (FA) as a by‐product of power station plants is known to consist of silicon dioxide similar to precipitated silica. The use of FA as filler in natural rubber (NR) was of interest to reinforce and/or reduce product cost. In this article, viscoelastic properties of FA‐filled NR composites with various FA loadings were investigated with the utilization of two different modes of shear flow, namely, oscillatory and steady shear flow. It is found that the addition of FA to NR increases storage modulus (G′) and shear viscosity under both oscillatory and steady shear flow. Moreover, the oscillatory test results exhibit the unexpected increase in magnitude of viscous response with increasing FA loading in FA‐filled NR compounds. The explanation is proposed in terms of the ball‐bearing effect of FA with spherical shape associated with the occurrence of molecular degradation induced by inorganic constituents particularly manganese, iron, and copper in nonrubber component of NR as well as the small amount of heavy metals including iron, copper in FA. An isoprene rubber (IR) containing no nonrubber component was used to validate the proposed explanation. In addition, with the use of Cox‐Merz concept, the results of both complex viscosity under oscillatory shear flow and apparent shear viscosity under steady shear flow can effectively be superimposed in the case of FA‐filled compounds, supporting the promotion of viscous response by FA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of poly(methyl methacrylate‐co‐butyl methacrylate) nanoparticles and their reinforcing effect on natural rubber

Poly(methyl methacrylate‐co‐butyl methacrylate) [P(MMA‐co‐BMA)] nanoparticles were synthesized via emulsion polymerization, and incorporated into natural rubber (NR) by latex compounding. Monodispersed, core‐shell P(MMA‐co‐BMA)/casein nanoparticles (abbreviated as PMBMA‐CA) were produced with casein (CA) as surfactant. The chemical structure of P(MMA‐co‐BMA) copolymers were confirmed by ¹H‐NMR and FTIR analyses. Transmission electron microscopy demonstrated the core–shell structure of PMBMA‐CA, and PMBMA‐CA homogenously distributed around NR particles, indicating the interaction between PMBMA‐CA and NR. As a result, the tensile strength and modulus of NR/PMBMA‐CA films were significantly enhanced. The tensile strength was increased by 100% with 10% copolymer addition, when the molar ratio of MMA:BMA was 8:2. In addition, scanning electron microscopy and atomic force microscopy results presented that the NR/PMBMA‐CA films exhibited smooth surfaces with low roughness, and PMBMA‐CA was compatible with NR. FTIR‐ATR analyses also suggested fewer PMBMA‐CA nanoparticles migrated out of NR. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43843.     

Surface modification of MWCNT to improve the mechanical and thermal properties of natural rubber nanocomposites

In this study, we focused on the synergistic effect between carbon black (CB) and multiwall carbon nanotube (MWCNT) hybrid fillers. In particular, the surface modification of pristine MWCNT (P-MWCNT) via an acid (oxidation) treatment was used to improve their dispersion, as well as the mechanical and thermal properties of their corresponding natural rubber (NR)-based nanocomposites. Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) were carried out to determine the presence of functional groups on the oxidized MWCNT (O-MWCNT). After vulcanization, dynamic mechanical analysis (DMA), tensile properties, hardness, thermal conductivity, swelling behaviour in toluene and SEM characterizations were performed on both NR/CB/P-MWCNT- and NR/CB/O-MWCNT-based nanocomposites. The results showed the positive effect of MWCNT surface oxidation on the fillers' dispersion and nanocomposites' properties.     

Research on Payne effect of natural rubber reinforced by graft‐modified silica

Silica (SiO₂) modified by in situ solid‐phase grafting was used for natural rubber (NR) reinforcement. The physical mechanical properties and Payne effect of natural rubber reinforced by SiO₂ and graft‐modified silica (G‐SiO₂) were analyzed systematically. The results showed the comprehensive performance of NR/G‐SiO₂ was better than that of NR/SiO₂. There was a proportional relationship between the filler loading and Payne effect. NR/G‐SiO₂ presented weaker Payne effect in comparison with NR/SiO₂. A qualitative analysis on the correlation of filler 3D network structure and filler loading was carried out according to the relationship between the bound rubber content and the shear modulus. The Payne effect mechanisms of rubber compounds differed according to the different filler loading. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43891.     

Reinforcing effect and electrical properties of ethylene‐propylene rubber filled with calcined sepiolite

A mineral sepiolite (magnesium silicate with microfibrilar morphology) was calcined at 325°C and its behavior as filler for ethylene‐propylene (EPM) compounds designed for electrical cable coating was studied. This calcined sepiolite is a material with good dielectric and physical properties and provides a reinforcing effect, increased when is treated with a coupling agent. The performance of this filler was compared to a commercial clay calcined at 1000°C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 714–718, 2001