Effect of crosslink structures on dynamic mechanical properties of natural rubber vulcanizates under different aging conditions

The effects of crosslink structures on the dynamic mechanical properties (DMPs) of unfilled and carbon black N330‐filled natural rubber (NR) vulcanizates cured with conventional (CV), semiefficient (SEV), and efficient (EV) cure systems and having about the same total crosslink densities were investigated before and after aerobic and anaerobic aging at 100°C. The three unfilled NR vulcanizates cured with the CV, SEV, and EV systems had about the same mechanical loss factor (tan δ) values at about 0°C but showed some apparent differences in the tan δ values in the order EV > SEV > CV at relatively high temperatures of 40–80°C before aging. However, N330‐filled NR vulcanizates gave higher tan δ values than the unfilled vulcanizates and showed little effect of the crosslink types on the tan δ at different temperatures over the glass‐transition temperature (T_g) before aging. Aerobic heat aging increased the T_g and tan δ values of the vulcanizates over a wide range of temperatures from ?80 to 90°C that was mainly due to the changes in the total density and types of crosslinks. The unfilled vulcanizates cured with the CV system showed the greatest change in DMP because of their poor resistance to heat aging. Aerobic heat aging of NR vulcanizates caused a more significant change in the DMP than anaerobic heat aging because of the dominant effect of the oxidative degradation during aerobic heat aging on the main‐chain structure, crosslink structures, and DMPs of the vulcanizates. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 710–718, 2001     

Dynamic mechanical properties of styrene‐butadiene rubber vulcanizate filled with electron beam modified surface‐treated dual‐phase filler

The influence of the electron beam modification of a dual‐phase filler on the dynamic mechanical properties of styrene‐butadiene rubber (SBR) is investigated in the presence and absence of trimethylol propane triacrylate or triethoxysilylpropyltetrasulfide. Electron beam modification of the filler results in reduction of the tan δ at 70°C, a parameter for rolling resistance, and an increase in the tan δ at 0°C, a parameter for wet skid resistance of SBR vulcanizates. These modified fillers give significantly better overall performance in comparison with the control dual‐phase filler. This variation in properties is explained in terms of filler parameters such as the filler structure that leads to rubber occlusion and filler networking. These results are further corroborated using the master curves obtained by the time–temperature superposition principle. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2992–3004, 2003     

The influence of in situ modification of silica on filler network and dynamic mechanical properties of silica‐filled solution styrene–butadiene rubber

The influence of in situ modification of silica with bis‐(3‐(triethoxysilyl)‐propyl)‐tetrasulfide (TESPT) on filler network in silica filled solution SBR compound was investigated. In situ modification greatly increased the bound rubber content. TEM observation of silica gel showed that bridging and interlocking of absorbed chains on the surface of silica particles formed the filler network. Rubber processing analyzer (RPA) was used to characterize the filler network and interaction between silica and rubber by strain and temperature sweeps. In situ modification improved the dispersion of silica, and in the meantime, the chemical bonds were formed between silica and rubber, which conferred the stability of silica dispersion during the processing. Compared to the compound without in situ modification, the compound with in situ modification of silica exhibited higher tan δ at low strains and lower tan δ at high strains, which can be explained in terms of filler network in the compounds. After in situ modification, DMTA results showed silica‐filled SSBR vulcanizate exhibited higher tan δ in the temperature range of ?30 to 10°C, and RPA results showed that it had lower tan δ at 60°C when the strain was more than 3%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Torrefied agro-industrial residue as filler in natural rubber compounds

This study explored the feasibility of using torrefied biomass as a reinforcing filler in natural rubber compounds. Carbon black was then replaced with the torrefied biomass in elastomer formulations for concentrations varying from 0% to 100% (60 parts per hundred rubber or phr total). Their influence on the curing process, dynamic properties, and mechanical properties was investigated. Results were compared with the properties of vulcanizates containing solely carbon black fillers. Time to cure (t₉₀) for compounds with torrefied biomass fillers increased, while filler-filler interactions (ΔG') decreased, compared to carbon black controls. At low strains, the tan δ values of the torrefied fillers vulcanizates were similar to the controls. Incorporation of torrefied biomass into natural rubber decreased compound tensile strength and modulus but increased elongation. Replacement with torrefied fillers resulted in a weaker filler network in the matrix. Still, results showed that moderate substitution concentrations (~20 phr) could be feasible for some natural rubber applications.     

Mechanical and dynamic mechanical properties of natural rubber blended with waste rubber powder modified by both microwave and sol–gel method

Waste rubber powder (WRP) was modified by microwave, sol–gel method, and both microwave and sol–gel method, respectively. The mechanical and dynamic mechanical properties of natural rubber (NR)/modified WRP composite were investigated. The influence of bis‐(3‐(triethoxysilyl)‐propyl)‐tetrasulfide (TESPT) content on curing characteristics and mechanical properties of vulcanizate was also studied. The results showed that NR/WRP modified by both microwave and sol–gel method composite owned the best mechanical properties. Rubber processing analyzer was used to characterize the interaction between silica and rubber chains and the dispersion of silica. With increase of TESPT content, the Payne effect decreased. Scanning electron microscopy indicated the coherency and homogeneity of in situ generated silica filled vulcanizate. Dynamic mechanical analyzer showed that NR/WRP modified by both microwave and sol–gel method composite with 5 phr TESPT exhibited the lower tan δ at temperature range of 50–80°C, compared with composite without TESPT and the higher tan δ at temperature of 0°C, compared with the conventional modification of WRP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dynamic Mechanical Properties of Carbon Black Filled Ethylene Vinyl Acetate Rubber

Abstract

The dynamic mechanical properties of ethylene vinyl acetate (EVA) rubber filled with different loadings of carbon black and at different degrees of crosslinking were studied over a wide range of temperatures (-150° to +200°C). The loss tangent (tan δ) versus temperature plots indicated presence of different transitions. The α-transition (or the glass-rubber transition) corresponding to the maximum in tan δ value, occurred at ?17°C, which is the principal glass-transition temperature (abbreviated as T _g) of EVA rubber. The γ-transition occurred in the temperature region of ?125° to ?135°C, while the β-transition appeared as a shoulder in the temperature region of ?65° to ?75°C. Besides, there was also a high tempeature transition around +62°C which is known as liquid to liquid transition (T _1.1). Incorporation of carbon black filler did not cause any shift of T _g, while the tan δ peak values at T _g decreased sequentially with increase in filler loading. The γ- and β-relaxations were found to be insensitive to filler loading. The T _1.1 transition, however, was found to be suppressed by incorporation of carbon black filler particularly at high loading. Extent of crosslinking did not influence the T _g But, the T _1.1 transition, which was prominent with the lightly crosslinked system was found to be suppressed at high level of crosslinking. Strain dependent dynamic mechanical properties under isothermal conditions showed that the secondary structure breakdown of carbon black filler under the effect of strain amplitude is influenced by the degree of crosslinking of EVA rubber.     

Migration behaviors of wax to surface in rubber vulcanizates

The migration behaviors of wax to the surface in rubber vulcanizates were studied using natural (NR), styrene–butadiene (SBR), and butadiene rubber (BR) vulcanizates. The migration experiments were performed in a convection oven at 60 and 80°C for 14 days. There were less than 10% of the normal alkanes of n-C₂₂H₄₆ to n-C₃₈H₇₈ that migrated to the surface in the vulcanizates and evaporated at 60°C for 14 days. The amount of normal alkanes that migrated to the surface in the vulcanizates and evaporated at 80°C for 14 days was decreased by increasing the molecular weight of the normal alkanes. The migration of the normal alkanes in the NR vulcanizate was more sensitive to the variation of the molecular size of the normal alkanes than those in the BR and SBR vulcanizates. The migration behaviors of the normal alkanes in the vulcanizates were very similar to their evaporation behaviors. Major factors influencing the migration behaviors of the wax were discussed using the calculations of structures of the normal alkanes and evaporation experiments of wax. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2587–2593, 1999     

Preparation of high‐performance damping materials based on carboxylated nitrile rubber: Combination of organic hybridization and fiber reinforcement

The dynamic mechanical properties denoted by storage modulus (E′) and loss factor (tan δ) of binary and ternary systems consisting of carboxylated nitrile rubber (XNBR) filled with organic hindered phenol compound 2,2′‐methylenebis(6‐tert‐butyl‐4‐methylphenol) (AO‐2246) or/and short carbon fiber (SCF) were investigated. DMA results of binary XNBR/AO‐2246 system showed that by addition of AO‐2246, the tan δ peak maximum of XNBR was remarkably increased up to 3.5, and its peak position was also significantly shifted to room temperature, demonstrating that XNBR/AO‐2246 composite is a promising damping material. Nevertheless, application of such XNBR/AO‐2246 composite is limited due to its relatively low E′ value above glass transition temperature. Therefore, to develop a high‐performance damping material with high tan δ peak and high modulus as well as controllable tan δ peak position, the combination of organic hybridization and fiber reinforcement were adopted. DMA analysis of various ternary XNBR/AO‐2246/SCF systems revealed that by introduction of SCF, the E′ value of XNBR/AO‐2246 was increased remarkably while the tan δ peak maximum was still higher than 2.5. Thus, a new type of XNBR‐based high‐performance damping material was developed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Dynamic viscoelastic properties of carbon black loaded closed-cell microcellular ethylene-propylene-diene rubber vulcanizates: Effect of blowing agent,temperature frequency,and strain

Dynamic mechanical analysis of carbon black loaded solid and closed-cell microcellular ethylene-propylene-diene (EPDM) vulcanizates was studied at four frequencies of 3.5, 11, 35, and 110 Hz and temperatures from −100 to 150°C. A plot of the log of the storage modulus bears a linear relationship with the log of density for solid as well as closed-cell microcellular rubber. The slope of the line is found to be temperature-dependent. The relative storage modulus decreases with decrease in the relative density. It was also observed that the storage modulus and tan δ are both frequency- and temperature-dependent. The storage modulus results are superposed to form master curves of the modulus vs. Iog temperature-reduced frequency, using shift factors calculated by the Arrhenius equation. Strain-dependent isothermal dynamic mechanical analysis was carried out for DSA varying from 0.07 to 5%. The effect of blowing agent loading on the storage modulus (E′) and loss tangent (tan δ) were also studied. Cole-Cole plots of microcellular rubber shows a circular arc relationship with the density. Plots of tan δ against E′ were found to exhibit a linear relationship. © 1996 John Wiley & Sons, Inc.     

Cardanol grafted natural rubber: A green substitute to natural rubber for enhancing silica filler dispersion

Natural rubber (NR) usage is wide‐spread from pencil erasers to aero tyres. Carbon black and silica are the most common reinforcing fillers in the rubber industries. Carbon black enhances the mechanical properties, while silica reduces the rolling resistance and enhances the wet grip characteristics. However, the dispersion of polar silica fillers in the nonpolar hydrocarbon rubbers like natural rubber is a serious issue to be resolved. In recent years, cardanol, an agricultural by‐product of the cashew industry is already established as a multifunctional additive in the rubber. The present study focuses on dispersion of silica filler in natural rubber grafted with cardanol (CGNR) and determination of its technical properties. The optimum cure time reduces and the cure rate increases for the CGNR vulcanizates as compared to that of the NR vulcanizates at all loadings of silica varying from 30 to 60 phr. The interaction between the phenolic moiety of cardanol and the siloxane as well as silanol functional groups present on the silica surface enhances the rubber–filler interaction which leads to better reinforcement. The crosslink density and bound rubber content are found to be higher for the silica reinforced CGNR vulcanizates. The physico‐mechanical properties of the silica reinforced CGNR vulcanizates are superior to those of the NR vulcanizates. The CGNR vulcanizates show lower compression set and lower abrasion loss. The dynamic‐mechanical properties exhibit less Payne effect for silica reinforced CGNR vulcanizates as compared to the NR vulcanizates. The transmission electron photomicrographs show uniform dispersion of silica filler in the CGNR matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43057.     

Influence of rubber composition on change of crosslink density of rubber vulcanizates with EV cure system by thermal aging

Variation of the crosslink density of a rubber vulcanizate depending on the rubber composition after the thermal aging was studied with single rubber, biblend, and triblend vulcanizates of natural rubber (NR), butadiene rubber (BR), and styrene‐butadiene rubber (SBR). The efficient vulcanization (EV) system was employed to minimize the influence of free sulfur in the vulcanizate on the change of the crosslink density. Thermal aging was performed at 40, 60, and 80°C for 20 days with 5‐day intervals. The crosslink densities of the vulcanizates after the thermal aging increase. For the single rubber vulcanizates, variation of the crosslink density by the thermal aging has the order: SBR > BR > NR. For the biblend vulcanizates, variations of the crosslink densities of the NR/SBR and SBR/BR blends are larger than that of NR/BR blend. Variation of the crosslink density of the vulcanizate increases by increasing the SBR content in the vulcanizate. Variation of the crosslink density of the rubber vulcanizate depending on the rubber composition was explained by miscibility of the blends, combination reaction of the pendent groups, and mobility of the pendent group. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1378–1384, 2000     

Mechanical and dynamic mechanical properties of rice husk ash–filled natural rubber compounds

A laboratory‐sized two‐roll mill was used to incorporate rice husk ash into natural rubber (NR). A conventional vulcanization system was used for curing and cure studies were carried out on a Monsanto rheometer. Physical testing of the NR vulcanizates involved determining tensile and tear resistances and hardness. Swelling behavior of NR compounds and scanning electron microscopy were used to investigate the interaction between rice husk ash and natural rubber. Also, dynamical mechanical thermal analysis was used to assess filler–rubber interactions in terms of storage modulus (E′) and loss tangent (tan δ). For comparison purposes, two commercial fillers, precipitated silica (Zeosil‐175) and carbon black (N774), were also used. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2331–2346, 2002     

Influence of rubber composition on migration behaviors of antiozonants in carbon black‐filled rubber vulcanizates composed of NR,SBR, and BR

Migration behaviors of antiozonants in carbon black‐filled rubber vulcanizates with different rubber compositions of natural rubber (NR), styrene–butadiene rubber (SBR), and butadiene rubber (BR) were studied at constant temperatures of 40–100°C and outdoors. Three single rubber‐based vulcanizates, three biblends, and three triblends were used. N‐Phenyl‐N′‐isopropyl‐p‐phenylenediamine (IPPD) and N‐phenyl‐N′‐(1,3‐dimethylbutyl)‐p‐phenylenediamine (HPPD) were employed as antiozonants. Migration rates of the antiozonants became faster with increasing the temperature. The order of the migration rates in the single rubber‐based vulcanizates was BR > NR > SBR. The migration rates in the vulcanizates containing SBR, on the whole, increased with decreasing the SBR content, while those in the vulcanizates containing BR decreased with decreasing the BR content. Difference in the migration behaviors of the antiozonants depending on the rubber composition was explained both by the intermolecular interactions of the antiozonants with the matrix and by interface formed between dissimilar rubbers in the blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 237–242, 2001     

反式-1,4-聚异戊二烯的结晶性对丁苯橡胶/反式-1,4-聚异戊二烯共混硫化胶动态力学性能的影响

用动态力学分析仪和差示扫描量热仪研究了丁苯橡胶(SBR)/反式-1,4-聚异戊二烯(TPI)共混硫化胶的动态力学性能和结晶性能。结果表明,SBR与TPI的两相相容性良好。随着TPI用量的增加,SBR/TPI共混硫化胶的玻璃化转变温度向低温方向移动,且损耗因子峰值逐渐降低。用炭黑填充CV体系硫化SBR/TPI共混胶的损耗因子峰值低于相应的未填充胶料;而当TPI晶体熔融后,炭黑填充胶料的损耗因子要大于未填充者。不同硫化体系硫化SBR/TPI共混胶的损耗因子峰值和玻璃化转变温度从大到小的变化依次为CV体系、EV体系和DCP体系。     

Properties of fullerene‐containing natural rubber

Addition of fullerene in concentration between 0.065 and 0.75 phr increases Schob elasticity, hardness, and modulus of NR‐based rubber. There is no substantial influence of fullerene on T_g, tan δ, and G‐modulus all evaluated by DMA at twisting within a temperature range ?150 to ?50°C (glassy state). At temperatures between 0 and 150°C (rubbery state) it is different, namely an increase in modulus and some changes in the slope of segments in G(T) curves were observed. It could be resulted from additional strong physical junctions of the rubber network. This suggests the growth of degradation energies of the branching junctions and related rise in the aging resistance as concentration of fullerene increases. Simultaneously, it could be expected some reduction of tire temperature at service. Because of this, introduction of fullerene could be reasonable for tread rubbers in case of reduction of its price. Permittivity and dielectric loss angle are correlated with fullerene concentration. Compounding technology when fullerene dispersed within carbon black is mixed with raw rubber on available machines could be easily implemented in the industry. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 390–398, 2006     

Effect of silica filler on dynamic mechanical properties of lonic elastomer based on carboxylated nitrile rubber

Variation of dynamic mechanical propeties like storage modulus (E′) and loss tangent (tan δ) with temperature show the presence of two transitions in the carboxylated nitrile rubber (XNBR) molded in the presence of zinc oxide (ZnO). The low-temperature transition is due to the glass–rubber transition (T_g) of XNBR, and the high-temperature transition is due to formation of ionic clusters. Incorporation of reinforcing silica filler makes the high temperature transition more prominent and high filler loading casues a shift of the transition temperature to the higer side. It is believed that the rubber–filler interaction in the cluster region causes striking changes in the variation of E′ and tan δ with a double-strain amplitude (DSA). © 1995 John Wiley & Sons, Inc.     

Effect of carbon black/nanoclay hybrid filler on the dynamic properties of natural rubber vulcanizates

In this study, natural rubber (NR) nanocomposites based on carbon black (CB) and two poly(ethylene glycol) (PEG)‐modified clay hybrid filler were fabricated. The morphology and mechanical properties were studied. The dynamic properties of NR vulcanizates were investigated over a range of strain amplitude at two temperatures. It was found that NR with hybrid filler exhibits superior mechanical properties over that with CB as single phase filler. The hybrid filler causes a significant alteration in the dynamic properties of rubber. The Payne effect becomes more pronounced in rubber with modified clay. A decrease in loss factor (tanδ) was observed for rubber with hybrid filler also. The results revealed that the inclusion of nanoclay (NC) could induce a stronger and more developed filler network. Because of the anisotropy of the nanolayers, NC would depress the reconstruction of filler network, or lower the reformation rates when broken down under deformation, giving rise to lower tanδ value at broad temperature range as well as strain amplitude. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Role of calcium stearate as a dispersion promoter for new generation carbon black‐organoclay based rubber nanocomposites for tyre application

A novel carbon black (CB) and nanoclay (NC) dual phase‐filled system in SBR matrix has been developed to be employed as a tyre tread compound with optimized performance properties. The nanocomposite has shown improved dynamic properties i.e. rolling resistance (tan δ at 60°C) and wet skid resistance (tan δ at 0°C), for relatively lower loading of NC (3 phr). However, the mechanical properties and wear resistance combined with above mentioned dynamic properties have been further improved by direct substitution of stearic acid with calcium stearate. This has been argued to be due to enhanced filler‐rubber interaction by the strong ionic interactions between the calcium ion (Ca⁺⁺) and layered silicates (NC) having anionic surface. Transmission electron microscopy and low angle X‐ray diffraction studies have revealed the role of calcium stearate as a dispersion promoter for organoclay. Fourier transform infra‐red spectroscopy study has shown a shift in the Si O Si bond towards lower wave number indicating better polymer‐clay interaction. A detailed investigation on the dynamic rheological behavior of SBR‐CB‐NC nanocomposites has been carried out using rubber process analyzer to invoke an insight into the processing behavior of these composites. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

New approach for preparation of dry natural rubber nanocomposites through acid‐free co‐coagulation: Effect of organoclay content

Natural rubber (NR) vulcanizates exhibit good mechanical properties compared to vulcanizates of synthetic rubbers. Incorporation of a conventional filler at higher loadings to NR enhances its modulus, while reduction in tensile strength and elongation. This paper presents a new strategy for development of a NR‐clay nanocomposite with enhanced mechanical properties by incorporation of lower loadings (2–8 phr) of cetyl trimethyl ammonium bromide modified montmorillonite clay (OMMT‐C) under acid‐free environment. The effect of OMMT‐C loading on cure characteristics, rubber‐filler interactions, crosslink density, dynamic mechanical thermal properties, and mechanical properties were evaluated. Incorporation of OMMT‐C accelerated the vulcanization process and enhanced mechanical properties. X‐ray diffraction analysis and scanning electron microscopy images revealed that the formation of intercalated clay structures at lower OMMT‐C loadings, and clay aggregates at higher loadings. A nanocomposite at OMMT‐C loading of 2 phr exhibited the best balanced mechanical properties, and was associated with highest crosslink density and rubber–filler interactions. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46502.     

Structural evolution of recycled tire rubber in asphalt

The performance of recycled‐tire‐rubber‐modified asphalt mainly depends on the structure of rubber in the asphalt. The effects of the curing temperature, mixing time, and shearing on the evolution of the chemical structure and morphological structure of crumb rubber in asphalt were investigated. The crosslink density, compositions, and morphological evolution of the residual crumb rubber were characterized. The results show that the structure evolution of tire rubber in asphalt was greatly affected by the curing temperature. At a low curing temperature (180°C), the crosslinking network of the tire rubber was broken down, and this led to the partial dissolution of natural rubber (NR). However, at high curing temperature (240°C), the dissolution of NR, synthetic rubber, carbon black, and inorganic filler was observed. The released carbon black covered with a thin layer of bound rubber dispersed at a microstructured or nanostructured size in the asphalt. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42954.