Influence of 1,2‐unit contents on retraction behaviors of SBR vulcanizates

Styrene‐butadiene rubber (SBR) has four different repeat units of styrene, cis‐1,4‐, trans‐1,4‐, and 1,2‐uints. Influence of the 1,2‐unit content on the retraction behaviors of SBR vulcanizates reinforced with silica or carbon black was studied. The retraction behaviors were compared in terms of the filler systems and the microstructures of SBR. The silica‐filled vulcanizates containing a coupling agent showed nearly the same retraction behaviors as the carbon black‐filled ones, but the silica‐filled vulcanizates without a coupling agent were recovered slower than the carbon black‐filled ones. The vulcanizates with lower 1,2‐unit content started to recover at lower temperature than that with higher 1,2‐unit content. The recovery rate increased with increase of the 1,2‐unit content of SBR. The experimental results were explained with the polymer‐filler interactions, filler dispersion, glass transition temperature, and modulus. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4707–4711, 2006     

NR原位改性炭黑对NR胶料性能的影响

分别采用高温转矩流变仪和常温两辊开炼机制备NR原位改性炭黑(GCB)和NR/炭黑共混物(KCB),并制备GCB/NR和KCB/NR硫化胶,对其性能进行研究.结果表明,与KCB相比,GCB的耐热性能提高,结合橡胶质量分数增大;当炭黑用量相同时,与KCB/NR硫化胶相比,GCB/NR硫化胶的交联密度、定伸应力、压缩永久变形和储能模量较大,拉伸强度和回弹值较小;当炭黑用量小于60份时,GCB/NR硫化胶耐疲劳性能优于KCB/NR硫化胶.     

A comparative study of aging characteristics and thermal stability of oil palm ash,silica, and carbon black filled natural rubber vulcanizates

Filler‐filled natural rubber (NR) vulcanizates were prepared by conventional laboratory‐sized two roll mills and cured using sulfuric system. The effect of thermal aging on physical properties and thermogravimetric analysis (TGA) of oil palm ash (OPA) and commercial fillers (i.e., silica vulkasil C and carbon black N330)‐filled NR vulcanizates at respective optimum loading and equal loading were studied. Before aging, the OPA‐filled vulcanizates showed comparable optimum strength as carbon black‐filled vulcanizates. The hardening of aged filler‐filled NR vulcanizates happened after aging, thereby tensile strength and elongation at break reduced while the modulus increased. Fifty phr carbon black‐filled vulcanizates showed better retention in tensile properties as compared to silica (10 phr) and OPA (1 phr). This was attributed to the addition of different filler loading and this finding was further explained when equal loading of filler‐filled vulcanizates was studied. Fourier transform infra‐red analysis showed chemical structure had changed and tensile fractured surface exhibited smooth appearance due to the deterioration in tensile properties after aging. TGA also denoted the thermal stability was depending on the amount of filler loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4474–4481, 2013     

Influence of polymer–filler interactions on retraction behaviors of natural rubber vulcanizates reinforced with silica and carbon black

In general, silica‐filled rubber compounds contain a silane coupling agent to improve the filler dispersion and polymer–filler interactions. The silane coupling agent modifies the silica surface and makes crosslinks between the rubber and the silica. Influence of the modification of silica on the retraction behaviors of natural rubber (NR) vulcanizates reinforced with silica and carbon black was studied. Variation of the retraction behaviors of NR vulcanizates with filler composition was also investigated. The vulcanizates containing the silane coupling agent were recovered faster than those without the silane coupling agent. The recovery difference between the vulcanizates without and with the silane coupling agent increased with increased silica content. For the vulcanizates containing the silane coupling agent, the retraction behaviors were nearly the same, irrespective of filler composition. But, for the vulcanizates without the silane coupling agent, the vulcanizate was recovered more and more slowly as the silica content increased. The experimental results are explained with the polymer–filler interactions, modification of silica surface, and formation of crosslinks between silica and rubber. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 691–696, 2006     

Utilization of bowstring hemp fiber as a filler in natural rubber compounds

The cure characteristics and physicomechanical properties of natural rubber (standard Nigerian rubber) vulcanizates filled with the fiber of bowstring hemp (Sansevieria liberica) and carbon black were investigated. The results showed that the scorch and cure times decreased, whereas the maximum torques increased, with increasing filler loadings for both bowstring hemp fiber and carbon black filled vulcanizates. The tensile strength of both bowstring hemp fiber and carbon black filled vulcanizates increased to a maximum at a 40 phr filler concentration before decreasing. The elongation at break and rebound resilience decreased, whereas the modulus, specific gravity, abrasion resistance, and hardness increased, with increasing filler contents. The carbon black/natural rubber vulcanizates had higher tensile strength, which was about 1.5 times that of bowstring hemp fiber/natural rubber vulcanizates. This superiority in the tensile strength was probably due to the higher moisture content and larger particle size of the bowstring hemp fiber. However, the bowstring hemp fiber/natural rubber vulcanizates showed superior hardness. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

An investigation on the reinforcing potential of red earth as filler for natural rubber compounds

Locally sourced red earth (RE) was air‐dried, pulverized, and screened with a sieve of mesh size 75 nm. It was characterized in terms of its moisture content, loss on ignition, silica content, iodine adsorption number, oil absorption, pH, and metal oxide compositions. Natural rubber, standard Nigerian rubber used for this work was first characterized in terms of its dirt, ash and nitrogen contents, volatile matter, plasticity retention index, and Mooney viscosity. The RE was applied as filler wholly and in blends with standard carbon black, CB (N330) filler in the natural rubber compounding using efficient vulcanization system. The cure and the physicomechanical properties of the compounds and vulcanizates were, respectively, measured as function of filler loading. The results were compared with those of the standard carbon black (N330)‐filled natural rubber. It was found, that the RE‐filled natural rubber showed substantial reinforcement of the rubber, though inferior to carbon black (N330) filled vulcanizates, the tensile strength of the carbon black‐filled vulcanizates is about one half times that of the RE‐filled vulcanizates. The tensile properties of the RE‐filled vulcanizates improved markedly by blending the RE‐filler with the carbon black (N330). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of carbon blacks on relaxation phenomenon of chlorobutyl vulcanizates

The effect of the types of carbon black on the physicomechanical, dynamic mechanical, and dielectric relaxation spectra in chlorobutyl vulcanizates was studied. The primary relaxation (α transition, the glass transition) was studied by dynamic mechanical analysis as a function of temperature (?60 to +100°C) and by positron annihilation lifetime spectroscopy (?70 to +100°C). Irrespective of the type of carbon black that was used, all composites showed glass‐transition temperatures in the range of ?29 to ?33°C, which was explained on the basis of the relaxation dynamics of polyisobutylene chains in the vicinity of the fillers. The secondary relaxation (α* or β relaxation) was studied using dielectric relaxation spectra in the frequency range of 100–10⁶ Hz. The nonlinear strain dependent dynamical parameters (Payne effect) were also evaluated at dynamic strain amplitudes of 0.07–5%. The nonlinearity in the tan δ and storage modulus was explained by the concept of filler–polymer interactions and the interaggregate attraction (filler networking). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1809–1820, 2006     

On the potential of organoclay with respect to conventional fillers (carbon black,silica) for epoxidized natural rubber compatibilized natural rubber vulcanizates

Onium modified montmorillonite (organoclay) was 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) in 10 parts per hundred rubber (phr) was used as a compatibilizer in this study. For comparison purposes, two commercial fillers: carbon black (grade N330) and silica (grade vulcasil‐S) were used. Cure characteristics were carried out on a Monsanto MDR2000 Rheometer. Organoclay filled vulcanizate showed the lowest values of torque maximum, torque minimum, scorch, and cure times. The kinetics of cure reaction showed organoclay could behave as a cocuring agent. The mechanical testing of the vulcanizates involved the determination of tensile and tear properties. The improvement of tensile strength, elongation at break, and tear properties in organoclay filled vulcanizate were significantly higher compared to silica and carbon black filled vulcanizates. In terms of reinforcing efficiency (RE), organoclay exhibited the highest stiffness followed by silica and carbon black filled vulcanizates. Scanning electron microscopy revealed that incorporation of various types of fillers has transformed the failure mechanism of the resulting NR vulcanizates compared to the gum vulcanizates. Dynamic mechanical thermal analysis (DMTA) revealed that the stiffness and molecular relaxation of NR vulcanizates are strongly affected by the filler–rubber interactions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2438–2445, 2004     

Deformation and energy-absorption characteristics of microcellular EPDM rubber

Compressive stress–strain properties of closed-cell microcellular EPDM rubber vulcanizates with and without a filler were studied with the variation of density. For filler variation studies, silica and carbon black (N330) were used. With a decrease in density, the stress–strain curve for microcellular EPDM behaves differently from that for the solid vulcanizates: The curve rises steeply when cell breakdown occurs. The compressive stress–strain properties are found to depend on the strain rate. The compression set at constant stress increases with decreasing density. The energy-absorption behavior was studied from the compressive stress–strain properties. The efficiency, E, and ideality, I, parameters were also determined as they are useful for the evaluation of closed-cell microcellular rubber as a cushioning and packaging material. These parameters were plotted against stress to find the maximum efficiency and maximum ideality region which will make these materials suitable for cushioning or packaging applications. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:263–269, 1998     

Curing characteristics,mechanical properties and morphology of butyl rubber filled with ground tire rubber (GTR)

The results on testing application of ground tire rubber (GTR), as potential filler for butyl rubber, are presented. The GTR content variation, within the range of 10–90 phr, was studied with respect to the vulcanization process, static mechanical properties (tensile strength, elongation-at-break, hardness and resilience), dynamic mechanical properties and the morphology of the obtained vulcanizates. Butyl rubber was characterized by its low compatibility to other elastomers [i.e., natural rubber and styrene–butadiene rubber (SBR)—the main ingredients of tires] and low degree of unsaturation. To evaluate the impact of these factors on curing characteristics and mechanical properties of butyl rubber vulcanizates filled with GTR, the same compositions of SBR compounds, cured under identical conditions, were used as reference samples. Based on the obtained data, it can be stated that butyl rubber vulcanizates containing 30 phr of GTR as filler revealed the highest tensile strength and elongation-at-break. The microstructural analysis of a sample containing 30 phr of GTR revealed strong interactions between the butyl rubber matrix and GTR. This phenomenon resulted mainly from two factors. First, the cross-link density of the butyl rubber matrix was affected by its competition against GTR for cross-linking agents. Secondly, the migration of carbon black particles from GTR into the butyl rubber matrix had a significant impact on properties of the obtained vulcanizates.     

Use of rice husk ash as filler in natural rubber vulcanizates: In comparison with other commercial fillers

Rice husk ash is mainly composed of silica and carbon black remaining from incomplete combustion. Both silica and carbon black have long been recognized as the main reinforcing fillers used in the rubber industry to enhance certain properties of rubber vulcanizates, such as modulus and tensile strength. In this study, two grades of rice husk ash (low‐ and high‐carbon contents) were used as filler in natural rubber. Comparison was made of the reinforcing effect between rice husk ashes and other commercial fillers such as talcum, china clay, calcium carbonate, silica, and carbon black. Fourier transform infrared spectroscopy (FTIR) analysis was employed to study the presence of functional groups on the ash surface. The effect of silane coupling agent, bis(3‐triethoxysilylpropyl)tetrasulfane (Si‐69), on the properties of ash‐filled vulcanizates was also investigated. It was found that both grades of rice husk ash provide inferior mechanical properties (tensile strength, modulus, hardness, abrasion resistance, and tear strength) in comparison with reinforcing fillers such as silica and carbon black. However, the mechanical properties of the vulcanizates filled with rice husk ash are comparable to those filled with inert fillers. The addition of silane‐coupling agent has little effect on the properties of the ash‐filled vulcanizates. This is simply due to the lack of silanol groups on the ash surface. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2485–2493, 2002     

Effect of Grafted Carbon Black on Properties of Vulcanized Natural Rubber

Summary To modify carbon black (CB) surface, in situ grafting of natural rubber (NR) onto the CB surface by solid-state method was used to get grafted carbon black (GCB). The vulcanization characters of NR compounds employed CB and GCB were investigated. Crosslinking density of vulcanized NR was measured by equilibrium swelling method. As a result, it was found that GCB could improve both cure rate and crosslinking density. Moreover, the mechanical properties of vulcanized NR filled with GCB were enhanced to a large extent compared with vulcanized NR filled with CB. No Payne Effect was observed in GCB filled NR compounds during dynamic properties testing, indicating that there was no filler network and GCB was dispersed uniformly in NR matrix, which was proved by SEM micrographs. Based on above results, it was considered that the grafting modification weakened filler-filler interaction and enhanced filler-polymer interaction.     

Comparative study of silica-, nanoclay- and carbon black-filled EPDM rubbers

Silica-, nanoclay-, and carbon black (CB)-filled ethylene–propylene–diene terpolymer (EPDM) mixtures were prepared and subsequently vulcanized. Rheological properties and cure characteristics of the mixtures and mechanical properties of vulcanizates were measured. Rheological property measurements indicated the storage modulus, loss modulus, and complex dynamic viscosity of silica-filled EPDM mixtures were much higher than those of CB-filled EPDM mixtures while tan δ values were lower. The optimum cure time of silica- and nanoclay-filled EPDM mixtures increased with filler loading, whereas the values for CB-filled mixtures slightly decreased with loading. The hardness, modulus, elongation at break, and tensile strength of all the vulcanizates increased with increasing filler loading. The elongation at break of CB-filled EPDM vulcanizates increased insignificantly with CB loading. Among the three fillers, the increase of the tensile strength and elongation at break was most significant for silica-filled EPDM vulcanizates. Remarkably, for 30 phr silica-filled EPDM vulcanizates, a tensile strength and elongation at break of 23.5 MPa and 1045% was achieved, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of fillers on the relaxation behavior of chlorobutyl vulcanizates

The effect of addition of fillers (carbon black (CB), carbon silica dual phase filler (CSDPF), and nanoclays) on the relaxation behavior of chlorobutyl vulcanizates has been studied. The primary relaxation (α‐transition, the glass transition) was studied by dynamic mechanical analysis as a function of temperature (?60 to +100°C) and positron annihilation life time spectroscopy (?70 to +110°C). Irrespective of the filler and its loading, all the composites showed the glass transition temperature in the range of –29 to –33°C, which was explained on the basis of relaxation chain dynamics of polyisobutylene in the vicinity of fillers. The secondary relaxation (α* or β relaxation) was studied using dielectric relaxation spectra in the frequency range of 100–10⁶ Hz. Nanoclays had a profound influence on the secondary relaxation, whereas CSDPF and CB had a marginal effect. The nonlinear strain dependent dynamical parameters were also evaluated at double strain amplitudes of 0.07–5%. The nonlinearity in tan δ and storage modulus has been explained on the concept of filler–polymer interactions and the interaggregate attraction (filler networking). The “percolation limit” of the fillers in the composites has been studied by DC conductivity measurements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3161–3173, 2006     

Use of ground pistachio shell as alternative filler in natural rubber/styrene–butadiene rubber‐based rubber compounds

Bio‐based polymers and fillers draw a significant interest. Focus of this work is to use ground pistachio shell as alternative filler in a model natural rubber/styrene–butadiene rubber‐based conveyor belt compound. Compounds were prepared using a laboratory two‐roll mill by partial replacing of carbon black with pistachio shell. Cure characteristics, mechanical, thermal, morphological, and abrasion properties of pistachio shell containing vulcanizates have been studied. Increasing pistachio shell loading causes lower cure extent and lower tensile strength. However, abrasion resistance is significantly improved by incorporation of pistachio shell. Benefits of using pistachio shell as filler may include producing low price, environmentally friendly, and high abrasion resistant vulcanizates when some loses in tensile properties can be tolerated. POLYM. COMPOS., 35:245–252, 2014. © 2013 Society of Plastics Engineers     

Dielectric relaxation of conductive carbon black reinforced chlorosulfonated polyethylene vulcanizates

The frequency dependent dielectric relaxation behavior of conductive carbon black reinforced chlorosulfonated polyethylene (CSM) vulcanizates has been studied for different filler loadings in the frequency range of 10²–10⁶ Hz over a wide range of temperatures (30–120°C). The effects of filler loadings on the dielectric permittivity (ε′), dielectric loss tangent (tan δ), impedance, and electrical conductivity were studied. The variation of the dielectric permittivity with the filler loadings was explained on the basis of interfacial polarization of the filler in the polymer matrix. The frequency dependence of ac conductivity has been investigated using percolation theory. The effect of filler loading on the complex and real parts of impedance was clearly observed, which can be explained on the basis of relaxation dynamics of polymer chains in the vicinity of fillers. The percolation threshold occurred near 30 phr of filler loading. Scanning electron microphotographs showed the agglomeration of the filler on and above these filler loadings. Additionally, the effect of temperature on dielectric loss tangent, dielectric permittivity, ac conductivity, and Nyquist plot of conductive black reinforced CSM vulcanizates has been studied. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

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     

Synergistic effect of carbon black and carbon–silica dual phase filler in natural rubber matrix

In this article, the synergistic effects of carbon black (CB) and modified carbon–silica dual phase filler (MCSDPF) on the properties of natural rubber (NR) were investigated. MCSDPF was prepared by modifying carbon–silica dual phase filler (CSDPF) with bis(3‐triethoxysilylpropyl)tetrasulphane (Si‐69). Fourier transform infrared spectroscopy and thermogravimetric analyzer analyses revealed that Si‐69 was successfully grafted to CSDPF. NR‐based compounds containing various combinations of MCSDPF and CB were prepared through a mechanical mixing. Investigations of mechanical properties, ageing resistance, abrasion resistance, dynamic mechanical properties, and morphology of tear fractured surface of MCSDPF/CB/NR vulcanizates were conducted. Our study shows that adding MCSDPF led to significant improvement in the tear resistance, fatigue life, and elongation at break of MCSDPF/CB/NR vulcanizates. Optimum stoichiometric combination of MCSDPF and CB inside the NR matrix was derived (ratio of MCSDPF and CB in wt% = 15/50), which showed synergistic effects of MCSDPF upon CB that was ultimately reflected in their tensile strength, wet skid resistance, and rolling resistance. POLYM. COMPOS., 35:1466–1472, 2014. © 2013 Society of Plastics Engineers     

Relaxation behavior of conductive carbon black reinforced EPDM microcellular vulcanizates

Dynamic mechanical analysis and dielectric relaxation spectra of conductive carbon black reinforced microcellular EPDM vulcanizates were used to study the relaxation behavior as a function of temperature (−90 to +100°C) and frequency (0.01–10⁵ Hz). The effect of filler and blowing agent loadings on dynamic mechanical and dielectric relaxation characteristics has been investigated. The effect of filler and blowing agent loadings on glass transition temperature was marginal for all the composites (T_g value was in the range of −39 to −35°C), which has been explained on the basis of relaxation dynamics of polymer chains in the vicinity of fillers. Strain-dependent dynamical parameters were evaluated at dynamic strain amplitudes of 0.07–5%. The nonlinearity in storage modulus has been explained based on the concept of filler–polymer interaction and interaggregate attraction (filler networking) of carbon black. The variation in real and complex part of impedance with frequency has been studied as a function of filler and blowing agent loading. Additionally, the effect of crosslinking on the dielectric relaxation has also been reported. POLYM. ENG. SCI., 47:984–995, 2007. © 2007 Society of Plastics Engineers     

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