Continuous ultrasonic devulcanization of carbon black‐filled NR vulcanizates

The continuous ultrasonic devulcanization of natural rubber (NR) filled with various concentrations of carbon black (CB) indicated a minimum of crosslink density and gel fraction at an intermediate amplitude, which is independent of CB content. An attempt was made to improve the efficiency of devulcanization by use of various chemicals (1,3 Diphenylguanidine, 2‐Mercaptobenzothiazole, Thianaphthene). However, these experiments did not indicate any improvement in comparison with devulcanization without chemicals. An idea of adding fresh CB into devulcanized compound, which has been shown to improve mechanical properties in the case of styrene–butadiene rubber (SBR), was tested in the present study for CB filled NR compound. The obtained result indicated that an addition of fresh CB to devulcanized CB‐filled NR did not lead to an improvement in mechanical properties upon revulcanization. The revulcanization recipe was optimized to improve the mechanical properties of revulcanized CB‐filled NR vulcanizates. It was found that CB‐filled NR upon revulcanization retained its strain‐induced cystallizability with the tensile strength and elongation at break at about 50 and 70% level of the virgin vulcanizates. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2340–2348, 2001     

Special electrical conductivity of carbon black‐filled two‐phased thermoplastic vulcanizates

The electrical properties of carbon black (CB)‐filled two‐phased thermoplastic vulcanizates (based on ethylene‐propylene‐diene copolymer and polypropylene, TPV) were investigated in this article. The results showed that the composites had a singularity in electrical conductivity compared with CB‐filled polypropylene composites. Both the loading of CB and the concentration of rubber phase in TPV had the remarkable effect on electrical property of composites. The rubber particles in TPV presented unique and competitive effects in constructing CB electrical conducting network, namely exclusion and block effects. The percolation threshold value of composites apparently decreased with rubber phase content. However, percolation behavior of composites was weakened when rubber phase content was very high. The percolation behavior of composites with loading of CB is weakened apparently by rubber particles. When annealing the composites in the melt state, the resistance‐time dependence of composites was strongly affected by the pressure of mold annealing. Although air aging had a negligible effect on the electrical properties, the microstructure of the CB/TPV composites had changed during air aging. CB/TPV composite only exhibited the negative temperature coefficient behavior even though the temperature was in the melting region of polypropylene, which was mainly attributed to the exclusive effect brought by the thermal expansion of rubber particles. The special electrical properties of CB/TPV can find potential application in many fields. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Crack growth and abrasion resistance of carbon black‐filled purified natural rubber vulcanizates

The influence of parameters contributing to rubber stiffness, including, crosslink density, hardness, and modulus, on the crack growth and abrasion resistance of carbon black‐filled purified natural rubber (PNR) vulcanizates as well as a whole natural rubber (WNR) vulcanizate counterpart or a control were elucidated. In addition, the tensile properties of PNR and WNR were also determined. PNR containing the same curative level as that of the control had lower stiffness and exhibited superior crack growth resistance. The results revealed that the improved crack growth resistance of PNR, compared to the control, was due to its lower crosslink density, hardness, and modulus. In addition, the tensile strength and abrasion resistance of PNR vulcanizates were not as sensitive as the crack growth resistance to the changes of their stiffness. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1793–1796, 2003     

Analysis of unbound materials in carbon‐black‐filled NR vulcanizates

Extraction of unbound materials from carbon‐black‐filled natural rubber (NR) vulcanizates with different cure systems was studied using various solvents with different dielectric constants of n‐hexane, toluene, THF, acetone, and acetonitrile. The extraction was performed at room temperature and 40°C for 2 days and in the boiling solvent for 8 h. Amounts of extracted materials from the NR vulcanizates increase by increasing the temperature. Amounts of extracted materials from the NR vulcanizates with n‐hexane, toluene, and THF are more than those with acetone and acetonitrile. Amounts of extracted materials from the NR vulcanizate with a high crosslink density are less than those from the NR vulcanizate with a low one. Thermogravimetric analysis of the NR vulcanizates before and after the extraction were carried out to investigate components of the extracted materials. It was found that there were polymer components and metal complexes, as well as organic matters with a low molecular weight in the extracted materials. Abilities of the solvents to extract unbound materials from the NR vulcanizates were discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1995–2005, 1999     

Step‐strain stress relaxation of carbon black‐loaded natural rubber vulcanizates

Step‐strain stress relaxation experiments were performed on natural rubber vulcanizates of various carbon black (HAF) concentrations by subjecting the samples to a very rapid strain and fixing its length at the deformed state. Time–temperature superposition in the viscoelastic region was evaluated to investigate the effect of temperature on the relaxation times of the rubbery composites. Remarkably, it was observed that, at higher HAF concentrations, increasing the temperature had a lesser effect on decreasing the overall stress values. That was attributed to the lower number of elastomeric chains per unit volume due to the agglomeration of the carbon black particles. The energy barrier resulting from the adsorption of the rubbery chains on the filler particles was insufficient to drastically reduce the diffusion and rearrangement of the polymer chains. The activation energy of the rubber‐like deformation calculated from the time–temperature superposition was shown to be independent of temperature. Interestingly, the viscosity coefficients showed a large increase with a modest addition of the carbon black. This is due to the long‐range nature of the temporary bonds formed between the polymer molecules and the surface‐active carbon black. The stress–strain of the rubbery composites was shown to behave in a Gaussian manner in accordance with the Mooney–Rivlin relationship. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3387–3393, 2004     

Effect of tackifiers on mechanical and dynamic properties of carbon‐black‐filled NR vulcanizates

This work focuses on the effect of tackifiers on mechanical and dynamic properties of carbon‐black‐filled vulcanizates. Three types of tackifiers with difference in softening points are selected for study including petroleum resin, phenolic resin, and gum rosin. The effect of tackifiers on the retardation of vulcanization is observed and the changes in mechanical properties due to the reduction in crosslink density are correlated. Good compatibility between natural rubber and all three tackifiers is verified by a single tan‐delta peak detected for each vulcanizate in temperature ramp test. A similar behavior to the Payne effect which usually found in the case of particulate‐filled rubbers is observed for the tackifier‐filled counterparts. The variation of temperature plays a crucial role in the dynamic behavior of tackified vulcanizates since the state of tackifiers determines its function during dynamic straining. As temperature passed through the softening point of a particular tackifier, substantial reduction in elastic response is observed; however, its relative damping to the untackified may still be maintained. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers.     

Stability of electrical properties of carbon black‐filled rubbers

Conducting composites were prepared by melt mixing of ethylene–propylene–diene terpolymer (EPDM) or styrene‐butadiene rubber (SBR) and 35 wt % of carbon black (CB). Stability of electrical properties of rubber/CB composites during cyclic thermal treatment was examined and electrical conductivity was measured in situ. Significant increase of the conductivity was observed already after the first heating–cooling cycle to 85°C for both composites. The increase of conductivity of EPDM/35% CB and SBR/35% CB composites continued when cyclic heating‐cooling was extended to 105°C and 125°C. This effect can be explained by reorganization of conducting paths during the thermal treatment to the more conducting network. EPDM/35% CB and SBR/35% CB composites exhibited very good stability of electrical conductivity during storage at ambient conditions. The electrical conductivity of fresh prepared EPDM/35% CB composite was 1.7 × 10⁻² S cm⁻¹, and slightly lower conductivity value 1.1 × 10⁻² S cm⁻¹ was measured for SBR/35% CB. The values did not significantly change after three years storage. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of hygrothermally decomposed polyurethane on the curing and mechanical properties of carbon black‐filled epoxidized natural rubber vulcanizates

Hygrothermally decomposed polyurethane (HD‐PUR) was mixed up to 20 phr in epoxidized natural rubber (with 50 mol % epoxidation; ENR50) recipes, and the curing and mechanical behaviors were studied. Mechanical testing of the ENR50/HD‐PUR vulcanizates determined the tensile, tear, compression‐set, hardness, abrasion, hysteresis, and resilience properties. No significant changes were observed in the tensile properties with the incorporation of HD‐PUR. The ENR50 compounds showed an increase in compression set with increasing HD‐PUR content. Rubbers cured by a semi‐efficient vulcanization system gave the best overall performance. A further improvement in curing and mechanical properties was achieved by the carbon black grade N330 being replaced with a more active grade (N375). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2265–2276, 2002     

Characterization of carbon black‐filled immiscible polypropylene/polystyrene blends

The electrical and rheological behaviors of carbon black (CB)‐filled immiscible polypropylene (PP)/polystyrene (PS) blends were investigated. The compounding sequence influences the phase morphology of the ternary CB/PP/PS composites and the distribution of CB aggregates. Simultaneous measurements of resistance and dynamic modulus were carried out to monitor the phase coalescence of the ternary composites and CB migration and agglomeration in the PS phase during annealing at temperatures above the melting point of PP. The variation of resistivity is mainly attributed to CB agglomeration in the PS phase and the interfacial region, while the variation of dynamic modulus is regarded as the superimposition of the phase coalescence and CB agglomeration in the PS phase. The ternary composites with the majority of CB particles distributed in the interfacial region show the lowest conductive percolation threshold and the most stable resistivity–temperature performance during heating–cooling cycles. Copyright © 2011 Society of Chemical Industry     

Mechanical properties of deproteinized natural rubber in comparison with synthetic cis‐1, 4 polyisoprene vulcanizates: Gum and black‐filled vulcanizates

Gum and black‐filled vulcanizates having various crosslink densities were prepared from 2 types of rubber, namely, deproteinized natural rubber (DPNR) and synthetic cis‐1, 4 polyisoprene vulcanizates (IR). Their mechanical properties, such as tensile strength, tear strength, abrasion loss, and heat buildup resistance, at various crosslink densities as well as at similar optimum crosslink density were compared. For both gum and black‐filled systems, IR possessed a higher crosslink density than that of DPNR at a fixed curative content. Tensile and tear strength of all vulcanizates passed through a maximum with increasing crosslink density. For gum vulcanizates, tensile and tear strengths of DPNR and IR below the maximum were not much different. However, IR had a narrower tear strength peak relative to DPNR. At a comparable optimum crosslink density, DPNR exhibited higher tensile strength and crack growth resistance than IR. For black‐filled vulcanizates, tensile and tear strengths, and heat buildup resistance of DPNR and IR at a given crosslink density were similar. The results revealed that the properties of gum samples were more dependent upon crosslink density than the black‐filled ones because the reinforcement by carbon black overshadowed the intrinsic properties of the rubbers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1139–1144, 2005     

Improvement of conductive network quality in carbon black‐filled polymer blends

Heat treatment of polymer‐based composites is critical for the enhancement of both stability and long‐term service life, especially when the materials function under an inconstant temperature environment. The present article discusses the effect of heat‐treatment conditions on the electrically conductive properties of carbon black (CB)‐filled low‐density polyethylene (LDPE) and ethylene–vinyl acetate copolymer (EVA) composites, which are candidates for positive temperature coefficient (PTC) materials. It was found that the dispersion mode of CB particles changes as a function of the matrix morphology. When the composites are irradiated to form crosslinked networks in the matrix for the elimination of negative temperature coefficient (NTC) behavior, some of the produced free radicals are also entrapped for quite a long time after the irradiation treatment. These residual radicals further enhance the interaction between CB and the matrix and further induce the crosslinking of the matrix so that the composites' conductivity changes with time as a result of the continuous variation in the contacts between the conductive fillers. To improve the quality of the conduction paths in the composites, appropriate post‐heat treatment should be carried out, which speeds up the formation of the above‐mentioned two kinds of crosslinked structures within a limited time. Annealing at 75°C for more than 10 h is believed to be an effective way. After the treatment, a balanced performance characterized by reduced room‐temperature resistivity and improved PTC intensity was obtained. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2768–2775, 2002     

Viscoelastic properties and filler dispersion in carbon black‐filled and silica‐filled cross‐linked natural rubbers

The activation energies (ΔE_{J ′} and ΔE_J″) calculated from the temperature dependence of the storage compliance (J′) and the loss compliance (J″) of carbon black (CB)‐filled, hydrophobic silica‐ and hydrophilic silica‐filled cross‐linked natural rubbers (NRs) were found to be less than 15 kJ mol^?1, which corresponds to the physical range of van der Waals interaction. The results of three‐dimensional‐transmission electron microscopy measurements indicate that the closest distance (d_p) between the two neighboring nanofiller aggregates centers decreased sharply with increasing nanofiller loading and tended to become constant at a nanofiller loading of around 30 phr or higher. For all samples examined, there were two regions related to the elastic deformation energy, and the critical d_p value between the two regions was in the order of CB > hydrophobic silica = hydrophilic silica. Additionally, ΔE_J′ developed in the region of longer d_p than that of ΔE_J″. On the other hand, ΔE_J″ occurred after the formation of the filler network and was larger than ΔE_J′. ΔE_J″ is assumed to be related to slippage of the junction and the rearrangement of the nanofiller network. Therefore, the dependence of ΔE_J′ and ΔE_J″ on d_p suggests that the interaction layer between the nanofiller and NR has at least two energy levels. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2594–2602, 2013     

Reversible electrical behavior with strain for a carbon black‐filled rubber

Most unfilled elastomers exhibit a high electrical resistance. Fillers are usually added to elastomers to enhance their mechanical properties. Frequently the filler type used is an electrically conductive carbon black and the inclusion of such fillers reduces the resistivity of the elastomer compound. Previous work has shown that for elastomers containing high abrasion furnace, carbon black fillers such as N330 (or N300 series) at a volume fraction above the percolation threshold the resistivity changes with strain, the precise resistivity versus strain behavior being nonlinear and irreversible for conventional carbon black fillers. A strain‐measuring device, deriving strain directly from a measure of the resistivity, requires that the behavior be reversible and reproducible from cycle to cycle. This work presents the electrical resistivity behavior of a natural rubber (NR) compound filled with Printex XE2 carbon black. This type of filler has a significantly different morphology to the N300 series blacks examined previously. The Printex was incorporated into the rubber at a volume fraction above its percolation threshold and its behavior is contrasted to that observed with N300 series carbon black‐filled NR. Here, and for the first time, reversible electrical resistivity dependence with strain is reported for an elastomer filled with Printex XE2. This reversible behavior under strain opens up the possibility of applications, such as a flexible load sensor, pressure sensor, or switch. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Study of carbon black‐filled poly(butylene succinate)/polylactide blend

In this study, carbon black (CB) was used to control the conductivity and the compatibility of immiscible poly(butylene succinate)/polylactide (PBS/PLA) blend. It is shown that most of the CB particles are selectively dispersed in the matrix PBS phase because of the viscosity ratio of the blend components. The increasing viscosity of PBS phase prevents the coalescence of the dispersed PLA domain during the melt mixing. The domain sizes of PLA are refined when compared with that of blank PBS/PLA blend. The ternary composite shows an onset of the electrical conductivity at low filler loadings (1.5 wt %), which is attributed to a percolation of CB in the insulating matrix polymer. Moreover, the composites exhibited remarkable improvement of rheological properties in the melt state when compared with that of blank PBS/PLA blend. According to the van Gurp‐Palmen plot, the rheological percolation threshold for ternary systems is lower than 1.5 wt %. Furthermore, the ternary composites present improved mechanical properties and thermal stability even at very low loading levels of the CB. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Crystallization behavior of carbon black‐filled polypropylene and polypropylene/epoxy composites

The crystallization behavior of polypropylene (PP)/carbon black (CB) and PP/epoxy/CB composites was studied with differential scanning calorimetry (DSC). The effects of compatibilizer MAH‐g‐PP and dynamic cure on the crystallization behavior are investigated. The nonisothermal crystallization parameters analysis showed that CB particles in the PP/CB composites and the dispersed epoxy particles in the PP/epoxy composites could act as nucleating agents, accelerating the crystallization of the composites. Morphological studies indicated that the incorporation of CB into PP/epoxy resulted in its preferential localization in the epoxy resin phase, changing the spherical epoxy particles into elongated structure, and thus reduced the nucleation effect of epoxy particles. Addition of MAH‐g‐PP significantly decreased the average diameter of epoxy particles in the PP/epoxy and PP/epoxy/CB composites, promoting the crystallization of PP more effectively. The isothermal crystallization kinetics and thermodynamics of the PP/CB and PP/epoxy/CB composites were studied with the Avrami equation and Hoffman theory, respectively. The Avrami exponent and the crystallization rate of the PP/CB composites were higher than those of PP, and the free energy of chain folding for PP crystallization decreased with increasing CB content. Addition of MAH‐g‐PP into the PP/epoxy and PP/epoxy/CB composites increased the crystallization rate of the composites and decreased the chain folding energy significantly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 104–118, 2006     

Electrical properties and morphology of carbon black‐filled HDPE/EVA composites

The sensitive effect of weight ratio of the high‐density polyethylene (HDPE)/ethylene‐vinylacetate copolymer (EVA) on the electrical properties of HDPE/EVA/carbon black (CB) composites was investigated. With the EVA content increasing from 0 wt % to 100 wt %, an obvious change of positive temperature coefficient (PTC) curve was observed, and a U‐shaped insulator‐conductor‐insulator transition in HDPE/EVA/CB composites with a CB concentration nearby the percolation threshold was found. The selective location of CB particles in HDPE/EVA blend was analyzed by means of theoretical method and scanning electron micrograph (SEM) in order to explain the U‐shaped insulator‐conductor‐insulator transition, a phenomenon different from double percolation in this composite. The first significant change of the resistivity, an insulator‐conductor transition, occurred when the conductive networks diffused into the whole matrix due to the forming of the conductive networks and the continuous EVA phase. The second time significant change of the resistivity, a conductor‐insulator transition, appeared when the amorphous phase is too large for CB particles to form the conductive networks throughout the whole matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Thermally stable conducting composites based on a carbon black‐filled polyoxadiazole matrix

New thermally stable conducting materials can be obtained by dispersing conducting carbon black into poly(4,4′‐diphenylether‐1,3,4‐oxadiazole) (POD–DPE) solution in NMP. The blend preparation process resulted in quite good dispersed composite and a relatively low percolation threshold (around 5 wt % of CB). The effect of the compressive stress on the resistivity of composite has been evaluated. The resistivity decreases continuously as the applied pressure is increased. In addition to the electrical conductivity, the presence of carbon black resulted in higher thermally stable materials. The thermal stability, electrical conductivity, and pressure‐sensible characteristics make this conducting material a good candidate for application in manufacture of pressure sensors for high temperature ambient. This material shows a typical semiconductor behavior, characterized by an increase of conductivity with the temperature. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1631–1637, 2004     

Percolation phenomena in carbon black–filled polymeric concrete

Percolation in carbon black‐filled polymeric concrete, is discussed based on the measured changes in electrical conductivity and morphology of the composite at different concentrations of carbon black. The percolation threshold ranged between 6 and 7 wt% (based on resin weight) of carbon black. Above this concentration, the filler particles formed agglomerates in contact with each other, suggesting that the conduction process is nearly ohmic in nature. A power law predicted by percolation theory described the behavior of the conductivity as a function of carbon black content. Microscopic analysis showed the presence of a continuous structure formed by the polyester resin and carbon black, in which silica particles were embedded.