High performance hybrid reinforcement of nitrile rubber using short pineapple leaf fiber and carbon black

Rubber composites with very high moduli at low elongation, high elongation at break and high ultimate breaking strength have been developed. The matrix was acrylonitrile butadiene rubber (NBR) and the hybrid (fibrous and particulate) reinforcements were short, fine pineapple leaf fiber (PALF) and carbon black. The amount of PALF was fixed at 10 parts (by weight) per hundred of rubber (phr) while that of carbon black was varied from 0 to 30 phr. Uniaxial NBR composites were prepared. Tensile strength, elongation at break, modulus and tear strength of the hybrid composites were characterized in both longitudinal (parallel to the fiber axis) and transverse (perpendicular to the fiber axis) directions. The addition of carbon black causes the slope of the early part of the stress–strain curve to increase and also extends breaking to greater strains. At carbon black contents of 20 phr and above, the stress–strain relation displays an upturn at high elongations, providing greater ultimate strength. Comparison with the usual carbon black filled rubber shows that the composite behavior at low strains is determined by the PALF, and at high strains by the carbon black. This high performance PALF-carbon black reinforced NBR shows great promise for engineering applications.     

Manipulation of mechanical properties of short pineapple leaf fiber reinforced natural rubber composites through variations in cross-link density and carbon black loading

The aim of this paper is to demonstrate that the stress–strain behavior of natural rubber reinforced with short pineapple leaf fiber (PALF) can easily be manipulated by changing the cross-link density and the amount of carbon black (CB) primary filler. This gives more manageable control of mechanical properties than is possible with conventional particulate fillers alone. This type of hybrid rubber composite displays a very sharp rise in stress at very low strains, and then the stress levels off at medium strains before turning up again at the highest strains. The composites studied here contain a fixed amount of PALF at 10 part (by weight) per hundred rubber (phr) and varying carbon black contents from 0 to 30 phr. To change the cross-link density, the amount of sulfur was varied from 2 to 4 phr. Swelling ratio results indicate that composites prepared with greater amounts of sulfur and carbon black have greater cross-link densities. Consequently, this affects the stress–strain behavior of the composites. The greater the cross-link density, the less is the strain at which the stress upturn occurs. Variations in the rate of stress increase (although not the stress itself) in the very low strain region, while dependent on fillers, are not dependent on the crosslink density. The effect of changes in crosslinking is most obvious in the high strain region. Here, the rate of stress increase becomes larger with increasing cross-link density. Hence, we demonstrate that the use of PALF filler, along with the usual carbon primary filler, provides a convenient method for the manipulation of the stress–strain relationships of the reinforced rubber. Such composites can be prepared with a controllable, wide range of mechanical behavior for specific high performance engineering applications.     

Comparative study of natural rubber and acrylonitrile rubber reinforced with aligned short aramid fiber

The aims of this paper are three-fold. The first is to determine the reinforcement of high performance short aramid fiber in two representative rubber matrices, namely natural rubber and acrylonitrile rubber. The second is to ascertain the effect of rubber polarity on the reinforcement. The third is to establish a pattern of reinforcement for use with less studied fibers. The rubbers were reinforced either with only aramid fiber or with a hybrid of aramid fiber and carbon black. The fiber contents were varied at 0, 2, 5 and 10 parts (by weight) per hundred rubber (phr) while those of carbon black were 0, 10, 20 and 30 phr. Conventional sulfur vulcanization was used. It was found that aramid fiber can reinforce both rubbers in the low strain region effectively, although to a significantly different degree. The hybrid carbon black provides additional reinforcement at low to medium strains and allows high strain stress upturn to occur in both rubber matrices. The findings enable the preparation of rubber composites having a wide, controllable range of mechanical behavior for specific high-performance engineering applications. Significantly, they also serve as a benchmark for developing reinforced systems from alternative fibers, particularly those from natural sources.     

Effect of mastication time on the low strain properties of short pineapple leaf fiber reinforced natural rubber composites

Pineapple leaf fiber (PALF), used as a reinforcing agent, does not have good adhesion to natural rubber (NR) due to the difference in their polarities. As a result, the degree of reinforcement of NR imparted by PALF remains low compared to that in a polar rubber like acrylonitrile butadiene (NBR). One of the factors that determines the adhesion between the rubber and the reinforcement is the rubber molecular weight. Thus, the aim of this paper is to demonstrate that the stress at very low strains of short pineapple leaf fiber (PALF) reinforced natural rubber (NR) can be significantly increased by lowering the matrix molecular weight. This can be achieved by increasing the matrix mastication time. The composites studied here contain a fixed amount of PALF at 10 part (by weight) per hundred rubber (phr). The PALF fibers were both untreated (UPALF) and sodium hydroxide treated (TPALF). Mastication times of 2, 4, 8 and 16 min were used. Stress-strain curves of PALF reinforced NR prepared with different mastication times were then compared. The most affected region of the curve is in the low strain region. The slopes of the stress-strain curves (moduli) increase with increasing mastication time, indicating better fiber-rubber interaction. The maximum stress achieved at 10% strain is almost 370% that obtained with the usual short mastication time (2 min). The effect remains up to very high strains, although becoming smaller as the strain is increased. Hence, we demonstrate that, by using long enough mastication time, stress-strain curves and stress at low strain of PALF reinforced NR can be improved without the need of any other adhesion promoters.     

Remarkable improvement of failure strain of preferentially aligned short pineapple leaf fiber reinforced nitrile rubber composites with silica hybridization

Preferentially aligned short fiber reinforced nitrile rubber (NBR) composites with very high moduli at low elongation and high elongation at break were developed by using short and fine pineapple leaf fiber (PALF) and silica as the hybrid (two component) reinforcement. The amount of PALF was fixed at 10 parts (by weight) per hundred of rubber (phr) while that of silica was varied from 0 to 30 phr. Uniaxial NBR composites were prepared and tested for their mechanical properties in the directions both parallel and perpendicular to the fiber axis. Comparison was made against silica-NBR composites of the same total filler loadings. All composites with PALF display very distinct stress-strain curves. The stress rises sharply when the composite is stretched, while that of silica filled composites with the same loading rises gradually. The addition of silica initially lowers the early part of the stress-strain curve but prolongs breaking to greater strains. Further addition of silica raises the early part of the stress-strain curve back to and above that of the lower silica contents. It also significantly increases the elongation at break. Observation of other properties is also reported. Considering all the properties evaluated, reinforcement of NBR with PALF-silica hybrid shows great promise for engineering applications.     

Improving the mechanical properties of short pineapple leaf fiber reinforced natural rubber by blending with acrylonitrile butadiene rubber

This work proposes a simple method for improving the rubber to filler stress transfer in short pineapple leaf fiber-reinforced natural rubber (NR). This was achieved by replacing some of the non-polar NR by polar acrylonitrile butadiene rubber (NBR). The amount replaced was varied from 0% to 20% by weight. The mixing sequence was designed so that the fiber would be coated with polar NBR before being dispersed in the NR matrix. A comparison system in which the mixing was carried out in a single step was also examined. Despite the fact that the two rubbers are immiscible, it was found that significant improvement of the stress transfer in the low strain region can be obtained. The mixing sequence affected the mechanical properties of the resulting composites. It is concluded that frictional stress transfer between the immiscible rubbers contributes more to the total stress transfer than does the frictional stress transfer between non-polar NR and polar cellulose fiber.     

Difference in bound rubber formation of silica and carbon black with styrene‐butadiene rubber

Formation of bound rubber is affected by the physical structure and surface chemistry of filler and the property of rubber. Variation of the bound rubber formation in styrene‐butadiene rubber compounds filled with silica and/or carbon black was studied. Influence of temperature on extraction of loosely bound rubber was also investigated. For the both silica and carbon black‐filled compounds, the bound rubber content increases with increase in the silica content ratio. The bound rubber content decreases with increasing the extracting temperature. The loosely bound rubber content of the silica‐filled compound is higher than that of the carbon black‐filled one. Activation energy for the extraction of the unbound and loosely bound rubbers becomes higher as the total filler content increases. The activation energy of the silica‐filled compound is higher (almost double the value) than for the carbon black‐filled one. Copyright­© 2002 John Wiley & Sons, Ltd.     

Fullerene-Like Structures as Interaction Sites between Carbon Black and Rubber

Ball-milling of N660 carbon black and graphite causes a deep activation of its surface activity which can be measured by a significant increase in the bound rubber level and in the amount of grafted rubber in comparison to the pristine untreated samples. The bound rubber measurement has been done also on a natural rubber masterbatch filled with extracted fullerene carbon black (EFCB). Also in this case extremely high levels of rubber grafting have been achieved in comparison to pure untreated graphite. It is discussed and demonstrated that the fullerene-like nanostructures in carbon blacks play a key role in the formation of bound rubber phenomenon and in grafting natural rubber on carbon black surface.     

Long-term mechanical performance of polyethylene pipe materials in presence of carbon black masterbatch with different carriers

In this paper, two types of carbon black (CB) masterbatch with different carriers, i.e. HDPE and LDPE, are used to produce black compounds using three PE100 resins with various short chain branching distributions. Due to difference in short chain branch (SCB) distribution, the used polyethylene resins behave differently in microstructure development and long-term creep behavior. The microstructural analysis using different DSC techniques and rheological measurements revealed more sensitivity of the polyethylene resin with uniform comonomer distribution to the carbon black aggregates and their polymeric carriers. The Full Notched Creep Test (FNCT) was performed to determine the long-term creep performance of the black compounds; it is shown that the sample having more uniform comonomer distribution is more resistant compared to other samples. On the other hand, by addition of carbon black masterbatch, resistance to slow crack growth in samples decreases since carbon black aggregates can act as stress concentration spots in the structure. However, with addition of the masterbatch with LDPE carrier polymer, the reduction of this value in samples is lower compared to one with HDPE carrier. The reason for this observation is that long branches of LDPE polymer enter the structure of lamellae in the PE100 resins, making them more coherent and increasing the number of tie molecules. The samples that are blended with LDPE polymer have a rougher surface, which means linkage between two sides of crack was stronger due to higher entanglement density in these samples. The impact test confirms the same trend as FNCT test, with the sample containing LDPE carrier having higher impact strength.     

Thermal property determination of hybridized kenaf/PALF reinforced HDPE composite by thermogravimetric analysis

This article presents the thermal degradation behavior of hybridized kenaf (bast)/pineapple leaf fiber (PALF) reinforced high density polyethylene (HDPE) composites by thermogravimetric and derivative thermogravimetric analyses (TG/DTG) with respect to the proportions of fiber in the composite, variation in fiber loading and fiber length. It was observed that the thermal decomposition of all the samples had taken place within the scheduled temperature range of 35?C615?°C. For hybrid composites prepared at 40% fiber loading, the initial peak between 236.9 and 331?°C corresponds to a mass loss of between 23 and 26%, and expectedly, PALF composite and 1:1 hybrid composite have the highest mass lost at this point. Main decomposition temperature as revealed from DTG curves occurred around 467?°C for all except composite prepared with 0.75 and 2?mm fiber length. The mass loss at this temperature was between 64.4 and 73.7%. However, at 464.87?°C, around 98% of neat HDPE had already degraded. Decomposition temperature of other composites was a little higher than the temperature at which HDPE concluded decomposition. Kenaf composite on its own showed initial thermal resistance, but above 240?°C, a sharp increase in decomposition occurred with temperature. Interestingly, hybridization took care of this. Kenaf and PALF composite have shown weaker thermal stability compared to neat HDPE at lower temperatures. The introduction of more fiber into the matrix at onset caused the thermal stability of the hybridized composite to decrease. This reduction in thermal stability of the hybrid with increase in fiber loading became obvious after the dehydration process. Decomposition of hybrid composite is directly proportional to increase in fiber loading. However, at 385?°C, where neat HDPE started decomposing, the percentage degradation of the hybrid showed inverse proportionality with increase in fiber loading. As observed, the size of the lignin and hemicelluloses shoulders in DTG curves deepen with increase in fiber loading, an indication of increased presence with increase in fiber loading.     

Influence of Carbon Black and Silica Filler on the Rheological and Mechanical Properties of Natural Rubber Compound

Rubber compounds are reinforced with fillers such as carbon black and silica. In general, filled rubber compounds shows smooth rheological behavior and mechanical properties. Variation in rheological behavior and mechanical properties was studied in terms of the filler composition using natural rubber compounds filled with both carbon black and silica CB/Si = 0/60, 20/40, 30/30, 40/20 and 60/0 phr (parts per hundred rubber is parts of any non-rubbery material per hundred parts of raw gum elastomer (rubbery material)). The rheological behaviour can be showed in measurement of Mooney viscosity and cure time. The Mooney viscosity of rubber compounds increase with the increasing the carbon black in the compounds. The compound filled with CB/Si of 30/30 and 60/0 showed abnormal rheological behaviour in which the cure time decreased suddenly and the increased at certain ratio during the measurement. The mechanical properties such as hardness, abrasion resistance and tensile stress at 300% elongation were studied. In the hardness and abrasion resistance measurement, the higher ratio CB/Si decrease contribution of silica, which resulting smaller of hardness value. Ratio CB/Si 40/20 gives an optimum filler blended. It is also clearly understood that higher abrasion resistance mainly due to the lower hardness value under the same condition. The tensile stress at 300% elongation of rubber compound increased with the increasing carbon black filler.     

Influence of filler type and content on properties of styrene‐butadiene rubber (SBR) compound reinforced with carbon black or silica

Rubber compounds are filled with reinforcing fillers to improve their physical properties. Carbon black and silica have different surface chemistries to each other. Differences in properties of carbon black‐ and silica‐reinforced styrene‐butadiene rubber (SBR) compounds were studied. Variation of properties of carbon black‐ or silica‐filled compounds with the filler content was also investigated. The silica‐filled compounds without any coupling agent and dispering agent were prepared to investigate the influence of polar materials‐adsorption on the silica surface. Viscosity and crosslink density increased with increase of the filler content. Hardness, modulus, tensile strength, and wear property were improved more and more by increasing the filler content. Viscosity of the silica‐filled compound was higher than that of the carbon black‐filled one. Cure rate of the silica‐filled compound became slower as the filler content increased, while that of the carbon black‐filled one became faster. Difference in properties between the carbon black‐ and silica‐filled compounds were explained by the poor silica dispersion and the adsorption of cure accelerator on the silica surface. Copyright © 2004 John Wiley & Sons, Ltd.     

Dispersion of carbon black

Satisfactory dispersion of the carbon black is essential to the production of rubber compounds possessing the maximum possible resistance to wear, tensile strength and abrasion resistance. The methods used to measure/estimate the degree of dispersion are reviewed in this paper.Most current methods are based on some form of microscopy. Light microscopy (at small magnifications) of cryomicrotomed rubber specimens in transmitted light is used to some extent. However, the preparation of the specimen is too time-consuming to warrant the use of the method for routine inspection. This has led to the development of an instrument—the Dispergator—which employs split field microscopy of freshly-cut samples to reduce the total time of testing (including the time required for specimen preparation) to about 1 min.     

A theory of green strength in polyisoprene

It is shown that, at ?25°C, natural rubber (NR) crystallizes more readily than synthetic polyisoprene (IR), the long induction period for nucleation in IR in particular being dependent on the carbon black loading. Both elastomers form bound rubber with carbon black but not with nonreinforcing fillers such as CaCO₃ and glass powder. At room temperature, in the presence of carbon black, NR has good green strength but not IR, while neither rubber has good green strength with nonreinforcing fillers. However, at 0°C CaCO₃ filled NR too has good green strength. A theory is proposed to account for the good green strenth characteristics found with certain compounds. In the model rubber molecules, already bound to the carbon black surface, are linked together, at low strains, via stress-induced crystal lamellae, giving a three-dimensional network in the compound. Such crystal lamellae are known to grow at right angles to the direction of strain from row nuclei formed at low strains. The coherence provided by the network permits the formation, at higher strains, of stress-induced crystals in which polymer chains are now aligned in the direction of strain. This leads to an upturn in the stress–strain curve. In the absence of either bound rubber or of crystal lamellae, a long range network structure cannot form and extension of the sample continues at constant stress.     

The influence of physical ageing on the electrical and swelling behaviour of ternary rubber vulcanizates

The effects of pre-annealing ageing time at 70 °C on the electrical properties and swelling behaviour in kerosene of a new tri-block rubber based on blends of natural rubber (NR) and different concentration ratios of both styrene-butadiene rubber (SBR) and butyl rubber (IIR), all incorporating 40 phr (parts per hundred parts of rubber by weight) of high abrasion furnace (HAF) carbon black, were investigated.

It was found that the interspacing distance, d, between carbon particles or aggregates is greatly affected by physical ageing and also by the rubber ratios in the test specimens.

Moreover, the degree of swelling, Q (%), in kerosene was found to decrease with both physical ageing and IIR content of the specimen.     

Effect of solvent and carbon black species on the rubber–carbon black interactions studied by pulsed NMR

The spin–spin relaxation time T₂ and the fraction of short T₂ component for composites of natural rubber with carbon black prepared under various conditions have been measured by pulsed NMR. Effect of swelling with a solvent (CCl₄), carbon black species (SAF, HAF, SRF) with different surface areas, and different initial carbon black loadings (35, 50, 70 phr) have been determined. Molecular motion in the rubber phase not in the immediate vicinity of the carbon black surface increases rapidly with increasing solvent concentration, yet it is still slightly restricted compared to rubber with solvent alone. On the other hand, molecular motion in the immobilized layer around carbon black and the fraction rubber in that layer are not affected by the solvent. This indicates strong restriction of molecular motion of polymers at the surface. For estimation of the thickness of the immobilized layer, the necessity of using an appropriate measure of surface area accessible to polymer molecules is pointed out. The degree of immobilization in the layer and the thickness of the layer do not vary appreciably with the nature of carbon black or the initial loading of carbon black.     

Room-temperature vulcanized silicone rubber/barium titanate–based high-performance nanocomposite for energy harvesting

Rubber composites were prepared for elastomer slab by mixing barium titanate (BaTiO₃), carbon nanotube (CNT), carbon black (CB), and room-temperature vulcanized (RTV) silicone rubber. An electrode was prepared from composite for energy harvesting with fillers such as CB and CNT, and RTV thinner was used to improve the processing of the specimen. At 50 phr of BaTiO₃, there is an increase in compressive modulus by 180%. There was a correlation between prestrain and biaxial strain in enhancing the energy generation. After poling of the rubber composite containing 50 phr of BaTiO₃ at 11 kV/mm, the energy harvesting was increased at all strains. In durability test at 70 phr of BaTiO₃ for 60% cyclic biaxial strain, the drop in voltage from the piezoelectric energy harvesting was almost zero for 3000 cycles.     

Nuclear magnetic resonance study of rubber–carbon black interactions

The mobilities of polymer chain segments in mixtures of rubber and carbon black were investigated by nuclear magnetic resonance. Spin–spin relaxation time (T₂) measurements on cis-polybutadiene and ethylene–propylene–diene rubber (EPDM) bound rubbers detected at least two relaxing regions: an immobile region and a relatively free region. The molecular motions in the relatively free region are still constrained compared to those of the pure gum.     

Recent developments in rubber processing,leading to new applications such as the “green tyre”

Rubber articles derive most of their mechanical properties from the admixture of reinforcing fillers. Most commonly, carbon black is used as reinforcing filler. If silica is used instead, tyres made with such rubber compounds may exhibit a rolling resistance reduction by ca. 30%, which translates in substantial fuel savings of a car. Such silicas are far more difficult to mix with rubber than carbon black. Coupling agents are used as a surface modification of the filler to enhance compatibility with the polymer. Additionally they improve the ease of mixing with the rubber. The development of proper coupling agents combined with improved mixing techniques has contributed to the final break-through of the silicareinforced “Green Tyre”.     

Effect of Ionizing Radiation on the Characteristics of EPDM/UHMW-PE Composites

Ultra high molecular weight polyethylene (UHMW-PE) fibers were used in a chopped form and at different concentrations as a reinforcing material in ethylene–propylene–diene terpolymers (EPDM). The effect of radiation dose and fiber concentration on the mechanical properties of the vulcanized rubber composites obtained was measured. It was found that γ-irradiation improves the interfacial adhesion between UHMW-PE fiber (Spectra 1000) and EPDM matrix which was detected by scanning electron microscopy (SEM). In addition, the Young modulus of the composites increases as the irradiation dose increases. Increasing the concentration of the fibers up to 40 phr leads to an enhancement in mechanical properties and swelling resistance of obtained composites, especially in the absence of carbon black. The absolute value of the modulus increased by a factor of at least two with the addition of carbon black. Moreover the tear strength of reinforced and filled EPDM was improved with respect to reinforced rubber. © 1997 John Wiley & Sons, Ltd.