Effect of low molecular weight polybutadiene as processing aid on properties of silica‐filled styrene–butadiene rubber compounds

Because silica has strong filler–filler interactions, a silica‐filled rubber compound shows a poor filler dispersion compared to a carbon black‐filled one. Improvement of the filler dispersion in silica‐filled styrene–butadiene rubber (SBR) compounds was studied using low molecular weight polybutadiene (liquid PBD) with the high content of 1,2‐unit. By adding the liquid PBD to the silica‐filled SBR compound, the filler dispersion and flow property are improved. The cure time and cure rate become faster as the 1,2‐unit content of the liquid PBD increases for the compounds containing the liquid PBD. The crosslink density increases linearly with increase in the 1,2‐unit content of the liquid PBD. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3135–3140, 2003     

Rheological and solid wall boundary condition characterization of unvulcanized elastomers and their compounds

An extensive fundamental investigation of the rheological properties and solid wall boundary condition shear stress of elastomers and elastomer–carbon black compounds has been carried out. The elastomers were an emulsion butadiene–styrene copolymer (SBR 1500) and a polybutadiene. Shear flow rheological properties were measured using a newly designed sandwich rheometer, in both constant shear rate and creep modes as well as in a capillary rheometer. A constant elongation rate rheometer for elastomers was developed. Stress relaxation measurements were also carried out in the sandwich rheometer. The shear viscosity of the gum elastomers exhibits a constant very high shear zero viscosity (8 × 10⁸ Pa.s for SBR 1500 at 100°C) and decreases with increasing shear rate. The compounds exhibit yield values of similar magnitude to carbon black compounds of molten plastics. Only the SBR 1500 and its compounds were studied in the elongational flow mode. It was not possible to achieve a steady state in these experiments. An apparatus for measurement of shear stress as a function of velocity (shear rate) at a specified pressure was developed. The instrument, which we call a friction tester, was used not only to determine wall shear stress but to investigate the regime of flow and potentially determine conditions for the onset of slip. Evidence of changing flow regimes were found, and the implications discussed.     

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     

Effects of carbon fillers on the rheology of highly filled liquid‐crystal polymer based resins

Adding conductive carbon fillers to insulating resins increases the composite electrical and thermal conductivity. Often, enough of a single type of carbon filler is added to achieve the desired conductivity while still allowing the material to be molded into a bipolar plate for a fuel cell. In this study, various amounts of three different carbons (carbon black, synthetic graphite particles, and carbon fiber) were added to Vectra A950RX liquid‐crystal polymer. The rheological properties of the resulting single‐filler composites were measured. In addition, the rheological properties of composites containing combinations of different carbon fillers were studied via a factorial design. In all cases, the viscosity increased with increasing filler volume fraction and followed a shear‐thinning power‐law model. The factorial design results indicated that each of the single fillers and all the filler combinations caused a statistically significant increase in the composite viscosity when compared at a shear rate of 500 s^?1 or at a stress of 10⁵ Pa. For composites containing synthetic graphite particles and/or carbon fiber, the viscosity variation with the volume fraction of carbon followed a modified Maron–Pierce equation. When compared at a constant volume fraction of carbon, composites containing carbon black showed viscosity enhancement above and beyond that shown by the other composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

炭黑用量对不同结构聚丁二烯橡胶流变行为的影响

研究了BR9000，BR9002,BR3505等3种不同结构的聚丁二烯橡胶／炭黑混炼胶的门尼粘度和毛细管流变行为。结果表明，增加炭黑用量能够显著提高3种聚丁二烯橡胶混炼胶的门尼粘度、流动屈服应力和表观剪切粘度。与BR9000相比，聚丁二烯橡胶的反式结构含量较高时（BR3505），混炼胶门尼粘度较大，但表观剪切粘度反而较低;相对分子质量分布较宽时（BR9002）,门尼粘度和表观剪切粘度较低。     

Synergistic effects of multiple carbon fillers on the rheology of liquid crystal polymer based resins

Adding conductive carbon fillers to insulating thermoplastic resin increases composite electrical and thermal conductivity. Often, as much of a single type of carbon filler is added to achieve the desired conductivity, while still allowing the material to be molded into a bipolar plate for a fuel cell. In this study, varying amounts of three different carbons (carbon black, synthetic graphite particles, and carbon fiber) were added to Vectra A950RX liquid crystal polymer. The rheology of resulting single filler composites was tested. In addition, the rheological properties of composites containing combinations of two different carbon fillers were studied via a factorial design. In all cases, viscosity increased with increasing filler volume fraction for all shear rates. Over the range of shear rates studied, the viscosity followed a shear‐thinning power law model. The factorial design results indicated that each of the single fillers and all of the two filler combinations caused a statistically significant increase in composite viscosity at a shear rate of 1,000 s⁻¹. The composites containing carbon black and synthetic graphite caused the largest increase in viscosity. It is possible that the highly branched, high surface area structure of carbon black ‘links’ with the synthetic graphite particles, which results in increased composite viscosity. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers.     

Electrical conductivity and rheology of carbon‐filled liquid crystal polymer composites

One emerging market for electrically conductive resins is for bipolar plates for use in fuel cells. Adding carbon fillers to thermoplastic resins increases composite electrical conductivity and viscosity. Current technology often adds as much of a single type of carbon filler as possible to achieve the desired conductivity, while still allowing the carbon‐filled thermoplastic matrix material to be extruded and molded into a bipolar plate. In this study, varying amounts of two different types of carbon, one carbon black and one synthetic graphite, were added to Vectra A950RX liquid crystal polymer. The resulting single filler composites were then tested for electrical conductivity and rheological properties. The electrical conductivity followed that typically seen in polymer composites with a percolation threshold at 4 vol % for carbon black and at 15 vol % for synthetic graphite. Over the range of shear rates studied, the viscosity followed a shear‐thinning power law model with power‐law exponent (n ? 1) = ?0.5 for neat Vectra A950RX and (n ? 1) = ?0.7 for highly filled composite materials. Viscosity increased with increasing filler volume fraction for all shear rates. The viscosity–enhancement effect was more rapid for the composites containing carbon black when compared with those containing synthetic graphite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2680–2688, 2006     

Nonlinear viscoelasticity and stress‐softening behavior of chloroprene rubber reinforced by multiwalled carbon nanotubes

The viscoelasticity and stress‐softening behavior of chloroprene rubber (CR) filled with multiwalled carbon nanotubes (MWCNT) and carboxylated multiwalled carbon nanotubes (MWCNT‐COOH) were studied using a Rubber Process Analyzer 2000 (RPA2000). In the strain sweep measurements, it is found that CR/MWCNT and CR/MWCNT‐COOH compounds have different behavior on storage modulus (G′). With increasing strain, G′ of CR/MWCNT (100/8) compound decreases at strain less than 2°, while G′ of CR/MWCNT‐COOH (100/8) compound stays at constant, indicating that MWCNT‐COOH has stronger filler–filler network and filler–rubber interactions as compared to MWCNT in CR matrix. CR/MWCNT (MWCNT‐COOH) vulcanizates have higher G′ but lower loss modulus (G″) than the corresponding uncured compounds. Repeated strain sweep scans were carried out to study the stress‐softening behavior of CR compounds. A stress‐softening effect of the filled CR compounds is observed and becomes more pronounced with increasing loading of MWCNT or MWCNT‐COOH. The correlation between the Payne effect and stress‐softening effect of CR/MWCNT (MWCNT‐COOH) vulcanizates is also studied. It is found that the difference of the storage moduli at 0.1° and 10° strain amplitudes and the difference of storage moduli of first and second strain sweeps at 0.1° strain amplitude show a positive linear correlation. POLYM. COMPOS., 35:2194–2202, 2014. © 2014 Society of Plastics Engineers     

Rheological properties of calcium silicate‐filled isotactic polypropylene

The melt rheological behavior of calcium silicate‐filled isotactic polypropylene, with filler volume contents of 0–17.8%, was determined at 493 K. The composites followed the power law in shear stress versus shear rate variations and were shear thinning. Initially, apparent melt viscosity decreased until a critical filler volume content of 8.5% was reached. However, on further increase in calcium silicate concentration, apparent melt viscosity increased. Melt elasticity also showed an initial decrease until 8.5% filler content was reached and then an increase beyond this filler content. Surface treatment of calcium silicate with a titanate coupling agent, LICA 38, modified the rheological properties because of the plasticizing/lubricating effect of LICA 38. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1511–1518, 2003     

Correlations in rheological behavior between large amplitude oscillatory shear and steady shear flow of silica-filled star-shaped styrene-butadiene rubber compounds: Experiment and simulation

The large amplitude oscillatory shear (LAOS) and steady shear behavior of star-shaped SSBR/silica 60 phr (21 vol%) compounds with various filler surface areas was measured and simulated. An SBR gum and SBR compounds containing four different silicas with surface areas of 55, 135, 160, and 195 m²/g were utilized. Rheological behavior indicated clear correlation with surface area. LAOS tests showed an increase in dynamic moduli, shear stress, and higher order harmonic contributions with surface area. Elastic and viscous Lissajous figures showed significant distortion at intermediate and higher strain amplitudes. Additionally, ratios of third and fifth order stress harmonics to the first stress harmonic (I_3/1 and I_5/1 , respectively) showed a ''bump'' at intermediate strain amplitudes for the three highest surface area compounds. With regards to steady shear, all materials showed strong shear thinning behavior, and an increase in shear viscosity with surface area. The Cox-Merz rule was shown to be valid for the SBR gum but not for the filled compounds. However, the complex viscosity as a function of shear rate amplitude at various frequencies at high strain amplitudes and the steady shear viscosity as a function of shear rate coincided. This correlation, referred to as the Philippoff approach, has important ramifications for the rubber industry, providing quick data for predicting processing behavior. The Simhambhatla-Leonov model was successfully employed to simulate rheological behavior for the SBR gum and the lowest surface area silica compound, but the model yielded mixed results for the higher surface area silica compounds.     

Effect of fillers on the rheological behavior of thermoplastic 1,2 polybutadiene rubber

The influence of fillers like clay, silica, and carbon black on the rheological properties of 1,2 polybutadiene has been studied using a capillary rheometer. Silica filled compound exhibited the highest viscosity and clay filled compound the lowest viscosity at all shear rates. The effect of filler loading and temperature on the Theological behavior has also been studied. Smooth extrudates were obtained in most of the cases and die swell was lower for silica and carbon black filled compounds than for clay filled compounds. Rheograms of different 1,2 polybutadiene systems have been found to merge into a master curve using modified viscosity and shear rate functions that contain melt flow index as a parameter.     

Rheological behavior of brominated isobutylene‐co‐paramethylstyrene: Effect of fillers,oil and blending with EPDM

The melt flow properties of unfilled and filled brominated isobutylene‐co‐paramethylstyrene (BIMS) were measured by means of a capillary viscometer at three different temperatures (90°C, 110°C and 130°C) and four different shear rates (61, 122, 245 and 306 s^?1). The effect of addition of EPDM rubber on melt flow properties of unfilled BIMS was also studied. Evaluation of the processability was done by measuring the extrudate roughness (ER) of the extrudates obtained from the MPT. The viscosity of the systems decreased with the shear rate, indicating their pseudoplastic or shear thinning nature. As expected, the viscosity of BIMS increased with the addition of fillers and decreased with the addition of oil. For the neat systems, viscosity increased with the addition of EPDM, and the blends showed a positive deviation, indicating interdiffusion of the polymer chains across the phase boundaries. The activation energy of the filled systems at constant filler loading increased with increasing filler surface area (N330 > N550 > N774, each at 30 phr loading), and filler loading (50 > 30 > 10 phr, for N330) and decreased with the addition of oil (2.5 > 5.0 > 7.5 phr, for system containing 30 phr of N330). The silica filled system showed a higher activation energy and ER than the carbon black‐filled systems. With addition of N330 and N550 carbon blacks to BIMS, the extrudate roughness (ER) decreased, whereas it increased with the addition of N774 carbon black. With an increase in filler loading, ER initially increased and then decreased as compared to the neat system. For the filled systems, ER initially decreased up to 5 phr of oil, beyond which it increased.     

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     

Melt flow behavior in capillary extrusion of nanosized calcium carbonate‐filled poly(L‐lactic acid) biocomposites

Nanosized calcium carbonate (nano‐CaCO₃)‐filled poly‐L ‐lactide (PLLA) biocomposites were compounded by using a twin‐screw extruder. The melt flow behavior of the composites, including their entry pressure drop, melt shear flow curves, and melt shear viscosity were measured through a capillary rheometer operated at a temperature range of 170–200°C and shear rates of 50–10³ s^?1. The entry pressure drop showed a nonlinear increase with increasing shear stress and reached a minimum for the filler weight fraction of 2% owing to the “bearing effect” of the nanometer particles in the polymer matrix melt. The melt shear flow roughly followed the power law, while the effect of temperature on the melt shear viscosity was estimated by using the Arrhenius equation. Hence, adding a small amount of nano‐CaCO₃ into the PLLA could improve the melt flow behavior of the composite. POLYM. ENG. SCI., 52:1839–1844, 2012. © 2012 Society of Plastics Engineers     

Melt rheological properties of nickel powder filled polypropylene composites

The melt rheological properties of nickel powder filled polypropylene composites were investigated. The effect of filler concentration on shear stress-shear rate data, melt viscosity and melt elasticity parameters were determined by using a capillary rheometer. The study shows that the materials follow a power law in viscous behavior over the entire range of shear rates investigated and that the viscosity increases and elasticity decreases as filler concentration is increased up to a critical value. However, beyond the critical filler content melt viscosity decreases while melt elasticity increases. The effect of temperature on the viscoelastic properties of filled polypropylene was also investigated.     

Effect of fillers on thermal and mechanical properties of polyurethane elastomer

The effects of five different types of fillers on the thermal and mechanical properties of hydroxyl-terminated polybutadiene-based polyurethane elastomers were explored to develop a filled polyurethane elastomeric liner for rocket motors with hydroxyl-terminated polybutadiene-based composite propellants. Two type of carbon black, silica, aluminum oxide, and zirconium(III) oxide were used as filler. Based on the improvement in the tensile properties and the erosion resistance achieved in the first part of the study, an ISAF-type carbon black was selected to be used as the main filler in combination with an additional filler. The second part involves the investigation of polyurethane elastomers containing a second filler in various amounts in addition to the ISAF-type carbon black used as the main filler. In addition to the thermal and mechanical properties, the processability of the uncured polyurethane mixtures were also explored by measuring the viscosity in this second part of the study. The studied fillers do not considerbly change the thermal degradation temperatures and the thermal conductivity of the polyurethane elastomers with a filler content up to 16 wt %. The best improvement in the erosion resistance and tensile strength of the polyurethane elastomers with additional fillers is also achieved when filled with the ISAF-type carbon black, whereas the use of zirconium(III) oxide as additional filler provides almost no improvement in these properties. Viscosity of the uncured polyurethane mixtures increases with the increasing filler content and with the decreasing particle size of the filler. Aluminum oxide-filled elastomers seem to be the most suitable compositions having sufficiently high thermal and mechanical properties, together with the processability of uncured mixtures. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1057–1065, 1998     

Flow Behavior of Polypropylene/Ethylene-Propylene Diene Terpolymer/Natural Rubber (PP/EPDM/NR) Blends by Torque Rheometer: The Effect of N,N-m-Phenylene Bismaleimide (HVA-2) Addition

Blends of polypropylene (PP)/ethylene-propylene diene terpolymer (EPDM)/natural rubber (NR) with different ratio were investigated using a Haake torque rheometer. The effect of N,N-m-phenylene bismaleimide (HVA-2) addition on the flow behavior of PP/EPDM/NR blends also was studied. The torque data was collected at different rotor speeds in the range of 30–60 rpm and different processing temperatures in the range of 170–190°C. The recorded data were interpreted in terms of apparent shear rate, apparent shear stress, and apparent viscosity. The shear stress–shear strain curve shows that all blends follow the power law where the pseudoplasticity behavior of melt viscosity increases with increasing NR content as well as addition of HVA-2. The apparent viscosity of the blends was found to increase with increasing NR content in the blend. The addition of HVA-2 increases the apparent viscosity due to the formation of cross-linking in rubber phase. However, blends with HVA-2 show lower flow activation energies than do similar blends without HVA-2. Scanning electron microscopy (SEM) shows good correlation with the flow properties of the blends.     

Viscosity of copolymers containing carbon black

The flow behavior of random copolymers of styrene and butyl methacrylate containing specific carbon blacks varying in surface area were studied at various temperatures and shear rates. Master curves of reduced viscosity as a function of shear rate were prepared for the pure copolymers at 150°C. The superposition required vertical and horizontal shifts, proportional to (a_T)^?1 and (a_T)^.53, respectively, where a_T is the shift factor. With the incorporation of carbon black, the viscous response is non-Newtonian exhibiting a yield stress at increasing filler concentration and surface area. Master curves of viscosity against shear rate were generated at fixed filler loadings and surface areas by using a single horizontal shift factor.     

Effects of temperature and strain amplitude on dynamic mechanical properties of EPDM gum and its carbon black compounds

The effects of carbon black loadings ℓ, Temperature T, and shear frequency ω on dynamic mechanical properties of EPDM gum elastomer and its carbon black compounds were investigated under sinusoidal shear flows. The regions of shear flows where the gum elastomer and its carbon black compounds exhibited characteristic plateau in viscoelastic properties were established and found to directly depend on temperature but were inversely proportional to carbon black loading. The gum rubber and its 20% carbon black compound showed rather unusual similar dynamic flow behaviors at 50 and 100°C attributed to the possible presence of crystallinity from the fractional ethylene components in the gum. This fraction could act as nucleation sites for macrogels that required higher temperature than 50 and 100°C for melting, particularly in the presence of carbon black particles. Dynamic properties were amplified due to carbon black filler. This effect was more pronounced at low frequencies and at 50 and 150°C, respectively. At 100°C, amplifications appeared to have been attenuated by the hydrodynamics of the continuum elastomer matrix. This observation helps the further understanding of the filler-elastomer interactions and the critical role played by temperature, particularly as it affects rubber processors. © 1996 John Wiley & Sons, Inc.     

Effect of bark flour on melt rheological behavior of high density polyethylene

The melt rheological behavior of neem bark flour (BF) filled high density polyethylene (HDPE) has been studied at varying volume fraction (?_f) from 0 to 0.26 at 180, 190, and 200°C in the shear rate range from 100 to 5000 s^?1 using extruded pellets of the composites. The melt viscosity of HDPE increases with ?_f because the BF particles obstruct the flow of HDPE. With the incorporation of the coupling agent HDPE‐g‐MAH, the viscosity decreased compared to the corresponding compositions in the HDPE/BF systems due to a plasticizing/lubricating effect by HDPE‐g‐MAH. The composites obeyed power law behavior in the melt flow. The power law index decreases with increase in the filler content and increases with temperature for the corresponding systems while the consistency index showed the opposite trend. The activation energy for viscous flow exhibited inappreciable change with either ?_f or inclusion of the coupling agent, however, the pre‐exponential factor increased with filler concentration. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012