Die‐swell behavior during the short‐tube flow of rubber compounds

In this study, the flow properties and die‐swell ratios (B's) of two kinds of rubber compounds (SI was a calcium carbonate filled natural rubber compound, and SII was a carbon‐black‐filled natural rubber/butadiene–styrene rubber/cis‐1,4‐butadiene rubber compound) in a short‐tube extrusion flow were measured by means of a capillary rheometer under test conditions with a temperature of 90°C and an apparent shear rate varying from 10 to 4000 s^?1 to identify the effects of extrusion conditions on the rheological behavior of the materials and to estimate B. The shear flow roughly obeyed the power law, whereas B increased nonlinearly with increasing extrusion rate. Under the same shear rates, the viscosity of SII was higher than that of SI, whereas the values of B of SI were higher than those of SII. Furthermore, B of the rubber compounds was estimated by means of an extrudate swell equation published in a previous work. The results show that the predictions of B were close to the measured data from the experiments. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Chemorheological study of compatibilized blends of low‐density polyethylene and polydimethyl siloxane rubber

Compatibilization of the blends of polydimethyl siloxane (PDMS) rubber and low‐density polyethylene (LDPE) was achieved through reactive processing during extrusion in a Monsanto Processability Tester (MPT). The chemorheological characteristics of 50 : 50 LDPE : PDMS blends with varying proportions (0–8 wt %) of ethylene comethyl acrylate (EMA) were investigated at three different temperatures (170, 190, and 210°C) and four different shear rates (61.3, 122.6, 306.6, and 613.1 s^?1). It was found that EMA reacts with vinyl groups of PDMS rubber at a temperature of 190°C during extrusion through the capillary of MPT, forming EMA‐grafted‐PDMS rubber (EMA‐g‐PDMS), which acts as the compatibilizer for the blend systems. The results are based on IR spectroscopy, melt rheology, and phase morphology of the blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 12: 2810–2817, 2003     

Hydrogenation of synthetic cis‐1,4‐polyisoprene and natural rubber catalyzed by [Ir(COD)py(PCy3)]PF6

In the presence of chlorinated solvents, the catalytic complex [Ir(COD)py(PCy₃)]PF₆ (where COD is 1,5‐cyclooctadiene and py is pyridine) was an active catalyst for the hydrogenation of synthetic cis‐1,4‐polyisoprene and natural rubber. Detailed kinetic and mechanistic studies for homogeneous hydrogenation were carried out through the monitoring of the amount of hydrogen consumed during the reaction. The final degree of olefin conversion, measured with a computer‐controlled gas‐uptake apparatus, was confirmed by Fourier transform infrared spectroscopy and ¹H‐NMR spectroscopy. Synthetic cis‐1,4‐polyisoprene was used as a model polymer for natural rubber without impurities to study the influence of the catalyst loading, polymer concentration, hydrogen pressure, and reaction temperature with a statistical design framework. The kinetic results for the hydrogenation of both synthetic cis‐1,4‐polyisoprene and natural rubber indicated that the hydrogenation rate exhibited a first‐order dependence on the catalyst concentration and hydrogen pressure. Because of impurities inside the natural rubber, the hydrogenation of natural rubber showed an inverse behavior dependence on the rubber concentration, whereas the hydrogenation rate of synthetic rubber, that is, cis‐1,4‐polyisoprene, remained constant when the rubber concentration increased. The hydrogenation rate was also dependent on the reaction temperature. The apparent activation energies for the hydrogenation of synthetic cis‐1,4‐polyisoprene and natural rubber were evaluated to be 79.8 and 75.6 kJ/mol, respectively. The mechanistic aspects of these catalytic processes were discussed on the basis of observed kinetic results. The addition of some acids showed an effect on the hydrogenation rate of both rubbers. The thermal properties of hydrogenated rubber samples were determined and indicated that hydrogenation increased the thermal stability of the hydrogenated rubber but did not affect the inherent glass‐transition temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4219–4233, 2006     

Acrylate‐based liquid rubber as impact modifier for epoxy resin

Carboxyl‐terminated poly(2‐ethyl hexyl acrylate) (CTPEHA) having various molecular weights were synthesized by bulk polymerization in the form of liquid rubber. The liquid rubbers (LR‐1 to LR‐4) were characterized by ¹³C‐NMR spectroscopic analysis, nonaqueous titration, and vapor‐pressure osmometry (VPO). The liquid rubber having the lowest molecular weight (M?_n = 3600) was prereacted with the epoxy resin and the modified epoxy networks were made by curing with an ambient temperature curing agent. The modified epoxy networks containing different concentrations of CTPEHA were evaluated with respect to their thermal and impact properties. The optimum properties were obtained at about 10–15 phr of CTPEHA concentration (phr stands for parts per hundred parts of epoxy resin). Fracture surface analysis by scanning electron microscopy (SEM) indicated the presence of a two‐phase microstructure. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1792–1801, 2001     

挤出过程中NR/CBR胶料壁滑移行为的研究——Ⅰ.压力振荡现象

聚合物流体流动过程中的壁滑移现象是其粘弹性的重要特征之一。应用Monsanto加工性能试验机考察了NR/CBR胶料在毛细管挤出流动中的壁滑移行为及其影响因素。在简化条件下,应用张量分析方法,导出描述产生壁滑移时的压力变化与挤出过程参变量及试样物性之间关系的数学模型,以及临界滑移距离的计算公式。研究结果表明,临界压力降测量数据与理论预测值软为吻合。     

Influence of die angles on pressure drop during extrusion of rubber compound

The factors affecting pressure losses during extrusion of polymer melts are discussed in the present article. The rheological properties of an unvulcanized rubber compound were examined by using a Monsanto processability tester (MPT) under experimental conditions of temperatures varied 90 to 120°C and shear rates from 10² to 10³ s^?1. Furthermore, a set of dies with different entry angle (2α) was selected to identify the effects of die angles on pressure losses in capillary extrusion of the sample fluid. It was found that the total pressure drop (ΔP) decreased when 2α < 75 degrees, and then increased with increasing 2α. The ΔP reached the minimum value when 2α is around 75°. It suggests that the natural converging angle of the sample fluid be about 75° under the experimental conditions, according to the research results presented in previous work. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1150–1154, 2001     

Thermoplastic elastomers based on recycled high‐density polyethylene,ethylene–propylene–diene monomer rubber,and ground tire rubber

High‐performance thermoplastic elastomers (TPEs), based on recycled high‐density polyethylene (HDPE^R), olefinic type ethylene–propylene–diene monomer rubber (EPDM), and ground tire rubber (GTR) treated with bitumen, were prepared by using dynamic vulcanization technology, and their structure–property relationships were investigated. It was established that special pretreatment of GTR by bitumen confers outstanding mechanical properties on the resulting TPEs. TPEs, containing GTR pretreated by bitumen, exhibit thermal behavior similar to that of the HDPE^R/EPDM basic blend in the temperature region up to about 340°C. Rheological measurements showed that bitumen acts as an effective plasticizer for the GTR‐containing TPEs. SEM, DSC, and DMTA results revealed improved adhesion between the particles of GTR treated by bitumen and the surrounding thermoplastic matrix, compared to that of the untreated GTR particles. It was concluded that bitumen acts as an effective devulcanizing agent in the GTR treatment stage. In the following steps of TPE production, bitumen acts simultaneously as a curing agent for the rubber components (EPDM/GTR) and as a compatibilizer for the blend components. GTR‐containing TPEs, prepared by extrusion technology, were reprocessed (by passing through the extruder six times) without any observable changes in their tensile properties, thermal stability, and melt viscosity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 659–671, 2005     

New synthesis methods for polypropylene‐co‐ethylene‐propylene rubber

In this research, the reinforcement of polypropylene (PP) was studied using a new method that is more practical for synthesizing polypropylene‐block‐poly(ethylene‐propylene) copolymer (PP‐co‐EP), which can be used as a rubber toughening agent. This copolymer (PP‐co‐EP) could be synthesized by varying the feed condition and changing the feed gas in the batch reactor system using Ziegler–Natta catalysts system at a copolymerization temperature of 10°C. The ¹³C‐NMR tested by a 21.61‐ppm resonance peak indicated the incorporation of ethylene to propylene chains that could build up the microstructure of the block copolymer chain. Differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and dynamic mechanical analysis (DMA) results also confirmed these conclusions. Under these conditions, the morphology of copolymer trapped in PP matrix could be observed and the copolymer T_g would decrease when the amount of PP‐co‐EP was increased. DMA study also showed that PP‐co‐EP is good for the polypropylene reinforcement at low temperature. Moreover, the PP‐co‐EP content has an effect on the crystallinity and morphology of polymer blend, i.e., the crystallinity of polymer decreased when the PP‐co‐EP content increased, but tougher mechanical properties at low temperature were observed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3609–3616, 2007     

Effects of extrusion conditions on rheological behavior of acrylonitrile–butadiene–styrene terpolymer melt

The influence of temperatures and flow rates on the rheological behavior during extrusion of acrylonitrile–butadiene–styrene (ABS) terpolymer melt was investigated by using a Rosand capillary rheometer. It was found that the wall shear stress (τ_w) increased nonlinearly with increasing apparent shear rates and the slope of the curves changed suddenly at a shear rate of about 10³ s^?1, whereas the melt‐shear viscosity decreased quickly at a τ_w of about 200 kPa. When the temperature was fixed, the entry‐pressure drop and extensional stress increased nonlinearly with increasing τ_w, whereas it decreased with a rise of temperature at a constant level of τ_w. The relationship between the melt‐shear viscosity and temperature was consistent with an Arrhenius expression. The results showed that the effects of extrusion operation conditions on the rheological behavior of the ABS resin melt were significant and were attributable to the change of morphology of the rubber phase over a wide range of shear rates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 606–611, 2002     

Extrusion of broad‐molecular‐weight‐distribution polyethylenes

The extrusion (single‐screw) characteristics of four high‐molecular‐weight, broad‐molecular‐weight‐distribution (MWD) polyethylene resins are discussed with an emphasis on the output rate. Despite the high molecular weights of the subject polyethylenes, their broad MWD (M_w/M_n range: 10 to 50) does not limit the pressure and torque developed during extrusion. However, the specific output of the four polymers was quite varied. First, the dynamics of the solids conveying section were examined with the highest‐molecular‐weight polyethylene exhibiting lower solids‐conveying rate than the other three. Further, a simple and quick method to evaluate the relative solids‐conveying efficiencies for various polyethylenes is presented. Finally, the dependence of the specific output on the melt rheology of the polymers is also addressed; specifically, the shear‐thinning extent of the melt in the metering section was found to influence output rate. The unique and counterintuitive temperature‐dependence of the shear‐thinning character for one of the four polymers will also be addressed in relation to its extrusion characteristics. Polym. Eng. Sci. 44:2266–2273, 2004. © 2004 Society of Plastics Engineers.     

Devulcanization of nitrile butadiene rubber in nitrobenzene

Sulfur‐crosslinked nitrile butadiene rubber (s‐NBR) was found to be devulcanized when it was heated with nitrobenzene at 200°C for 3 h. The tetrahydrofuran (THF)‐soluble fraction from s‐NBR heated with nitrobenzene was purified by reprecipitation with THF/n‐hexane, chloroform/n‐hexane, and THF/n‐hexane systems and was then characterized by means of Fourier transform infrared (FTIR) spectroscopy, ¹H‐NMR, gel permeation chromatography, dynamic thermogravimetry/differential thermal analysis (DTA), and differential scanning calorimetry (DSC). FTIR and ¹H‐NMR results revealed that the THF‐soluble fraction contained aromatic rings derived from nitrobenzene. Furthermore, the molecular weight of the THF‐soluble fraction was much lower than that of the parent noncrosslinked poly(acrylonitrile‐co‐butadiene). Although the weight loss of THF‐soluble fraction began at a lower temperature than that of the nonheated original nitrile butadiene rubber, the residual weight at 700°C tended to be higher for the former. This tendency became more marked with increasing time of heat treatment with nitrobenzene. The DSC‐determined glass‐transition temperature of the THF‐soluble fraction was higher than that of the original s‐NBR. To elucidate the devulcanization mechanism, we investigated two types of model reactions; one was the reaction of diphenyl disulfide with nitrobenzene, and the other was the reaction of polybutadiene with nitrobenzene. The former reaction, carried out at 250°C in diphenyl ether, yielded diphenyl sulfide with a loss of diphenyl disulfide and nitrobenzene. The use of a higher molar ratio of nitrobenzene to diphenyl disulfide resulted in a depression of diphenyl sulfide formation. The reaction of p‐chloronitrobenzene with diphenyl disulfide also gave diphenyl sulfide. The reaction of polybutadiene with nitrobenzene at 200°C resulted in the backbone scission of the polymer. The THF‐soluble solid product of the latter model reaction was found by FTIR and ¹H‐NMR to contain aromatic rings derived from nitrobenzene. The devulcanization mechanism is discussed on the basis of a comparison of the results of the model reactions with those of the s‐NBR devulcanization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3342–3353, 2004     

Failure behavior of resorcinol–formaldehyde latex coated aramid short‐fiber‐reinforced rubber sealing under transverse tension

Composites composed of rubber, sepiolite fiber, and resorcinol–formaldehyde latex‐coated aramid short fibers were prepared. Mechanical and morphological characterizations were carried out. To investigate the effect of interfacial debonding on the failure behavior of short‐fiber‐reinforced rubber composites, a micromechanical representative volume element model for the composites was developed. The cohesive zone model was used to analyze the interfacial failure. We found that computational results were in good agreement with the experimental results when the interfacial fracture energy was 1 J/m² and the interfacial strength was 10 MPa. A parametrical study on the interface and interphase of the composite was conducted. The results indicate that a good interfacial strength and a choice of interphase modulus between 40 and 50 MPa enhanced the ductile behavior and strength of the composite. The ductile properties of the composite also increased with increasing interfacial fracture energy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41672.     

ABS modified with hydrogenated polystyrene‐grafted‐natural rubber

Natural rubber (NR) latex was grafted by emulsion polymerization with styrene monomer, using cumene hydroperoxide/tetraethylene pentamene as redox initiator system. The polystyrene‐grafted NR (PS‐g‐NR) was hydrogenated by diimide reduction in the latex form using hydrazine and hydrogen peroxide with boric acid as a promoter. At the optimum condition for graft copolymerization, a grafting efficiency of 81.5% was obtained. In addition, the highest hydrogenation level of 47.2% was achieved using a hydrazine:hydrogen peroxide molar ratio of 1:1.1. Hydrogenation of the PS‐g‐NR (H(PS‐g‐NR)) increased the thermal stability. Transmission electron microscopy analysis of the H(PS‐g‐NR) particles revealed a nonhydrogenated rubber core and hydrogenated outer rubber layer, in accordance with the layer model. The addition of H(PS‐g‐NR) at 10 wt % as modifier in an acrylonitrile–butadiene–styrene (ABS) copolymer increased the tensile and impact strengths and the thermal resistance of the ABS blends, and to a greater extent than that provided by blending with NR or PS‐g‐NR. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Melt rheology and morphology of uncompatibilized and in situ compatibilized nylon‐6/ethylene propylene rubber blends

Melt rheology and morphology of nylon‐6/ethylene propylene rubber (EPR) blends were studied as a function of composition, temperature, and compatibilizer loading. Uncompatibilized blends with higher nylon‐6 content (N90 and N95) and rubber content (N5 and N10) had viscosities approximately intermediate between those of the component polymers. A very clear negative deviation was observed in the viscosity–composition curve over the entire shear rate range studied for blends having composition N30, N50, and N70. This was associated with the interlayer slip resulting from the high‐level incompatibility between the component polymers. The lack of compatibility was confirmed by fracture surface morphology, given that the dispersed domains showed no sign of adhesion to the matrix. The phase morphology studies indicated that EPR was dispersed as spherical inclusions in the nylon matrix up to 30 wt % of its concentration. A cocontinuous morphology was observed between 30 and 50 wt % nylon and a phase inversion beyond 70 wt % nylon. Various models based on viscosity ratios were used to predict the region of phase inversion. Experiments were also carried out on in situ compatibilization using maleic anhydride–modified EPR (EPR‐g‐MA). In this reactive compatibilization strategy, the maleic anhydride groups of modified EPR reacted with the amino end groups of nylon. This reaction produced a graft copolymer at the blend interface, which in fact acted as the compatibilizer. The viscosity of the blend was found to increase when a few percent of modified EPR was added; at higher concentrations the viscosity leveled off, indicating a high level of interaction at the interface. Morphological investigations indicated that the size of the dispersed phase initially decreased when a few percent of the graft copolymer was added followed by a clear leveling off at higher concentration. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 252–264, 2004     

Analysis of the phase partitioning of additives in rubber‐modified plastics

The phase partitioning of additives in polymer blends has a large impact on the performance of the blend. Therefore, it is necessary to be able to quantify the level of the additives in each phase. A ¹H–NMR method is presented to determine the partitioning of additives between the rubber and rigid phases of a high‐impact polystyrene (HIPS) material. In one case, a HIPS material was modified with 2,6‐di‐tert‐butyl‐4‐methyl‐phenol (Ionol, CAS# 128‐37‐OMF) as a stabilizer for both phases. HIPS materials with varying levels of Ionol were melt‐blended by extrusion and the total level of additives was determined analytically for these standard materials. The ¹H–NMR method was used to determine the level of Ionol in the poly(butadiene) rubber phase. The Ionol was found to preferentially partition into the rubber phase with a partition coefficient of about 2. A second example of the same concept, instead utilizing ¹³C–NMR, involved the analysis of the partition coefficient for both Tinuvin P and Tinuvin 770 (CAS# 2440‐22‐4 and 52829‐07‐9), partitioning between the rigid and rubber phases of an ethylene–propylene–diene‐modified (EPDM) toughened styrene–ran–acrylonitrile (SAN) copolymer. The partition coefficient was determined to be 0.5 for Tinuvin P and 1.3 for Tinuvin 770. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1963–1970, 2001     

Structural morphology and properties of star styrene–isoprene–butadiene rubber and natural rubber/star styrene–butadiene rubber blends

Star styrene–isoprene–butadiene rubber (SIBR) was synthesized with a new kind of star anionic initiator made from naphthalene lithium and an SnCl₄ coupled agent. The relationship between the structure and properties of star SIBR was studied. Star block styrene–isoprene–butadiene rubber (SB‐SIBR), having low hysteresis, high road‐hugging, and excellent mechanical properties, was closer to meeting the overall performance requirements of ideal tire‐tread rubber according to a comparison of the morphology and various properties of SB‐SIBR with those of star random SIBR and natural rubber/star styrene–butadiene rubber blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 336–341, 2004     

Effect of molecular weight of epoxidized‐natural rubber on viscosity and tack of pressure‐sensitive adhesives

The effect of molecular weight of rubber on viscosity and loop tack of rubber‐adhesives were studied using two grades of epoxidized‐natural rubber, i.e., ENR 25 and ENR 50. Coumarone–indene resin, gum rosin, and petro resin were used as tackifiers. Toluene was used as the solvent throughout the experiment. The adhesive was coated on polyethylene terephthalate (PET) substrate using a SHEEN hand coater. Viscosity was determined by a HAAKE Rotary Viscometer, whereas loop tack was measured by a Llyod Adhesion Tester operating at 10 cm/min. Results show that viscosity increases gradually upto a critical molecular weight of 6.8 × 10⁴ and 3.9 × 10⁴ for ENR 25 and ENR 50, respectively, before a rapid increase in viscosity is observed. Loop tack indicates maximum value at the respective critical molecular weights for the three tackifiers investigated suggesting the culmination of wettability. For both rubbers, loop tack increases with coating thickness due to the concentration effect of adhesive. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Properties of a new synthetic rubber: High‐trans 1,4‐poly(butadiene‐co‐isoprene) rubber

A high‐trans 1,4‐butadiene/isoprene copolymer (TBIP) was synthesized in a 5‐L autoclave with hydrogen as an effective molecular weight modifier. The effects of hydrogen on the catalyst efficiency and molecular weight of the copolymers were investigated. The processability and physicomechanical properties of TBIP and their relationship to the composition, composition distribution, and molecular weight of TBIP were examined in detail. Increasing the H₂ pressure effectively reduced the molecular weight of TBIP. The optimum Mooney viscosity of TBIP and the 1,4‐butadiene molar content in the feed were 30–50 and 5–25%, respectively. No cis–trans isomerization was observed during the roll processing procedure for TBIP. The vulcanization characteristics of TBIP were similar to those of general rubbers, and no reverse vulcanization was observed for TBIP. A high green strength was the typical characteristic of TBIP. Vulcanized TBIP (TBIR) with an optimum composition and molecular weight presented outstanding antifatigue properties and low heat buildup in comparison with general rubbers. Compared with general sidewall stock [natural rubber (NR)/butadiene rubber (BR) = 50/50], TBIR exhibited a greater than 15‐fold increase in its crack‐initiation resistance. The other mechanical properties of TBIR were similar to those of 50/50 NR/BR. The heat‐aging mechanism of TBIR was crosslinking aging. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2941‐2948, 2004     

Structural characterization of reactor blends of polypropylene and ethylene‐propylene rubber

Blends of isotactic polypropylene (PP), ethylene‐propylene rubber copolymer (EPR), and ethylene‐propylene crystalline copolymer (EPC) can be produced through in situ polymerization processes directly in the reactor and blends with different structure and composition can be obtained. In this work we studied the structure of five reactor‐made blends of PP, EPR, and EPC produced by a Ziegler‐Natta catalyst system. The composition of EPR was related to the ratio between ethylene and propylene used in the copolymerization step. The ethylene content in the EPR was in the range of 50–70 mol %. The crystallization behavior of PP and EPC in the blends was influenced by the presence of the rubber, and some specific interactions between the components could be established. By preparative temperature rising elution fractionation (P‐TREF) analysis, the isolation and characterization of crystalline EPC fractions were made. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2155–2162, 2004     

Rheological behavior of uncured styrene‐butadiene rubber at low temperatures,pure and filled with carbon black

The flow behavior of an uncured styrene‐butadiene rubber (SBR) has been studied by using a specific preshearing capillary rheometer in the range of temperatures encountered in extrusion, i.e. between 40°C and 90°C. A pure SBR and various SBR compounds filled with different amounts of carbon black (from 17 to 33 wt%) have been characterized. It was observed, for all tested materials, that the flow curve could be divided in different parts: at low shear rate, the material exhibits a classical behavior, where stress increases regularly with the shear rate. Above a certain critical stress, flow features changed, characterized by the simultaneous onset of wall slip and upstream instabilities. This critical stress is independent of temperature but increases linearly with carbon black amount. Flow curves at different filler contents were superimposed, using a shift factor that varies with filler content. Two theories for time/filler content superposition were proposed. Finally, a general viscosity law for uncured SBR compounds was introduced. This law is based on a Carreau‐Yasuda equation, where zero‐shear viscosity and characteristic time depend on both temperature and filler content, through Arrhenius and Krieger‐Dougherty expressions, respectively. POLYM. ENG. SCI., 55:2156–2162, 2015. © 2015 Society of Plastics Engineers