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     

Shear viscosity of carbon black filled polypropylene at very low shear stresses

The shear viscosity of carbon black filled polypropylene with a range of different carbon blacks was investigated. This was accomplished using (a) a constant shear stress creep instrument, (b) a cone-plate rotational rheometer, (c) a capillary extrusion rheometer. It was found that stresses exist for these compounds below which there are only finite deformations and no steady flow, Much attention was given to measurements of creep at low stresses, especially in the neighborhood of yield values. The magnitudes of yield stresses obtained from such creep measurements are significantly lower than those obtained using standard extrapolation to zero shear rate of higher stress data from rotational instruments. The shear viscosity behavior near the yield value differs significantly depending upon the carbon black used. A high viscosity was observed (～10⁹ to 10¹⁰ Pa.s) plateau in some 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.     

Effects of wall slip on the rheological measurement and extrusion die design of a filled rubber compound

We investigate the rheological properties of a filler-reinforced rubber compound using a rotorless shear rheometer specially designed for rubber and a rotational rheometer with parallel-plate geometry. Our aim is to evaluate the effects of wall slip on both the oscillatory and steady shear modes of the rotational rheometer. The rheological measurements show that the slip generally does not affect the oscillatory shear but does exist in the steady shear flow and tends to make the measured shear viscosity lower than the true value. Besides, we extend the investigation into engineering applications. The extrusion die for a given extrudate profile is obtained using a finite-element model in which the wall slip is considered as a boundary condition. To validate the die design, an extrusion experiment is carried out and the results confirm that, for filled elastomers, it is necessary to consider the effect of wall slip in the extrusion die design.     

Rheological investigations of suspensions of talc,calcium carbonate,and their mixtures in a polystyrene melt

An experimental study of the rheological properties of talc, calcite, and mixed particle compounds of polystyrene (PS) compounds has been carried out on a range of instruments at 200°C. We investigated the shear viscosity over a very wide range of shear rates in capillary, cone-plate, and sandwich rheometers. Shear stresses below which there is no flow, i.e. yield stresses, were found. A uniaxial elongational rheometer based on floating samples on a silicone oil bath was used to study the uniaxial extensional flow characteristics. The compounds were found to absorb silicone oil. It was, however, possible to estimate yield values of highly filled compounds in uniaxial extension by investigating the stretching of vertical filaments in a chamber filled with nitrogen.     

Rheology of polymers containing carbon black

In order to elucidate the flow behavior of electrophotographic toner systems, shear stress was measured as a function of shear rate in a cone and plate rheometer for polymer melts containing carbon blacks of surface area 24 and 625 m²/g at several concentrations and temperatures. Polymers included high and low molecular weight polystyrene and poly(butyl methacrylate). The addition of carbon black to the polymers caused a large increase in viscosity, especially at low shear rates and shear stresses. As the concentration of carbon black was increased, the viscosity at low shear rates became unbounded below a value of the shear stress designated the yield stress. The absolute magnitude of the yield stress depended primarily on the concentration and surface area of the carbon black and was independent of the polymer and temperature. Apparently, carbon black forms an independent network within the polymer at low shear rates which precludes flow. In some cases, the viscosity of polymers filled with carbon black was lower than that of the pure polymer. This effect was favored for polystyrene compared to poly(butyl methacrylate) and was facilitated by increasing the molecular weight of polystyrene, reducing the surface area and concentration of carbon black, and by increasing the temperature and shear rate.     

Flow of carbon black loaded styrene-butadiene (SBR)-cis-polybutadiene blends through capillary dies—influence of mixing and the location of carbon black

The flow behavior of carbon black loaded styrene-butadiene (SBR)-cis-polybutadiene (BR) is investigated as a function of mixing and the location of carbon black. The blends consist of an 80:20 weight ratio of SBR and BR with the incorporation of 20 phr carbon black via three different schemes to control the location of carbon black in the individual rubber phases. These are: (A) free black mixing of the three components, (B) mixing of SBR-black masterbatch with BR, and (C) mixing of BR-black masterbatch with SBR. Dynamic Mechanical Analysis (DMA) was used to characterize carbon black distribution. The damping characteristics indicate that when carbon black is masterbatched into either one of the rubbers, it continues to remain incorporated in that particular rubber phase upon blending with the second rubber. The flow behavior is measured with an Instron capillary rheometer. The results indicate that the viscosity function of these blends is not sensitive to the mixing conditions. However, the elasticity is always, dependent on mixing. Elasticity is expressed as ΔPe/σ, where ΔPe is the entrance pressure drop from the Bagley plot and σ the shear stress. In general, ΔPe/σ of the blend decreases with increasing mixing.     

Measurement of the rheological properties of thermoplastic elastomers

Using the Han slit/capillary rheometer, measurements were taken of the rheological properties of commercially available thermoplastic elastomers, namely, styrene–butadiene–styrene (SBS) block copolymer (Shell, Kraton), ethylene–propylene copolymer (Exxon, Vista), olefinic-type thermoplastic rubbers (UniRoyal, TPR 1600, TPR 1900, and TPR 2800), and urethane thermoplastic elastomers (UniRoyal, Roylar A863 and Roylar E9). The rheological properties determined were shear viscosity and first normal stress difference at various melt temperatures. Depending on the material and the melt temperature tested, the range of shear rates tested was 50 to 700 sec^?1, and the range of shear stresses tested was 10⁵ to 10⁶ dyn/cm². For comparison purposes, rheological measurements were also taken for a few materials using the Weissenberg rheogoniometer although its use was limited to low shear rates (or shear stresses). It was demonstrated clearly that the Han slit/capillary rheometer is a unique instrument for determining the rheological properties of thermoplastic elastomers in the range of high shear rates (or high shear stresses) often encountered in various polymer processing operations.     

A Survey of Rheological Properties of One-Component Epoxy Adhesives

Flow characteristics of seven commercially available one-component epoxy adhesive pastes were measured using a controlled shear stress rheometer and a controlled shear rate rheometer over a temperature range from 5°C to 60°C. Combining data obtained from both controlled rate and controlled stress experiments over a wide range of shear rates, we observed Newtonian flow (shear stress proportional to shear rate) at very low shear rates, a plateau “shear thinning” region at intermediate shear rates, and a second region of linear dependence of shear stress on shear rate at high shear rates. The adhesive pastes exhibited a very broad range of rheological behavior. Two flow parameters important to adhesive application technology, the plastic viscosity and the apparent yield stress, were measured for each adhesive. The plastic viscosity ranged from 11.6 to 329.5 Pa. s; the apparent yield stress ranged from 56.2 to 413 Pa. The temperature dependence of the rheological parameters of the epoxy adhesive pastes was also determined. The results are reported as the activation energies, E_η and E_σ, of plastic viscosity and apparent yield stress, respectively. The apparent yield stress of each adhesive paste was much less sensitive to changes in temperature than was the plastic viscosity. This suggests that the processing characteristics are likely to show qualitative as well as quantitative changes with temperature.     

Effect of Wood Fibers on the Rheological and Mechanical Properties of Polystyrene/Wood Composites

The effects of wood fibers on the rheological and mechanical properties of polystyrene/wood (PS/wood) composites were investigated. The composites with different ratios of PS and wood were prepared by means of internal mixer and, additionally, two different sizes of the wood particles were used, such as ～100 and ～600 µm. The rheological properties were studied using capillary rheometer, apparent shear rate, apparent shear stress, apparent viscosity, power law index, and flow activation energy at a constant shear stress were determined. The rheological results showed that the shear stress–shear rate variations obeyed a power law equation, and the composites exhibited shear thinning. The flow activation energy of the composites increased with the addition of wood particles. Mechanical results showed that stress at break of the composites was higher than that of pure PS, whereas the strain at break and impact strength of the composites were lower than that of PS. In addition, the mechanical properties of the present composites were improved when the small size of wood particles were incorporated.     

Shear viscosity of rubber modified thermoplastics: Dynamically vulcanized thermoplastic elastomers and ABS resins at very low stress

The shear viscosity of PP-EPDM dynamically vulcanized thermoplastic elastomers and ABS resins were investigated using (a) a constant shear stress creep instrument, (b) a rotational rheometer, and (c) a capillary extrusion rheometer. It was found that stresses exist for some of these materials below which they exhibit only finite deformations. This indicates they exhibit yield values. Much attention was given to measurements of creep at low stresses especially in the neighborhood of yield values. The magnitudes of the yield stresses obtained from these low stress measurements are significantly lower than those obtained using standard extrapolation to zero shear rate of higher stresses from rotational instruments. We also observed a high shear viscosity (～10⁹ PA s) plateau in the materials of high rubber content. We contrasted our results to those found in the literature.     

一种阻燃抗静电聚丙烯的流变性能

采用毛细管流变仪和旋转流变仪分别研究了溴系阻燃剂、炭黑填充对聚丙烯熔体高剪切挤出畸变和动态黏弹特性的影响。发现低含量下随填充量的提高,发生挤出畸变的临界剪切速率提高,扩大了加工窗口。动态流变试验表明树脂中添加更多炭黑后剪切变稀时的复数黏度、储能模量和损耗模量都增大,但损耗因子下降。进一步用缠结模型和Cross模型定量分析表明,填料吸附高分子链段而减少其壁面吸附,减轻挤出畸变,进而提高临界剪切速率;粒子分布网络提高了平台模量和缠结密度,缩短了松弛时间,恢复更快而减小挤出胀大比。复合材料中添加3.5%（质量）炭黑后形成逾渗网络,表现为高零切黏度和长松弛时间,发生“类液-类固”转变;同时材料表面电阻下降明显,此时黏弹逾渗点与导电逾渗点基本一致。     

Experimental study of rheological properties of solid propellant slurry at low-shear rate and numerical simulation

The steady state rheological properties of a three-component hydroxyl-terminated polybutadiene binder (HTPB) solid propellant slurry at low shear rate were investigated using a rotational rheometer. The data were analyzed and the rheological characteristics of the slurry were determined. The effect of shear rate on apparent viscosity and shear stress as well as the viscosity–time effect of the slurry were also analyzed. Herschel–Bulkley (H-B) model was applied for the simulation of the flow process of a two-dimensional container using CFD Ansys-polyflow software. Experimental results showed that solid propellant slurry had yield pseudoplasticity. Yield characteristics were determined based on the fact that when shear stress was greater than yield stress, the slurry began to flow and the relationship between shear stress and shear rate obeyed power law function. Simulation results further verified the correctness of experimental results.     

A Survey of Rheological Properties of One-Component Epoxy Adhesives

Flow characteristics of seven commercially available one-component epoxy adhesive pastes were measured using a controlled shear stress rheometer and a controlled shear rate rheometer over a temperature range from 5°C to 60°C. Combining data obtained from both controlled rate and controlled stress experiments over a wide range of shear rates, we observed Newtonian flow (shear stress proportional to shear rate) at very low shear rates, a plateau “shear thinning” region at intermediate shear rates, and a second region of linear dependence of shear stress on shear rate at high shear rates. The adhesive pastes exhibited a very broad range of rheological behavior. Two flow parameters important to adhesive application technology, the plastic viscosity and the apparent yield stress, were measured for each adhesive. The plastic viscosity ranged from 11.6 to 329.5 Pa. s; the apparent yield stress ranged from 56.2 to 413 Pa. The temperature dependence of the rheological parameters of the epoxy adhesive pastes was also determined. The results are reported as the activation energies, E_η and E_σ , of plastic viscosity and apparent yield stress, respectively. The apparent yield stress of each adhesive paste was much less sensitive to changes in temperature than was the plastic viscosity. This suggests that the processing characteristics are likely to show qualitative as well as quantitative changes with temperature.     

Rheological behavior of a microcellular,oil-extended ethylene–propylene–diene rubber compound: Effects of the blowing agent curing agent,and conductive carbon black filler

The rheological behavior of microcellular, oil-extended ethylene–propylene–diene rubber (EPDM) compounds was studied in extrusions containing a blowing agent. The cell morphology development and rheological properties were studied for unfilled and conductive carbon black (Vulcan XC72, Cabot Corp., Ltd., Alpharetta, GA) filled compounds with variations of the blowing agent, extrusion temperature, and shear rate. The apparent shear stress, apparent viscosity, die swell (%), and total extrusion pressure of the Vulcan XC72 filled, oil-extended EPDM compounds were determined with a Monsanto processability tester (St. Louis, MO). The effects of the curing agent and blowing agent on the rheological properties of the compounds were also studied. A significant reduction in the stress and viscosity with the blowing agent was observed in the compound in the presence of the curing agent in comparison with those without the curing agent. The viscosity reduction factor was found to be dependent on the blowing agent loading, shear rate, and temperature. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Capillary extrusion behavior of phenolphthalein poly(ether-ether-sulphone) (PES-C)

The capillary extrusion flow properties of novel engineering thermoplastic phenolphthalein poly(ether-ether-sulphone) (PES-C) have been investigated using capillary rheometer. The dependence of viscosity on the wall shear rate and temperatures were obtained. The flow activation energy was found to decrease with shear rate but to be constant with shear stress. The entrance effect was calculated and from which the extensional behavior was estimated using Cogswell's method. From the extrudate swell ratio the principal normal stress was evaluated and a temperature-independent correlation was observed when they were plotted against shear stress. The melt fracture phenomena were checked and discussed also. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:951–958, 1997     

Rheological behaviour of copoly(ethylene/octene) elastomer compunds: Effect of blowing agent and precipitated CaCO3 filler

Abstract

An experimental study of the rheological behaviour of ethylene/octene copolymer compounds in extrusion containing blowing agent has been carried out. The cell morphology development was studied using scanning electron microscopy. Rheological properties of unfilled and precipitated CaCO₃ filled systems with various blowing agents, extrusion temperatures, and shear rates were studied using a capillary rheometer. The total extrusion pressure, apparent shear stress, apparent viscosity, and die swell of the unfilled and CaCO₃ filled compounds were also determined and the effect of blowing agent on the rheological properties of the compounds studied. It was observed that there is reduction of stress and viscosity with blowing agent loading. Incorporation of blowing agent led to decreased shear thinning behaviour resulting in an increase in the power law index. The viscosity reduction factor of the unfilled compound was found to be dependent on the concentration of blowing agent, the shear rate, and the temperature.     

Die extrusion behavior of carbon black-filled block copolymer thermoplastic elastomers

The properties of carbon black-filled thermoplastic elastomers were studied. We compared the extrudate swell behavior and the rheological properties of carbon black-filled polymers with those of raw polymers. The shear viscosity increases with increasing amount of carbon black. The extrudate swell becomes smaller with increasing carbon black amount, indicated by the decreased elasticity of the material when adding carbon black. © 1993 John Wiley & Sons, Inc.     

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.     

定向碳纳米管/高密度聚乙烯复合材料体系流变行为的研究

对定向碳纳米管进行酸化处理以后，采用机械共混法制备了定向碳纳米管／高密度聚乙烯复合材料，利用毛细管流变仪研究了高密度聚乙烯和定向碳纳米管／高密度聚乙烯复合材料的流变行为．讨论了剪切应力、剪切速率、温度以及定向碳纳米管的加入对体系流变行为的影响。结果表明：高密度聚乙烯和定向碳纳米管／高密度聚乙烯复合材料都属于假塑性流体．高密度聚乙烯的非牛顿性要大于定向碳纳米管／高密度聚乙烯复合材料；随剪切速率和剪切应力的增大及温度的升高．熔体表现粘度均减小；随着定向碳纳米管含量的增加，定向碳纳米管／高密度聚乙烯复合材料的表观粘度先减小后增大。