From melt flow index to rheogram

A knowledge of the complete flow curve or rheogram of a polymeric melt depicting the variation of the melt viscosity over industrially relevant range of shear rate and temperature is essential in the design of polymer processing equipment, process optimization and trouble-shooting. These data are generated on sophisticated rheometers that are beyond the financial and technical means of most plastics processors. The only flow parameter available to the processor is the melt flow index of the material. In the present work, a method has been proposed to estimate the rheograms of a melt at temperatures relevant to its processing conditions with the use of a master curve, knowing the melt flow index and glass transition temperature of the material. Master curves that coalesce rheograms of different grades at various temperatures have been generated and presented for low density polyethylene, high density polyethylene, polypropylene, polystyrene and styrene-acrylonitrile copolymer.     

Effect of temperature on rheological properties of suspensions

A parameter, the product of viscosity of the suspension medium and applied shear rate, is introduced to describe the effect of temperature on the rheological properties of suspensions, considering the mechanism of agglomeration in suspensions. It is found that, by plotting rheograms of the shear stress versus this parameter, a single master curve can be obtained independently of temperature. The dependence of viscosity on temperature and the flow of suspensions are shown to be well described.     

Shear flow rheological properties of vinylon- and glass-fiber reinforced polyethylene melts

Shear viscosity, shear stress and first normal-stress difference have been investigated for glass- and vinylon-fiber filled polyethylene melts over a wide range of shear rate by means of three kinds of instruments. The influence of fiber content and fiber properties on the rheological properties is discussed. The viscosity increases with increasing aspect ratio and fiber content, and the influence of these parameters on the flow properties is evident at low shear rates. The first normalstress difference increases more rapidly with increasing glass fiber content, especially at low shear stresses. The influence of vinylon fibers on the first normal stress-difference vs. shear-stress relationship is different from that of glass fibers.     

Correlation between thermal and rheological studies to characterize the behavior of bitumen

The objective of this work is a comprehensive thermo-rheological study of pure bitumen. The bitumen is a complex material consisting of asphaltenes dispersed in a maltene matrix. As a consequence, its flow behavior is characterized by the presence of a yield stress, which depends on temperature below 50°C. Applying the Cox–Merz rule, a master curve of viscosity can be obtained over a wide range of shear rates for temperatures above 50°C. It can be accurately modeled by a Carreau–Yasuda law with a yield stress. This specific rheological behavior can be explained by the changes induced by the temperature on the microstructure, evidenced by modulated differential scanning calorimetry measurements.     

On the time-dependency of the flow-induced dynamic moduli of a liquid crystalline hydroxypropylcellulose solution

Some unusual rheological features of a liquid crystalline solution of hydroxypropylcellulose (HPC) in water have been investigated. Measurements have been performed by using a variety of different apparatuses with cone and plate geometries. Particular attention has been devoted to the experimental procedures, including the use of different sealing techniques, which are necessary to avoid solvent evaporation during the very long transients. Shear fracture effects, and their dependence on the type of sealing agents have also been studied. In steady shear, the HPC solution shows some rheological features which are common to other lyotropic systems, such as a three-region viscosity curve, and a double sign change in the first normal stress difference vs shear rate curve. The structural changes which take place after cessation of shear flow have been investigated by following the evolution of the dynamic moduli as a function of the time elapsed after the shear flow is stopped. It was found that the rate of the previously applied shear strongly affects both the kinetics and the asymptotic, long time values of the dynamic properties. Possible explanations for such behavior in terms of microstructure evolution are presented and discussed.     

Quiescent and shear-induced crystallization of polyprophylenes

In this paper, the effect of shear on the flow-induced crystallization (FIC) of several polypropylenes of various macrostructures was studied using rheometry combined with polarized microscopy. Generally, an increase in strain and strain rate or decrease of temperature is found to decrease the thermodynamic barrier for crystal formation and thus enhancing crystallization kinetics at temperatures between the melting and crystallization points. Secondly, popular models based on suspension theory which are used to relate the degree of crystallinity to normalized rheological functions (such as viscosity) are validated experimentally. For this purpose, the space filling of crystals in the polarized micrographs determined from image processing was plotted as a function of normalized viscosity under various shear rates. It is found that the constant(s) of various suspension models should be dependent on the flow parameters in order for the suspension models to describe the effect of shear on FIC, particularly at higher shear rates.     

The rheology of bread dough made from four commercial flours

 A selection of four commercial flours has been subjected to extensive rheological measurements as part of a comprehensive program of wheat improvement. The results have been used to determine which of the many types of rheological measurements provide significant discrimination between various types of modern baker's flours (including biscuit flours) and to procure data suitable for use in mathematical models describing the dough rheology. The rheological measurements undertaken include oscillatory shear at low amplitude, steady shear at a low shear rate, stress relaxation and extensional viscosity testing. Although oscillatory shear data show minor differences between these flours, the other tests show significant variations and these provide very good discrimination between the different flour types in comparison with conventional dough testing (e.g. by the extensograph). The current dough rheological measurements provide further insight into molecular structure. In the future, mathematical (constitutive) models are expected to provide a means of predicting processing and baking behaviour of bread dough. Received: 27 June 2001 Accepted: 28 August 2001     

Flow instability and shear localization in a drilling mud

To have a better knowledge of problems occurring with drilling fluids in complex wells, we carried out a detailed rheological analysis of a typical drilling mud at low shear rates using both conventional rheometry and MRI velocimetry. We show the existence of a viscosity bifurcation effect: Below a critical stress value, the mud tends to completely stop flowing, whereas beyond this critical stress, it reaches an apparent shear rate larger than a finite (critical) value, and no stable flows can be obtained between this critical shear rate value and zero. These results are confirmed by MRI velocity profiles, which exhibit a slope break at the interface between the solid and the liquid phases inside the Couette geometry. Moreover, this viscosity bifurcation is a transient phenomenon, the progressive development of which can be observed by MRI. A further examination of MRI data shows that, in the transient regime, the shear rate does not vary monotonously in the rheometer gap and is particularly large along the outer (rough) cylinder, which might be at the origin of the development of a region of constant shear rate in the apparent flow curve.     

Rheological behaviour of nano-composites based on polyamide 6 under shear and elongational flow at high strain rates

In this work, the rheological behaviour of high molecular mass polyamide 6 (PA6)/organo-montmorillonite nano-composites, obtained via melt blending, was investigated under shear and extensional flow. Capillary rheometry was used for the measurement of high shear rate steady state shear viscosity and die entrance pressure losses; further, by the application of a converging flow method (Cogswell model) to these experimental results, elongational viscosity data were indirectly calculated. The extensional behaviour was directly investigated by means of melt spinning experiments, and data of apparent elongational viscosity were determined. The results evidenced that the presence of the organo-clay in filled PA6 melts modifies the rheological behaviour of the material, with respect to the unfilled polymer, in dependence on the type of flow experienced by the fluid. In shear flow, the nano-composites showed a slightly lower viscosity than neat PA6, whereas in elongation, they appeared much more viscous, in dependence on the organo-clay content.     

Specific rheology – morphology relationships for some blends containing LCPs

For the blend melts of isotropic polysulfone (PSF) and LC polyester (PES), differing in viscosity more than 10 times, the flow curves with maxima were observed in cone and plate geometry. The low shear rate branch is located near the PSF flow curve, and the high shear rate branch is close to the PES flow curve. At high strains, the formation of the ring-like morphology of the blend sample, accompanied by appearance of maximum on flow curve, was registered. The scaling analysis of the reasons for the ring morphology formation was based on stretching of the large, low-viscous LC droplet, embedded to the high-viscous polymer matrix, in a homogeneous shear field. It was shown that, if the critical Taylor radius is not exceeded, the droplet may form the closed torus. Under strong flows, the PSF melt manifests the “spurt effect”, consisting of a drastic increase of the shear rate when the critical value of the shear stress is reached. The pattern of the blend flow curves with maxima may be explained by a vanishing PSF input to the total shear stress, inherent for blends, while the PES melt continues to be in a liquid state and, consequently, is responsible for the blend viscosity at the high shear rates. The presence of regular heterogeneities in the blend in the form of LC rings may initiate the rupture of the entanglements network of the matrix PSF (close to LC rings) under strong shear flows. The appearance of the low-viscous “cracks” at the critical shear stress will diminish the contribution of the PSF to the blends rheological response. Received: 20 April 1999 Accepted: 28 January 2000     

Flow properties of oven-curing high solids white enamels

For the characterization of the rheological behaviour of a white, high solids, oven-curing enamel for household equipment with regard to its industrial application, attention was focused on the flow aspects involved in laying down process and film formation phenomena, i.e. viscosity at very high and very low shear rate, structural build-up in rest conditions, presence and magnitude of elastic components. Hence, investigations were aimed at (1) the determination of the equilibrium flow curve; the application of the Shangraw-Grim-Mattocks model led to the evaluation of parameters to describe infinite shear-rate viscosity and yield stress; (2) obtaining information about particle aggregation state in shear conditions. Quemada model gave indication that, even at very high shear, particle aggregates are stable; (3) the determination of time-dependent behaviour: elastic components were found to be almost negligible; the Trapeznikov-Fedotova procedure allowed thixotropic build-up in rest conditions to be evaluated, as concerns both amount and kinetics. Remarkable flow features found were: differences in the temperature dependence of viscosity at low shear rate and of yield value for enamels formulated with different pigment volume concentrations and the strong effect of the pigment volume concentration on the initial rate of thixotropic build-up in rest conditions.     

Flow instability for binary blends of linear polyethylene and long-chain branched polyethylene

The rheological properties and flow instability are studied for binary blends composed of a long-chain branched polyethylene and a linear polyethylene. It is found that the blends containing a linear-polyethylene with high shear viscosity exhibit higher oscillatory moduli, drawdown force, and strain-hardening behavior. The blends showing the anomalous rheological phenomena show sharkskin failure in low shear rate region as compared with a pure linear polyethylene. Moreover, the blends exhibit severe gross melt fracture at low output rate. Enhanced strain-hardening in elongational viscosity and large entrance angle at a die entry will be responsible for the severe gross melt fracture for the blends.     

Molecular theory for moderately concentrated polymer solutions in shear flow

A molecular theory for the rheological properties of moderately concentrated polymer solutions is developed on the basis of a model of interacting dumbbells. The interaction is treated in a mean field approximation, leading to an effective one-particle potential and a Gaussian stationary distribution function. Various rheological functions such as birefringence, shear viscosity and first normal-stress coefficient for simple shear flow and the Trouton viscosity for simple extensional flow are calculated. Good qualitative agreement with experimental observations is found, especially at intermediate flow rates. It is predicted, for example, that the birefringence increases approximately linearly with shear rate at intermediate shear rates and that the concentration dependence of the gradient varies asc ^1/2. The typical non-Newtonian behaviour is obtained for the shear viscosity. For small concentrations the onset of shear rate dependence decreases asc ^–1/2. At intermediate shear rates an apparent power law is obtained with an exponent between – 0.5 and – 1.0, decreasing with concentration.     

Generic properties of rheological flow curves

The interpretation and comparison of viscosity data for fluids in planar Couette flow are discussed using a generic rheological function, familiar from studies of polymeric liquids. The particular data are generated by non-equilibrium molecular dynamics (NEMD) simulations of model fluids, however the analysis has wider validity. The mathematical properties of the established flow curves are investigated and, inter alia, a consistent definition of the critical shear rate is established. It is also shown that the use of inappropriate, but commonly used, independent variables leads to curves whose qualitative behaviour is extremely sensitive to the physical parameters. Such a range of qualitative behaviour can lead to erroneous quantitative conclusions when interpreting physical (or model) data. A particular example is the assumption of a linear dependence of the viscosity on the square-root of the shear rate, as often used in the NEMD literature. The developed framework also enables the systematic comparison of simulations of the same molecular fluid performed at different state points. This is illustrated for the case of three recently published and apparently conflicting NEMD results for n-butane.     

Time-dependent plane Poiseuille flow of a Johnson–Segalman fluid

We numerically solve the time-dependent planar Poiseuille flow of a Johnson–Segalman fluid with added Newtonian viscosity. We consider the case where the shear stress/shear rate curve exhibits a maximum and a minimum at steady state. Beyond a critical volumetric flow rate, there exist infinite piecewise smooth solutions, in addition to the standard smooth one for the velocity. The corresponding stress components are characterized by jump discontinuities, the number of which may be more than one. Beyond a second critical volumetric flow rate, no smooth solutions exist. In agreement with linear stability analysis, the numerical calculations show that the steady-state solutions are unstable only if a part of the velocity profile corresponds to the negative-slope regime of the standard steady-state shear stress/shear rate curve. The time-dependent solutions are always bounded and converge to different stable steady states, depending on the initial perturbation. The asymptotic steady-state velocity solution obtained in start-up flow is smooth for volumetric flow rates less than the second critical value and piecewise smooth with only one kink otherwise. No selection mechanism was observed either for the final shear stress at the wall or for the location of the kink. No periodic solutions have been found for values of the dimensionless solvent viscosity as low as 0.01.     

Modeling of blood rheological behavior in unsteady-state shearing flows

Issues of blood flow modeling under unsteady-state conditions at moderate shear rates are considered using a blood rheological model accounting both for the viscoelastic properties and the thixotropy caused by erythrocyte aggregation. The resulting shear stress versus time relations for single shear rate steps and the dependence of the complex viscosity components on the shear rate amplitude in oscillating shear flow show good qualitative correspondence with the experimental data reported in the literature.Moscow. Translated from Izvestiya Rossiiskoi Akademii Nauk, Mekhanika Zhidkosti i Gaza, No. 6, pp. 26–30, November–December, 1995.     

A study on the limitations of a vane rheometer for mineral suspensions using image processing

This study presents the results from the rheological measurement of clay suspensions using vane geometry in a wide gap configuration. It focuses on how measurement of viscosity cannot be effective for two reasons: the limits of the vane geometry itself and the limits of the material depending on its content of solid particles. Image analysis of the flow while shearing the material is carried out to relate the flow behavior. Several approaches to compute the shear flow curve from torque-rotational velocity data are used. The results demonstrate that the applied setpoint while applying a logarithmic shear rate ramp can be very different from the calculated shear rate from existing theories. Depending on the solid volume fraction of the particles in the mixture, we relate the macroscopic behavior using image analysis and the shear flow curves to the rheophysical regime of the flow of the suspensions. Therefore, this paper has two simultaneous goals: the first one is to describe the physical phenomena which control macroscopic behavior and the second one is to highlight the limits of the vane geometry for viscosity measurement of mineral suspensions like kaolinite pastes.     

Linear viscoelastic behavior of asphalt and asphalt based mastic

The rheological properties of an asphalt mastic and its matrix are investigated. For the purpose of comparison a sample of thermal aged asphalt matrix is also considered. Dynamic and creep shear measurements are reported. The reduced shear rate concept proposed by Ohl and Gleissle is used to correlate mechanical properties of the three materials at the same temperature. We found that the concept gives only qualitative trends. A similar conclusion is found concerning the applicability of the time-temperature superposition principle for each sample. Our experimental results show also that the increase in viscosity due to thermal treatment or to the inclusion of solid particles is not uniform with temperature. The differences in the increase of the Vogel temperature from the asphalt to the mastic, or to the thermally aged asphalt, relate to the different mechanisms involved. Sedimentation of steel spheres in asphalt and mastic, is studied next. The Newtonian wall correction factor for the Stokes drag law holds for the three samples. Despite the similar behavior observed in conventional shear tests, Stokes' law gives the correct trend for the two asphalts although it overestimates the experimental settling velocity by a factor of approximately two in the case of the mastic. Received: 8 June 1999/Accepted: 19 October 1999     

Possibility of a master plot for material functions of high-polymer solutions

A new systematic method has been developed for estimating rheological properties (such as relaxation time, viscosity, primary normal stress difference) for various polymer solutions form the zero-shear-rate specific viscosity and a dimensionless shear rate.A linear relation has been found between the relaxation time and the zero-shear-rate specific viscosity on a double-logarithmic plot, and a new master plot for the primary normal stress difference has been established. In addition the applicability of the FENE-P dumbbell model to high-polymer solutions is discussed.     

活性流体流变行为的布朗动力学模拟研究

活性流体在用于开发新材料方面具有巨大潜力, 满足这一需求就要定量掌握活性流体所表现的特殊力学行为, 特别是流变行为. 扩展布朗运动方程, 建立自驱动活性粒子的运动模型, 基于反向非平衡法确定活性流体的黏度, 考察活性粒子体积分数、直行速度和转向扩散系数对活性流体流变行为的影响规律, 确定活性流体特殊流变行为的形成机理. 结果表明, 活性流体的流变曲线可被划分为黏度下降区、过渡区和牛顿区; 活性粒子体积分数越高, 活性流体的非牛顿特性越显著, 活性粒子的直行运动引起活性流体在低剪切速率区域黏度下降, 直行运动和转向运动的耦合作用导致中剪切速率区域流变曲线非单调变化, 活性粒子频繁发生转向运动会导致活性流体非牛顿特性受到抑制; 活性流体的宏观流变学特性和粒子的涨落直接相关, 活性粒子体积分数越高、直行速度越快和转向扩散系数越小, 活性流体中活性粒子越容易产生显著的涨落; 低剪切速率区域内活性粒子涨落明显, 随着剪切速率增大, 活性粒子的涨落逐渐被削弱, 粒子的聚集结构不断被破坏, 最终体系的流变行为类似一般被动流体.