Quantitative evaluation of extrudate swell from viscoelastic properties of polystyrene

A theory of extrudate swell for short, intermediate or long dies is presented. In our experiment, we consider that the swelling phenomenon is mainly due to the recoverable elongational strain induced by the converging flow at the die entrance, as well as by recoverable shear strain originating within the die. From these concepts, an equation has been derived for the quantitative prediction of extrudate swell from the elastic material properties such as the entrance pressure drop, the relaxation modulus and the recoverable shear strain. Excellent agreement is found between predicted and measured values of extrudate swell obtained on commercial polystyrene melt, using capillaries of length-to-diameter ratios ranging from 1 to 20 and in a wide range of shear rates.     

Exponential shear flow of branched polymer melts

  The behavior of a low-density polyethylene melt in exponential shear strain histories is examined and compared to its behavior in constant rate planar elongation. A new set of shear stress and first normal stress difference data in exponential shear are presented and used in several different material functions that have been previously proposed. Viscosities composed of principal stress differences for the two flows showed no correspondence suggesting that, contrary to previous assertions, exponential shear and constant rate planar elongation flows are fundamentally different. It is further suggested that the presence of vorticity makes exponential shear a weak, rather than strong, flow. Received: 5 March 1999/Accepted: 1 September 1999     

Time-dependent,non-Newtonian behavior of viscoelastic materials

Summary The present paper is a further development in our effort to describe non-Newtonian flow behavior. As in the past, the thixotropic shear stress or shear rate is characterized by the kinetic theory and currently a modified form ofOldroyds model provides the elastic contribution. Presented here are further modifications of the model in order to predict the first normal stress difference and logical changes to make the model more internally consistent.In order to test the approach, transient and steadystate data have been obtained with aWeissenberg rheogoniometer on a solution of polymethylmethacrylate in diethylphthalate. Both constant stress and constant shear rate data have been taken over a broad range of the parameters involved. To facilitate data acquisition, a PDP-15, model 30 computer was programmed to gather data at rates of 1000 points per second. Of the data obtained there is a great deal of uncertainty about the normal stress results.By optimization methods, the constants of the model were evaluated from steady-state data and transient results on stress growth and shear rate growth. Comparisons of the model with stress growth results as well as the prediction of the first normal stress difference are given. The inadequacies of the analysis are emphasized and possible points for improvement are made.With 8 figures     

Rheology of concentrated microgel solutions

Viscosity, modulus, and yield stress for 0–6 wt% aqueous solutions of Carbopol 941 were investigated using constant shear rate, constant shear stress, and dynamic oscillatory experiments. The microgel character of the polymer was evident from the solid-like behavior of the solutions above 1 wt%. Yield stress increased with concentration, but yield occurred at a critical shear strain of 40%, independent of concentration. The static stress-strain relationship became non-linear at ~ 25% strain, in fair agreement with the onset of non-linear response in the storage modulus at ~ 10% strain. Small strain moduli from static and low frequency measurements agreed rather well; modulus values obtained from the recoverable strain after yielding were 30–40% smaller. Solutions flowed at near-constant stress in the low shear rate regime; at higher rates the stress increases with shear rate more rapidly. The viscosity did not obey the Cox-Merz rule. Steady-state viscosity scaled with polymer concentration to the 3/4 power. Results were interpreted using a cellular, deformable sphere model for the polymer, in analogy to emulsions and foams.     

Elongational flow behavior of polymeric fluids according to the Leonov model

The viscoelastic behavior of polymeric systems based upon the Leonov model has been examined for (i) the stress growth at constant strain rate, (ii) the stress growth at constant speed and (iii) the elastic recovery in elongational flow. The model parameters have been determined from the available rheological data obtained either in steady shear flow (shear viscosity and first normal-stress difference as a function of shear rate) or oscillatory flow (storage and loss moduli as a function of frequency in the linear region) or from extensional flow at very small strain rates (time-dependent elongation viscosity in the linear viscoelastic limit). In addition, the effect of the parameter characterizing the strain-hardening of the material during elongation has also been studied. The estimation of this parameter has been based upon the structural characteristics of the polymer chain which include the critical molecular weight and molecular weight of an independent segment. Five different polymer melts have been considered with varying number of modes (maximum four modes). Resulting predictions are in fair agreement with corresponding experimental data in the literature.     

Elastic flow-front fingering instability in flowing polymer solutions

An experimental investigation of the flow-front behavior of dilute and semi-dilute polymer solutions has been carried out to gain a better understanding of the underlying mechanisms leading to the occurrence of an unstable flow at the advancing flow-front during the filling of a rectangular Hele-Shaw cell. Our experimental results have revealed the existence of an elastic finger-like instability at the advancing flow-front that develops in semi-dilute solutions of high molecular weight polymers, with an onset time of approximately a few hundred milliseconds. Although at shear rates above critical, narrow finger patterns develop at the flow-front, their amplitude and number remain roughly constant throughout the flowing. At critical condition, no secondary flow was observed in the vicinity of the front region where the unstable flow develops. Transient response of the normal stress difference and the shear stress in the plate-and-plate geometry at shear rate above critical (for the elastic fingering instability in the Hele-Shaw cell) did not reveal any anomalous that could lead to the formation of such finger-like instabilities. These instabilities were observed for both the ideal elastic Boger fluids and shear thinning viscoelastic fluids.     

Orthogonal superposition of small and large amplitude oscillations upon steady shear flow of polymer fluids

The orthogonal superposition of small and large amplitude oscillations upon steady shear flow of elastic fluids has been considered. Theoretical results, obtained by numerical methods, are based on the Leonov viscoelastic constitutive equation. Steady-state components, amplitudes and phase angles of the oscillatory components of the shear stress, the first and second normal stress differences as functions of shear rate, deformation amplitude and frequency have been calculated. These oscillatory components include the first and third harmonic of the shear stresses and the second harmonic of the normal stresses. In the case of small amplitude superposition, the effect of the steady shear flow upon the frequency-dependent storage modulus and dynamic viscosity has been determined and compared with experimental data available in literature for polymeric solutions. The predicted results have been found to be in fair agreement with the experimental data at low shear rates and only in qualitative agreement at high shear rates and low frequencies. A comparison of the present theoretical results has also been made with the predictions of other theories.In the case of large amplitude superposition, the effect of oscillations upon the steady shear flow characteristics has been determined, indicating that the orthogonal superposition has less influence on the steady state shear stresses and the first difference of normal stresses than the parallel superposition. However, in the orthogonal superposition a more pronounced influence has been observed for the second difference of normal stresses.     

Rheology and flow-birefringence from viscoelastic polymer-clay solutions

 The shear orientation of viscoelastic clay-polymer solutions was investigated by means of rheology and flow birefringence (Δn). The polymer chains are in dynamic adsorption/desorption equilibrium with the clay particles to form a “network”. The elastic behavior of the network was characterized by constant stress, oscillatory shear, and stress relaxation experiments. Constant stress experiments indicated a yield stress upon which shear flow started and no strain recovery could be observed. Oscillatory shear experiments showed a broad elastic region followed by flow when a critical strain was reached. Stress relaxation experiments showed several relaxation times when the same critical strain was reached. Experiments under steady flow characterized the transient behavior of the network. With increasing steady shear rate a pronounced minimum in birefringence was observed at a critical shear rate. The shear rate dependent viscosity showed near power law behavior and no corresponding critical feature. While birefringence detects orientational effects on a microscopic length scale, rheology averages over macroscopic changes in the sample. The same degree of orientation could be achieved under constant shear rate or constant stress conditions. Received: 25 January 2001 Accepted: 22 May 2001     

Nonlinear viscoelasticity of PP/PS/SEBS blends

The nonlinear viscoelastic behavior of polypropylene/polystyrene (PP/PS) blends compatibilized or not with the linear triblock copolymer (styrene-ethylene-/butylene-styrene, SEBS) was investigated. Start-up of steady-shear at rates from 0.1 to 10 s^–1 was carried out using a controlled strain rotational rheometer and a sliding plate rheometer for strain histories involving one or several shear rates. The shear stress and first normal shear stress difference were measured as functions of time, and the morphologies of the samples before and after shearing were determined. For each strain history except that involving a single shear rate of 0.1 s^–1 the blends showed typical non-linear viscoelastic behavior: a shear stress overshoot/undershoot, depending on the history, followed by a steady state for each step. The first normal stress difference increased monotonically to a steady-state value. The values of the stresses increased with the addition of SEBS. The shear stress overshoot and undershoot and the times at which they occurred depended strongly on the strain history, decreasing for a subsequent shear rate step performed in the same direction as the former, and the time at which stress undershoot occurred increased for a subsequent shear rate step performed in the opposite direction, irrespective of the magnitude of the shear rate. This behavior was observed for all the blends studied. The time of overshoot in a single-step shear rate experiment is inversely proportional to the shear rate, and the steady-state value of N₁ scaled linearly with shear rate, whereas the steady-state shear stress did not. The average diameter of the dispersed phase decreased for all strain histories when the blend was not compatibilized. When the blend was compatibilized, the average diameter of the dispersed phase changed only during the stronger flows. Experimental data were compared with the predictions of a model formulated using ideas of Doi and Ohta (1991), Lacroix et al. (1998) and Bousmina et al. (2001). The model correctly predicted the behavior of the uncompatibilized blends for single-step shear rates but not that of the compatibilized blends, nor did it predict morphologies after shearing.     

Nonlinear shear creep and constrained elastic recovery of a LDPE melt

Summary Shear creep and constrained elastic recovery experiments on a well characterized low-density polyethylene melt are reported. The temperature dependence of the shear strain and the primary normal stress difference is discussed in detail. Comparison is made with predictions of a strain-dependent single integral constitutive equation, which has already been successfully used for the same polymer melt to describe the stress growth after sudden imposition of a constant shear rate flow and stress relaxation after cessation of steady shear flow. It should be emphasized that this constitutive equation contains no adjustable parameters. The linear-viscoelastic part of the memory function is related to the linear-viscoelastic relaxation spectrum, while the nonlinear, strain-dependent part was determined from rapid-strain experiments.In the case of a prescribed shear stress history the resulting integral equation cannot be solved by closed integration but has to be inverted by numerical methods. Agreement between theoretical predictions and experimental data is rather encouraging for shear strain and primary normal stress difference during creep and retardation tests. Within experimental error, the strain and shear rate dependence of the recoverable portion of the total strain can be correctly predicted.

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Zusammenfassung Es wird über Kriech- und Retardationsversuche an einer bekannten Polyäthylen-Schmelze niedriger Dichte berichtet, die mit Hilfe eines Weissenberg-Rheogoniometers durchgeführt wurden. Die Temperaturabhängigkeit der Scherdeformation und der 1. Normalspannungsdifferenz wird diskutiert. Die Ergebnisse der Messungen werden mit den Voraussagen einer rheologischen Zustandsgleichung in Integralform verglichen, die, wie bereits früher für die gleiche Schmelze gezeigt wurde, das Anlaufverhalten beim Anlegen einer konstanten Schergeschwindigkeit und das Relaxationsverhalten nach Beendigung einer stationären Scherströmung richtig beschreibt. Dabei muß betont werden, daß diese Zustandsgleichung keine anpassungsfähigen Parameter enthält. Der linear-viskoelastische Teil der Gedächtnisfunktion hängt mit dem linear-viskoelastischen Relaxationsspektrum zusammen, während der nicht-lineare, deformationsabhängige Teil mit Hilfe von rapid-strain-Experimenten bestimmt wurde.Schreibt man, wie bei Kriech- und Retardationsexperimenten, die Spannungsgeschichte vor, so kann die Zustandsgleichung nicht geschlossen gelöst werden, sondern muß mit numerischen Methoden invertiert werden. Die Übereinstimmung zwischen den berechneten und den gemessenen Werten der Scherdeformation und der 1. Normalspannungsdifferenz bei Kriech- und Erholungsversuchen ist recht zufriedenstellend. Innerhalb der experimentellen Fehlergrenzen läßt sich auch die Abhängigkeit der reversiblen Scherung von der Scherdeformation und der Schergeschwindigkeit berechnen.

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With 5 figures and 4 tables     

Numerical simulations of Boger fluids through different contraction configurations for the development of a measuring system for extensional viscosity

This paper reports the flow behaviour of Newtonian and Boger fluids through various axisymmetric contraction configurations by means of numerical predictions. A principal aim has been to evaluate the geometrical design choice of the hyperbolic contraction flow. The FENE-CR model has been used to reflect the behaviour of Boger fluids, with constant shear viscosity, finite (yet large) extensional viscosity and less than quadratic first normal stress difference. Numerical calculations have been performed on six different contraction configurations to evaluate an optimized geometry for measuring extensional viscosity in uniaxial extensional flow. The influence of a sharp or rounded recess-corner on the nozzle has also been investigated. Few commercial measuring systems are currently available for measurement of the extensional rheology of medium-viscosity fluids, such as foods and other biological systems. In this context, a technique based on the hyperbolic contraction flow would be a suitable alternative. The pressure drop, the velocity field, the first normal stress difference and the strain rate across the geometry have each been evaluated for Newtonian and Boger fluids. This numerical study has shown that the hyperbolic configuration is superior to the other geometry choices in achieving a constant extension rate. In this hyperbolic configuration, no vortices are formed, the measuring range is broader and the strain rate is constant throughout the geometric domain, unlike in the alternative configurations tested. The difference between sharp and rounded recess-corner configurations proved to be negligible and a rise in excess pressure drop (epd) for increasing deformation rates has been observed.     

Melt shear rheology of carbon nanofiber/polystyrene composites

The rheological behavior and morphology of carbon nanofiber/polystyrene (CNF/PS) composites in their melt phase have been characterized both through experimental measurements and modeling. Composites prepared in the two different processes of solvent casting and melt blending are contrasted; melt-blended and solvent-cast composites were each prepared with CNF loadings of 2, 5, and 10 wt%. A morphological study revealed that the melt blending process results in composites with shorter CNFs than in the solvent-cast composites, due to damage caused by the higher stresses the CNFs encounter in melt blending, and that both processes retain the diameter of the as-received CNFs. The addition of carbon nanofiber to the polystyrene through either melt blending or solvent casting increases the linear viscoelastic moduli, G′ and G″, and steady-state viscosity, η, in the melt phase monotonically with CNF concentration, more so in solvent cast composites with their longer CNFs. The melt phase of solvent-cast composites with higher CNF concentrations exhibit a plateau of the elastic modulus, G′, at low frequencies, an apparent yield stress, and large first normal stress difference, N ₁, at low strain rates, which can be attributed to contact-based network nanostructure formed by the long CNFs. A nanostructurally-based model for CNF/PS composites in their melt phase is presented which considers the composite system as rigid rods in a viscoelastic fluid matrix. Except for two coupling parameters, all material constants in the model for the composite systems are deduced from morphological and shear flow measurements of its separate nanofiber and polymer melt constituents of the composite. These two coupling parameters are polymer–fiber interaction parameter, σ, and interfiber interaction parameter, C _I. Through comparison with our experimental measurements of the composite systems, we deduce that σ is effectively 1 (corresponding to no polymer–fiber interaction) for all CNF/PS nanocomposites studied. The dependence of CNF orientation on strain rate which we observe in our experiments is captured in the model by considering the interfiber interaction parameter, C _I, as a function of strain rate. Applied to shear flows, the model predicts the melt-phase, steady-state viscosities, and normal stress differences of the CNF/PS composites as functions of shear rate, polymer matrix properties, fiber length, and mass concentration consistent with our experimental measurements.     

Shear viscosity of slightly-elastic concentrated suspensions at low and high shear rates

A quasi-static asymptotic analysis is employed to investigate the elastic effects of fluids on the shear viscosity of highly concentrated suspensions at low and high shear rates. First a brief discussion is presented on the difference between a quasi-static analysis and the periodic-dynamic approach. The critical point is based on the different order-of-contact time between particles. By considering the motions between a particle withN near contact point particles in a two-dimensional “cell” structure and incorporating the concept of shear-dependent maximum packing fraction reveals the structural evolution of the suspension under shear and a newly asymptotic framework is devised. In order to separate the influence of different elastic mechanisms, the second-order Rivlin-Ericksen fluid assumption for describing normal-stress coefficients at low shear rates and Harnoy's constitutive equation for accounting for the stress relaxation mechanism at high shear rates are employed. The derived formulation shows that the relative shear viscosity is characterized by a recoverable shear strain,S _R at low shear rates if the second normal-stress difference can be neglected, and Deborah number,De, at high shear rates. The predicted values of the viscosities increase withS _R , but decrease withDe. The role ofS _R in the matrix is more pronounced than that ofDe. These tendencies are significant when the maximum packing fraction is considered to be shear-dependent. The results are consistent with that of Frankel and Acrivos in the case of a Newtonian suspension, except for when the different divergent threshhold is given as [1 ? (Φ/Φ _m )^1/2] ? 1.     

On the relaxation of shear and normal stresses of viscoelastic fluids following constant shear rate experiments

By means of a cone and plate rheometer the relaxation of the shear stress and the first normal stress difference in polymer liquids upon cessation of a constant shear rate were examined. The experiments were conducted mostly in a high shear rate region of relevance for the processing of these materials. The relaxation behavior at these shear rates can only be measured accurately under extremely precise specifications of the rheometer. To determine under which conditions the integral normal thrust is a convenient measure for the relaxing local first normal stress difference the radial distribution of the pressure in the shear gap was measured. The shape of relaxation of both the shear stress and the first normal stress difference could be closely approximated for the entire measured shear rate and time range by a two parameter statistical function. In the range of measured shear rates, one of the parameters, the standard deviationS, is equal for the shear and the normal stress, and is independent of the shear rate within the limit of experimental error. The second parameter, the mean relaxation timet _50, of the shear stress andt _50, of the first normal stress difference, can be calculated approximately from the viscosity function and only a single relaxation experiment.     

The normal stress behaviour of suspensions with viscoelastic matrix fluids

 We investigate the variations in the shear stress and the first and second normal stress differences of suspensions formulated with viscoelastic fluids as the suspending medium. The test materials comprise two different silicone oils for the matrix fluids and glass spheres of two different mean diameters spanning a range of volume fractions between 5 and 25%. In agreement with previous investigations, the shear stress–shear rate functions of the viscoelastic suspensions were found to be of the same form as the viscometric functions of their matrix fluids, but progressively shifted along the shear rate axis to lower shear rates with increasing solid fraction. The normal stress differences in all of the suspensions examined can be conveniently represented as functions of the shear stress in the fluid. When plotted in this form, the first normal stress difference, as measured with a cone and plate rheometer, is positive in magnitude but strongly decreases with increasing solid fraction. The contributions of the first and the second normal stress differences are separated by using normal force measurements with parallel plate fixtures in conjunction with the cone-and-plate observations. In this way it is possible for the first time to quantify successfully the variations in the second normal stress difference of viscoelastic suspensions for solid fractions of up to 25 vol.%. In contrast to measurements of the first normal stress difference, the second normal stress difference is negative with a magnitude that increases with increasing solid content. The changes in the first and second normal stress differences are also strongly correlated to each other: The relative increase in the second normal stress difference is equal to the relative decrease of the first normal stress difference at the same solid fraction. The variations of the first as well as of the second normal stress difference are represented by power law functions of the shear stress with an unique power law exponent that is independent of the solid fraction. The well known edge effects that arise in cone-and-plate as well as parallel-plate rheometry and limit the accessible measuring range in highly viscoelastic materials to low shear rates could be partially suppressed by utilizing a custom- designed guard-ring arrangement. A procedure to correct the guard-ring influence on torque and normal force measurements is also presented. Received: 20 December 2000 Accepted: 7 May 2001     

An experimental test of equations predicting the load bearing capacity of squeeze films of elastico-viscous liquid

A form of squeeze film apparatus was recently described in which the movement of one plate towards the other was simulated by the continuous volume generation of liquid over the plate area. The liquid exuded from a large number of holes in the lower plate surface and formed a “continous flow” version of squeeze film apparatus with no moving parts [1]. A later paper gave derivations of equations from which squeeze film load bearing capacity could be evaluated, taking into account viscous, inertial and normal stress effects in the liquid film [2].In order to find the total load in a squeeze film system, it was necessary to obtain the relationship between the first normal stress difference and shear rate for the liquid in use, using an experimental method. At high shear rates, the jet thrust method provided these data [3,4] and from them the load bearing capacity of squeeze films of hot, polymer-thickened oil were predicted [2].A more complete test of the method is possible with a highly elastic liquid because considerable load enhancement due to extra stress is present at moderate deformation rates in squeeze film systems [1,5,6,7]. Thus a 0.1 per cent aqueous polyacrylamide solution gives well-defined load enhancement and (quite independently) the jet thrust method gives the relationship between normal stress and shear rate from which predictions of load enhancement may be made. Furthermore, convergent nozzles may be used in the jet thrust apparatus [3] to measure the stress development in an elastic liquid which is being simulateneously sheared and stretched, a situation which more closely resembles the squeeze film case than that of steady shear.     

The effect of pre-shear on the extensional rheology of wormlike micelle solutions

The effect of initial microstructural deformation, alignment, and morphology on the response of wormlike micelle solutions in transient uniaxial extensional flows is investigated using a pre-shear device attached to a filament stretching rheometer. In filament stretching experiments, increasing the strength and the duration of the pre-shear just before stretch is found to delay the onset of strain hardening. In these experiments, the wormlike micelle solution filaments fail through a rupture near the axial midplane. The value of the elastic tensile stress at rupture is found to decrease with increasing pre-shear rate and duration. The most dramatic effects are observed at shear rates for which shear banding has been independently observed. The reduction in the strain hardening suggests that pre-shear before filament stretching might break down the wormlike micelles reducing their size before stretch. Strain hardening is also observed in capillary breakup rheometry experiments; however, the pre-sheared wormlike micelle solutions strain harden faster, achieve larger steady-state extensional viscosities and an increase in the extensional relaxation time with increasing shear rate and duration. The difference between the response of the wormlike micelles in filament stretching and capillary breakup experiments demonstrates the sensitivity of these self-assembling micelle networks to pre-conditioning.     

Torsional-impact apparatus

A torsional-impact machine has been developed to investigate the dynamic behavior of metals at large strains and high strain rates. Two machines are described; the first was used to continuously monitor stress, strain profile and temperature profile during deformation; the second was designed specifically to investigate the thermal-instability strain. In both machines, the use of a shear pin made independent control of the ultimate strain possible, permitting essentially constant strain rate throughout the test. Shear-strain rates of up to 2300/sec and ultimate shear strains of up to 400 percent were obtained on machine No. 1. Some experimental results are presented to indicate the type of data obtained and the error limits on measurements.     

电磁加载下7075铝环的膨胀断裂模式转变研究

利用电磁膨胀环实验技术,研究了7075铝环在2700～8700 s?1拉伸加载应变率下的断裂模式转变现象。实验结果表明:在低应变率下,铝环的断裂受最大正应力控制,发生拉伸断裂;在高应变率下,铝环的断裂受最大剪应力控制,发生剪切断裂;在中应变率下,铝环的断裂同时受最大正应力和最大剪应力控制,为拉伸和剪切同时存在的拉剪混合断裂模式;随着应变率的增加,铝环的破片数量呈先增加、再减小、最后增加的趋势,破片数量变化拐点与断裂模式转变点基本吻合。     

Fingerprinting the processing behavior of polyethylenes from transient extensional flow and peel experiments in the melt state

The flow curves of linear (linear-low and high density) and branched polyethylenes are known to differ significantly. At increasing shear rates, the linear polymers exhibit a surface melt fracture or sharkskin region that is followed by an unstable oscillating or stick-slip flow regime when a constant piston speed capillary rheometer is used. At even higher shear rates, gross melt fracture appears. Unlike their linear counterparts, branched polyethylenes rarely exhibit sharkskin melt fracture and although gross melt fracture appears at high shear rates there is no discontinuity in their flow curve. The various flow regimes of these two types of polyethylenes are examined by performing experiments in the melt state using a unique extensional rheometer (the SER by Xpansion Instruments) that is capable of performing accurate extensional flow and peel experiments at very high rates not previously realized. The peel strength curves of these linear and branched polyethylenes exhibit all of the distinct flow regimes exhibited in their respective flow curves, thereby providing a fingerprint of their melt flow behavior. Moreover, these extensional flow and peel results in the melt state provide insight into the origins and mechanisms by which these melt flow phenomena may occur with regard to rapid tensile stress growth, melt rupture, and adhesive failure at the polymer wall interface.