Assessment of nonlinear strain measures for extensional and shearing flows of polymer melts

From stress-strain experiments in extensional and shearing flows, nonlinear strain measures and effective damping functions are derived for a polyisobutylene melt. The strain measures determined in planar extensional flow and in simple shear flow coincide. Experimental results are compared with predictions of two molecular theories, the Doi-Edwards model and the molecular stress function approach of Wagner and Schaeffer. Discrepancies between theories and experiment lead to a reconsideration of the classification of extensional flows. The symmetry of the flow field is identified and quantified as an important parameter influencing the strain measure, and a unifying strain measure for general extensional and shearing flows of polymer melts is presented.     

Rheology of rodlike polymers in the nematic phase with tumbling or shear orientation

The theory of rodlike polymers in the nematic phase is now sufficiently well developed as to allow predictions of the rheological behaviour that qualitatively compare well with the experimental observations. One of the main results of the theory is the prediction that rodlike polymers are nematics of the tumbling type at low shear rates, whereas they become shear oriented at high rates: a nonlinear effect, which is absent in low molecular weight nematics. This aspect is here reviewed in an effort to highlight the intuitive aspects of the matter. First, the low shear-rate situation is discussed in order to investigate the conditions that determine the existence of a stationary solution as opposed to a periodic one (tumbling). Then, the high shear-rate range is considered, where the shear-oriented situation prevails under all conditions. The intermediate range of shear rates is the most interesting one for its peculiar rheological behavior.Delivered as a Keynote Lecture at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.     

Some tests of constitutive equations for entangled polymers based on planar-extension flow histories in a periodically constricted channel

Stress and velocity were determined locally by birefringence measurements and laser Doppler velocimetry for a mildly entangled polystyrene solution flowing at steady state in a rectangular channel with sinusoidally varying wall spacing. Having measured both the velocity and stress fields, we were able to test constitutive equations locally, i.e., without solving the equations of motion for the entire flow. Four were examined for the periodic planar extensions on the channel centerplane: the Newtonian model, the Lodge network model, the Doi-Edwards tube model, and the Wagner-Schaeffer modification of Doi-Edwards. High enough Weissenberg and Deborah numbers were reached to produce sizable departures from the Newtonian predictions. The Doi-Edwards model underpredicted the stress, as did Wagner-Schaeffer, although to a lesser extent. Predictions of the Lodge model were best of all, a surprising result in view of its inadequacy for simple shear deformations. The predictions of the Lodge model, without parameter adjustment, agreed remarkably well with the planar extension data over the accessible range for our apparatus: Deborah numbers up to 2.0, extensional Weissenberg numbers up to 6.5, and a maximum extension ratio of about 2.3.     

Relaxation dynamics of selected polymer chain segments and comparison with theoretical models

Simultaneous measurement of infrared dichroism and birefringence is used to study selected polymer segment dynamics in isotopically labeled block copolymers. Two different polymers were studied: polybutadiene and poly (ethylene propylene). The first type consisted of a triblock with a short middle block labeled and a diblock with a short end block labeled, while the second type consisted of a triblock with three equal blocks and the end blocks labeled. Results of step strain experiments at –10°C for polybutadiene and at room temperature for poly(ethylene propylene) indicated that segments located at chain ends relax faster than segments located at chain centers. These experimental data were compared to the predictions of two molecular models: the bead-spring model of Rouse and the tube model of Doi and Edwards, and it was found that both models correctly predict the qualitative features of segmental relaxation. However, the tube-model predictions were closer to the experimental results. In addition, when the effects of orientational coupling interactions between segments in the melt were incorporated into this model, its predictions quantitatively agreed with the experimental results. The orientational coupling coefficient for poly(ethylene propylene) was 0.45 as measured from previous work, and for polybutadiene it was found to be 0.4.Delivered as a Keynote Lecture at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.Dedicated to Prof. R.S. Stein, University of Massachussets at Amherst, USA, on the occasion of his 65th birthday.     

An outline of the non-linear viscoelastic behaviour of wheat flour dough in shear

Creep and creep recovery, stress relaxation and small- and large-amplitude oscillatory shear experiments have been used to study the steady-state flow behaviour and the transient viscoelastic response of wheat flour dough in shear over large ranges of time, stress and strain. The results are discussed with reference to the limited body of reliable literature data. Dough does display a linear viscoelastic domain. The complex character of its non-linear viscoelastic properties is essentially due to the extremely low shear rate limit of the initial Newtonian plateau and to the onset of time-dependent flow behaviour above a certain strain threshold, which explain qualitatively the discrepancies observed in certain cases on a part of the range of the rheological variables explored, despite global self-consistency of the results. Comparison of gluten and dough linear viscoelastic properties shows that dough cannot be viewed simply as a concentrated suspension of starch granules in the hydrated viscoelastic gluten matrix.Paper presented at the second Annual European Rheology Conference (AERC 2005) held in Grenoble, France on April 21–23, 2005.     

Elastic properties of polyethylene melts at high shear rates with respect to extrusion

At high shear rates a steady state of shear flow with constant shear rate, constant shear stress, and constant recoverable shear strain is observed in the short-time sandwich rheometer after some few shear units already. The melt exhibits rather high elastic shear deformations and the recovery occurs at much higher speed than it is observed in the newtonian range. The ratio of first normal stress difference and twice the shear stress, being equal to the recoverable strain in the second-order fluid limit, significantly underestimates the true elastic shear strains at high shear rates. The observed shear rate dependence of shear stress and first normal stress difference as well as of the (constrained) elastic shear strain is correctly described on the basis of a discrete relaxation time spectrum. In simple shear a stick-slip transition at the metal walls is found. Necessary for the onset of slip is a critical value of shear stress and a certain amount of elastic shear deformation or orientation of the melt.     

A microstructural investigation of the nonlinear response of electrorheological suspensions

In the preceding paper, Part 1, the transition from linear to nonlinear behavior for electrorheological (ER) suspensions under start-up of steady shear flow was found to first arise from the slight rearrangement of unstable structures. In this paper, we investigate the transition to nonlinear behavior for ER suspensions under oscillatory shear flow, focusing on the role of the rearrangement of unstable structures, and employing experimental and simulation results. Again, we find that nonlinear deformation first arises from these rearrangements, as opposed to the gross rearrangement or rupture of particulate chains. The Fourier transform of the simulated time-dependent shear stress is employed to quantify the dependence of the critical strain on the deformation frequency and electric field strength. The predicted behavior is consistent with experimental trends. Methods for verifying the predictions are discussed, as well as possible avenues for exploiting this information in improved operating strategies and improved ER fluids.     

Non-linear rheology of a face-centred cubic phase in a diblock copolymer gel

The viscoelastic behaviour of a poly(oxyethylene)-poly(oxybutylene) diblock copolymer in aqueous solution forming a face-centred cubic (fcc) micellar phase has been investigated using oscillatory shear rheometry. With increasing strain amplitude, the micellar solution was observed to undergo a transition from linear to non-linear behaviour, characterized by strong shear thinning. The non-linear behaviour observed in the stress response was analyzed by Fourier transformation of the waveform. Fourier analysis revealed that the high harmonic contributions to the shear stress response increased with strain amplitude and up to the 81st harmonic was observed for very large amplitudes. The onset of non-linear response as defined from the dependence of isochronal dynamic shear moduli on strain amplitude was found to be in good agreement with that defined by the appearance of a higher harmonic in the stress waveform. The amplitudes of the harmonic coefficients are compared to the predictions of a model for the nonlinear rheological response of a lyotropic cubic mesophase based on the stress response to a periodic lattice potential (Jones and McLeish 1995). It is found that the model is able to account for qualitative trends in the data such as the development of finite higher harmonics with increasing strain, but it does not describe the full frequency and strain dependence of these coefficients. Received: 31 May 2000 Accepted: 21 August 2000     

The prediction of time-dependent non-linear stresses in viscoelastic materials: II. Prediction of shear and uniaxial elongation behaviour

Stress predictions have been made for two materials using the new strain measure developed in Part I. For the startup of steady-shear flow, the predictions show increasing overshoot of shear and normal stresses at increasing shear rates, and both qualitatively and quantitatively there is good agreement with the experimental results for a polymer solution and a melt. The information contained in Part I on the strain measure is found to be insufficient for making exact predictions for flows other than shear flows, but it is shown here that uniaxial elongational flow is sufficiently similar to shear flow for predictions to be made with only a low degree of inaccuracy. Data on the elongational behaviour of the melt are available from the literature and the predictions made here are found to be in satisfactory agreement with the reported behaviour. All of the predictions require as input information only the linear viscoelastic behaviour of the material.     

The reptation model with segmental stretch

The Doi-Edwards model with segmental stretch and a non-linear finitely extensible spring law is described and examined in simple flow situations where analytic results are derivable; namely oscillatory flow and steady state flow at high deformation rates. The model is shown to be consistent with the Bueche-Ferry hypothesis in fast large strain unidirectional flows but to violate this rule in small strain reversing flows. The discrepancy is identified with a preaveraging approximation used to describe the relative tube-chain velocity. Experimentally verifiable scaling rule for the birefringence as a universal function of a planar flow-type parameter and deformation rate are identified. Sensitivity to the extensional flow character, absent in the original tube model, manifests itself with the introduction of segmental stretch. Although the model generates a non-separable memory function kernel the deformation dependence of the memory function is quantitatively shown to have negligible impact on the predicted theological properties relative to the original Doi-Edwards model. With this simplification, relatively uncomplicated approximations to the segmental stretch model can be deduced.     

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     

Anisotropic conduction of heat in a flowing polymeric material

In this paper a theory is presented which relates the thermal conductivity tensor of an amorphous polymeric material to the history of deformation of the material. The basis of the theory is formed by the network theory for polymeric materials. It will be shown that the results obtained here are in good agreement with experimental results on rubber. The effect of anisotropic heat conduction on the flow of a polymeric material will be demonstrated by the simple example of viscous heating in shear flow.Presented at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.     

Comparison of optical and mechanical measurements of second normal stress difference relaxation following step strain

Relaxation of the second normal stress difference (N ₂) following step strain of a concentrated monodisperse polystyrene solution has been studied using mechanical and optical rheometry. Measurements of normal thrust in a parallel plate geometry are corrected for strain inhomogeneity and combined with independent measurements of the first normal stress difference (N ₁) to determine N ₂. Optical experiments were performed using a novel configuration where flow birefringence data collected using multiple light paths within the shear plane are combined with the stress-optical law to determine all three independent stress components for shearing deformations. This technique eliminates end effects, and provides an opportunity to oversample the stress tensor and develop consistency checks of experimental data. N ₂ is found to be nonzero at all accessible times, and relaxes in roughly constant proportion to N ₁. This reflects nonaffine distribution of chain segments, even well within the regime of chain retraction at short times. Data collected with the two techniques are reasonably consistent with each other, and with results of previous studies, generally lying between the predictions of the Doi-Edwards model with and without the independent alignment approximation. The normal stress ratio –N ₂/N ₁ shows pronounced strain thinning in the nonlinear regime.     

Normal stress measurements

A review of the methods for obtaining the normal stress differences in simple shear flow from force measurements on the walls of apparatus in which curvilinear shear flows are generated is given. Indirect methods, for example the flow birefringence method, are considered. Some new work on normal stress measurement using cone and plate, parallel plate pressure distribution and total thrust measurements in conjunction with flow birefringence methods are reviewed. The difficulties found in obtaining consistant results are discussed.Paper presented at the Conference on Experimental Rheology, University of Bradford, April 17–19, 1968. — Original paper published in Rheo. Acta,7, 368 (1968).     

The determination of the first normal stress coefficient of an exopolysaccharide solution by rheo-optical measurements

This paper illustrates how rheo-optical techniques may be utilized to determine the first normal stress coefficient for an exopolysaccharide (EPS) produced by the Lactobacillus delbrueckii ssp. bulgaricus LY03, which is widely used in yoghurt production. In this technique both shear stress, optical birefringence and extinction angle are measured simultaneously as a function of shear rate. From the stress optical rule the first normal stress difference can be determined directly without relying on any specific rheological model. Of special interest is the point where the first normal stress difference become comparable in magnitude to the shear stress. Here we expect to find a notable influence of the first normal stress difference on mouthfeel.This paper was presented at the first Annual European Rheology Conference (AERC) held in Guimarães, Portugal, September 11-13, 2003.     

Dynamic properties of shear thickening colloidal suspensions

The transient shear rheology (i.e., frequency and strain dependence) is compared to the steady rheology for a model colloidal dispersion through the shear thickening transition. Reversible shear thickening is observed and the transition stress compares well to theoretical predictions. Steady and transient shear thickening are observed to occur at the same value of the average stress. The critical strain for shear thickening is found to depend inversely on the frequency at fixed applied stress for low frequencies (high strains), but is limited to an apparent minimum critical strain at higher frequencies. This minimum critical strain is shown to be an artifact of slip. Lissajous plots illustrate the transition in material properties through the shear thickening transition, and the energy dissipated by a shear thickening suspension is analyzed as a function of strain amplitude.     

Shear and extensional flow of polyacrylamide solutions

As part of an EEC Science Stimulation programme on extensional viscosity two major conferences were organised on the subject. The second of these was devoted to the results obtained on a standard fluid, M 1. The data obtained in shear flow was remarkably consistent from laboratory to laboratory. Extensional flow results presented quite a different picture. Using a series of nonequilibrium techniques such as the spinline rheometer, opposing jet, falling drop and converging flow, extensional viscosity results were obtained which differed by as much as two to three orders of magnitude. Nevertheless, it was apparent that consistancy did exist between similar techniques. It is in the context of this information that the measurements described below have been made.The shear and extensional flow properties of partially ionised polyacrylamide in solution at concentrations ranging from 5 ppm were measured. The method of solution preparation was found to have a profound effect on the behaviour of the solutions in shear flow. The influence of salt concentration and pH was investigated and is discussed in the context of molecular shape in solution.Extensional flow measurements, using the spinline rheometer, show that the solutions are strongly strain thickening even at concentrations as low as 5 ppm. These results are considered in the light of polymer entanglement and association in the strong flow field.Delivered as a Keynote Lecture at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.     

Theoretical correlation of linear and non-linear rheological symptoms of long-chain branching in polyethylenes irradiated by electron beam at relatively low doses

Dynamic and transient shear and elongation flow experiments along with gel permeation chromatography (GPC) and differential scanning calorimetry (DSC) analysis are performed on linear low-density polyethylenes (LLDPEs) irradiated at doses below 25 kGy. GPC data indicate no changes in the molar mass distribution, and there are almost no changes in melt and crystallization temperatures, likewise. Contrary, dynamic shear rheological behavior including thermorheological complexity, type of reduced van Gurp-Palmen curves, and zero shear-rate viscosities all disclose growing levels of long-chain branching with irradiation dose. An inverse tube model is developed for binary blend of linear and star chains and used to extract the fraction of the branched components. Modeling results reveal progressive increase in the length and fraction of star chains, as evidenced by appearance of an anomalous double overshoot in the transient shear viscosities. Detection of strain hardening in extensional stress growth coefficient data, well-quantified by molecular stress function model, is also in agreement with the predictions of tube model.     

Viscoelastic plastic rheological model for particle filled polymer melts

A viscoelastic plastic model for suspension of small particles in polymer melts has been developed. In this model, the total stress is assumed to be the sum of stress in the polymer matrix and the filler network. A nonlinear viscoelastic model along with a yield criterion were used to represent the stresses in the polymer matrix and the filler network, respectively. The yield function is defined in terms of differential equations with an internal parameter. The internal parameter models the evolution of structure changes during floc rupture and restoration. The theoretical results were obtained for steady and oscillatory shear flow and compared with experimental data for particle filled thermoplastic melt. The experimental data included the steady state shear strress over a wide range of shear rates, the transient stress in a start up shear flow, stress relaxation after cessation of a steady state shear flow, the step shear and the oscillatory shear flow at various amplitudes.     

Time-dependent Viscoelastic Behavior of an LDPE Melt

Two differential constitutive equations, i.e. Giesekus model and Johnson–Segalman model were employed here to predict the time-dependent viscoelastic behavior of an LDPE melt in thixotropy-loop experiments and step shear rate experiment. Multiple relaxation modes were adopted, and the parameters used to describe the nonlinear viscoelasticity in the two models were obtained by fitting the shear-thinning viscosity. The predictions on those transient shear characteristics by the two models are found in qualitative agreement with our previous experiments. Johnson– Segalman model predicts oscillation behavior in the thixotropy-loop and step shear rate experiments, whereas Giesekus model does not. Both models predict higher shear stresses than the experimental data in the case of long time shearing, implying that both models are not able to completely characterize the time-dependent shear stress of the melt at high shear rate.The project was supported by the National Natural Science Foundation of China (10402024, 50335010).The English text was polished by Yunming Chen.