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Journal of Rheology

Volume 41, Issue 6 (November-December 1997)


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Contents

NMR Visualisation of Anomalous Flow in Cone-and-Plate Rheometry
Melanie M. Britton and Paul T. Callaghan
A Model of Adaptive Links in Nonlinear Viscoelasticity
Aleksey D. Drozdov
Simulating Complex Flows of Liquid Crystalline Polymers Using the Doi Theory
J. Feng and L.G. Leal
Dynamic Viscosity of Macroscopic Suspensions of Bimodal Sized Solid Spheres
Philippe Gondret and Luc Petit
Interfacial Phenomena in the Capillary Extrusion of Metallocene Polyethylenes
Savvas G. Hatzikiriakos, Igor B. Kazatchkov, and Dimitris Vlassopoulos
Shear Induced Textures of Thermotropic Acetoxypropylcellulose
J.B. Riti, M.T. Cidade, M.H. Godinho, A.F. Martins, and P. Navard
Testing the Structure of Magnetic Paints With and Without Superimposed Shear
Andrei A. Potanin, Suresh M. Shrauti, David W. Arnold, Alan M. Lane, and Jorrit Mellema
Direct Measurement of Adhesion between Viscoelastic Polymers: A Contact Mechanical Approach
Afshin Falsafi, Pascal Deprez, Frank S. Bates, and Matthew Tirrell
A Viscoelastic Model for Dense Granular Flows
D.Z. Zhang and R.M. Rauenzahn

NMR Visualisation of Anomalous Flow in Cone-and-Plate Rheometry

Melanie M. Britton and Paul T. Callaghan
Department of Physics, Massey University
Palmerston North, New Zealand

Abstract

We demonstrate the use of NMR microscopy to image the velocity distribution for fluids sheared within the gaps (4º and 7º) of cone-and-plate rheometers. These measurements employ a specially-constructed rheogoniometer which fits within the NMR probe system. While the uniform shear rate assumption is verified in the case of simple Newtonian and non-Newtonian fluids, a range of anomalous behaviour (apparent slip, shear-banding and fracture) is observed in other systems, including wormlike surfactants, semi-dilute solutions of 18 MDa polyacrylamide, and dispersed silica in silicone grease.

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A Model of Adaptive Links in Nonlinear Viscoelasticity

Aleksey D. Drozdov
Institute for Industrial Mathematics
Ben-Gurion University of the Negev
22 Ha-Histadrut Street
Be'ersheba, 84213 Israel

Abstract

A new constitutive model is derived for the nonlinear viscoelastic behavior of polymers which do not possess the separability property. The model is based on the concept of adaptive links (a version of the theory of transient networks). It is assumed that the response of a link is essentially nonlinear, and the rates of breakage and reformation depend on the strain intensity. With reference to the Eyring concept of thermally activated processes, a new equation is proposed to describe the effect of strains on reformation of adaptive links. Adjustable parameters of the model are found by using experimental data for polycarbonate and an epoxy glass in the standard relaxation tests. Comparison of experimental data in dynamic tests with results of numerical simulation shows that the model correctly predicts the nonlinear viscoelastic response.

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Simulating Complex Flows of Liquid Crystalline Polymers Using the Doi Theory

J. Feng and L.G. Leal
Department of Chemical Engineering
University of California - Santa Barbara
Santa Barbara, CA 93106-5080, USA

Abstract

We simulate the startup flow of lyotropic liquid crystalline polymers (LCPs) in an eccentric cylinder geometry. The objectives are to explore the mechanisms for the generation of disclinations in a non-homogeneous flow and to study the coupling between the flow and the polymer configuration. The Doi theory, generalized to spatially varying flows and approximated by the quadratic closure, is used to model the evolution of LCP configurations. This, along with the equations of motion for the fluid, is solved by a finite element method. The flow modification by the polymer stress is mild for the parameters used, but the LCP exhibits complex orientational behavior in different regions of the flow domain. For relatively weak nematic strength, a steady state is reached in which the director is oriented either along or transverse to the streamline depending upon local flow conditions and the deformation history. A pair of disclinations, with strength ±1/2, are identified in the steady state and the LCP configuration at the disclinations confirms the model of a structured defect core proposed by Greco & Marrucci (1992). For strong nematic strength, director tumbling occurs in the more rotational regions of the flow field, giving rise to a polydomain structure. The boundary of the tumbling domain consists of two disclinations of ±1/2 strength, a structure very similar to previous experimental observations of LCP domains.

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Dynamic Viscosity of Macroscopic Suspensions of Bimodal Sized Solid Spheres

Philippe Gondret*
Laboratoire Fluides, Automatique et Systèmes Thermiques - URA 871 du CNRS
Universités Paris-Sud et P. & M. Curie, Bât. 502, Campus Universitaire
F-91405 Orsay Cedex, France

Luc Petit
Laboratoire de Physique de la Matière Condensée - UMR 6622 du CNRS
Université de Nice, Parc Valrose
F-06108 Nice Cedex 2, France

*Corresponding author

Abstract

In this paper, we present experimental measurements for the dynamic viscosity of macroscopic (non-Brownian and non-colloidal) suspensions of bimodal sized spheres when submitted to an oscillating plane Couette flow. The measured viscosity is what we call the dynamic viscosity at finite frequency. Concerning the viscosity of such systems, numerous experimental studies have been done under steady flow conditions, i.e., at zero frequency, but few ones concern the dynamic case. Our measurements have been performed for different values of the three relevant parameters, namely the size ratio l, the fraction x of small spheres to total solids and the total solid volume fraction F. Our results show a viscosity reduction upon mixing which increases as the total solid volume fraction F is increased. We analyze our results by a model that takes into account the volume fraction F and the maximum volume fraction Fm, which depends itself on the two parameters l and x. On the other hand, we compare our experimental results with recent numerical simulations performed by Chang and Powell (1993, 1994a) by Stokesian dynamics and Monte Carlo method, which lead respectively to viscosity at zero and infinite frequency. Our experimental results lie between these two different simulation results.

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Interfacial Phenomena in the Capillary Extrusion of Metallocene Polyethylenes

Savvas G. Hatzikiriakos* and Igor B. Kazatchkov
Department of Chemical Engineering
The University of British Columbia
Vancouver, B.C., Canada

Dimitris Vlassopoulos
Institute of Electronic Structure and Laser
Foundation of Research and Technology Hellas
Heraklion, Crete, Greece

*Corresponding author

Abstract

Metallocene catalysts are known to produce homogeneous random polyolefin copolymers with narrow molecular weight distribution and controlled long/short chain branching. Two such linear low-density polyethylenes were studied by using both constant stress and capillary rheometry, in order to assess their rheological and processing behaviour, as well as to identify critical conditions for the onset of flow instabilities. It was found that these polymers are thermorheologically complex liquids, apparently due to the presence of long chain branching. Compared with conventional linear low-density polyethylenes, these metallocene polyethylenes exhibit quite unusual behaviour in capillary flow, not previously reported to our knowledge. Specifically, we have encountered long transients in start-up of capillary experiments, and in some cases the capillary reservoir had to be loaded several times before a steady-state pressure was obtained. In addition, we found that these polymers slip at shear stresses higher than about 0.05 MPa. This critical value is much smaller than the critical value of 0.10 MPa reported for other conventional polyethylenes. A simple qualitative model is proposed to rationalise these findings. It suggests that the molecular mechanism of slip is dominated by a competition between flow-induced chain detachment from the wall and disentanglement of the chains in the bulk from those attached to the wall.

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Shear Induced Textures of Thermotropic Acetoxypropylcellulose

J.B. Ritil, M.T. Cidade2, M.H. Godinho2, A.F. Martins2, and P. Navardl*

l
Ecole des Mines de Paris, Centre de Mise en Forme des Matériaux,
URA CNRS 1374, BP 207, F-06904 Sophia Antipolis Cedex, France

2
Departamento de Ciência dos Materiais, Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, 2825 Monte de Caparica, Portugal

*To whom correspondence should be addressed.

Abstract

Acetoxypropylcellulose is a thermotropic cellulose derivative which is cholesteric from below room temperature up to 170ºC. Its textures during and after shear flow were studied by optical microscopy and SALS light scattering. The main features are similar to those occurring in hydroxypropylcellulose solutions, i.e. a polydomain texture evolving into a striated texture, as seen by optical microscopy. Elliptical or else four lobes with a streak are seen in the SALS patterns. Defects appearing as short dark lines not aligned with the flow direction are shown to be responsible for the existence of the four lobes of the SALS patterns. In addition these defects seem to be the location where the band texture which develops during relaxation.

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Testing the Structure of Magnetic Paints With and Without Superimposed Shear

Andrei A. Potanin*, Suresh M. Shrauti, David W. Arnold, Alan M. Lane
Center for Materials for Information Technology
The University of Alabama, Tuscaloosa, AL 35487

Jorrit Mellema
Rheology Group, Twente University
7500AE, Enschede, The Netherlands

*Current address: Quantegy Inc., P.O. Box 190, 2230 Marvyn Parkway, Opelika, AL 36803-0190

Abstract

The structure development in dispersions of magnetic barium ferrite particles in cyclohexanone with PVC wetting resin was tested by oscillatory rheological measurements and orthogonal superposition of steady and oscillatory shear. The optimum dispersion is achieved at the resin concentration c = c0, which corresponds to a minimum in the viscoelastic modulii. At c < c0 the system is highly elastic, brittle (G' drops sharply and G" goes through a strong maximum at high strain), thixotropic and its relaxation spectrum, H(t), is dominated by long relaxation times, t, which indicates the existence of a strong network. At c > c0 the system becomes less elastic, more flexible, less thixotropic and H(t) is dominated by short t, which indicates that the structure formation in this case is dominated by small aggregates rather than a network. By superimposing steady and oscillatory shear we show that the steady shear dramatically break the structure and shifts H(t) to very short t.

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Direct Measurement of Adhesion between Viscoelastic Polymers: A Contact Mechanical Approach

Afshin Falsafi, Pascal Deprez, Frank S. Bates, and Matthew Tirrell*
Department of Chemical Engineering and Materials Science
University of Minnesota, Minneapolis, Minnesota 55455

*To whom correspondence should be addressed

Abstract

We have measured the surface energies of several viscoelastic polymers, using contact mechanics methods. The materials studied were diblock copolymers of poly(ethylene)-poly(ethylene-propylene) (PE-PEP) having different PE volume fractions and molecular weights. The materials exhibit differing viscoelastic relaxation functions in the bulk. Surface energies were determined from contact mechanics experiments in the loading mode, analyzed by incorporating the bulk viscoelastic effects into the Johnson Kendall-Roberts (JKR) theory of adhesive elastic contacts. The samples were made of spherical caps of the materials formed by first melting, and then cooling to room temperature. The measured values of the surface energies are close to the reported value for that of the surface-active PEP block, based on prior contact angle measurements, indicating that reliable surface energy values can be extracted from contact mechanics experiments, suitably analyzed to account for viscoelastic behavior. We believe that this method may be generalizable to surface and interfacial energy studies of a wide range of viscoelastic polymers.

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A Viscoelastic Model for Dense Granular Flows

D.Z. Zhang and R.M. Rauenzahn
Los Alamos National Laboratory
Theoretical Division, Fluid Dynamics Group
T-3, B216, Los Alamos, NM 87545

Abstract

In traditional kinetic theory for a granular flow, it is usually assumed that particle interactions are instantaneous and binary. For a dense granular system these assumptions are usually invalid. In this paper, we use an ensemble averaging technique to examine the effects of finite particle interaction time and multi-particle collisions. The main objectives of this paper are to develop a method and to provide a tool to study dense granular materials. As an example, we study flows of granular particles coated with thin layers of resin. To model particle elasticity and resin viscosity, the force between a pair of particles is approximated by a serial connection of a linear spring and a dashpot. Subsequently, a viscoelastic model is developed from the averaging method. In order to determine coefficients in the constitutive model, direct numerical simulations are performed. When the particle concentration is relatively low, the shear stress is quadratically proportional to the shear rate, in agreement with kinetic theories. At a high particle concentration, the shear stress depends linearly on the rate of strain. The transition between this quadratic and linear dependence is similar to a phase transition. In a dense system, when the shear rate exceeds a critical value, shear band formation is also observed.

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