Showing papers in "Rheologica Acta in 1999"

High Sensitivity Fourier-Transform Rheology

Abstract: The application of oscillatory shear strain leads, in the non-linear regime, to the appearance of higher harmonic contributions in the shear stress response. These contributions can be analyzed as spectra in Fourier space with respect to their frequencies, amplitudes and phase angles. In this article, we present several theoretical and practical aspects of measuring Fourier rheology spectra with high sensitivity. Using the hardware of a conventional rheometer, Fourier rheology spectra with a signal-to-noise ratio of about 18,000:1 for a single acquisition were obtained. This allowed the observation of harmonics up to the 21st harmonic. Signal averaging can further increase the sensitivity.

Magnetorheology in viscoplastic media

Abstract: Suspensions of iron particles in media with yield stresses were investigated to determine the effect of the continuous phase yield stress on the magnetorheological (MR) response. The steady-shear MR response was independent of the continuous phase yield stress for yield stresses in the range 0.9–37 Pa. The field-induced suspension yield stress increased sub-quadratically with the flux density. The small amplitude oscillatory shear response exhibited history dependence. The storage modulus depended not only on the magnitude of the applied magnetic field, but also on its history. This history dependence can be explained in terms of the field-dependent evolution of the suspension microstructure.

Rheology of polymer blends: linear model for viscoelastic emulsions

Abstract: Kerner's model for flow of composite elastic media is extended to an emulsion of viscoelastic phases with interfacial tension undergoing deformations of small amplitude. A privileged internal structure inside the suspended drops is discussed in terms of fluid circulation across the interface. It is shown that for usual drop radius and interfacial tension values of emulsions, the rheological behavior predicted by the model, with very simple expression for the complex shear modulus, is quantitatively similar to that predicted by Palierne's model. Predictions of the model are compared with experimental data obtained on a polystyrene/polyethylene blend sheared in a small-amplitude oscillatory mode.

Non-linear viscoelastic behavior of fumed silica suspensions

Abstract: Suspensions of fumed silica exhibit a wide range of rheological properties depending on the nature and magnitude of the interparticle forces. In a non-polar fluid, the particles interact through hydrogen bonding and can form a three-dimensional network. The microstructure formation is responsible for the non-linear viscoelastic behavior of fumed silica suspensions, even at very small strain. These non-linear rheological properties have been studied in small amplitude oscillatory experiments as a function of particle size, surface treatment of particles, suspending medium polarity and solids concentration. The non-linear viscoelastic behavior is characterized by a non-sinusoidal waveform of the signal response. For suspensions in a non-polar fluid, both the elastic and the loss moduli are shown to be sensitive to the strain amplitude: the elastic modulus is decreasing with increasing strain whereas the loss moduli is initially increasing with strain. We have chosen to examine the dissipated energy which is clearly related to the breakup of the suspension structure. A comparison of model predictions and the experimental data shows the limitations of these models, recently proposed in the literature to describe the behavior of colloidal suspensions.

Rheological properties of gluten plasticized with glycerol: dependence on temperature, glycerol content and mixing conditions

Abstract: The rheological behaviour of a gluten plasticized with glycerol has been studied in oscillatory shear. The mixing operation in a Haake batch mixer leads to a maximum torque for a level of specific energy (500–600 kJ/kg) and temperature (50–60 °C) quite independent of mixing conditions (rotor speed, mixing time, filling ratio). The gluten/glycerol dough behaves as a classical gluten/water dough, with a storage modulus higher than the loss modulus over the frequency range under study. A temperature increase induces a decrease of moduli, but the material is not thermorheologically simple. Glycerol has a plasticizing effect, which can be classically described by an exponential dependence. Mixing conditions influence the viscoelastic properties of the material, mainly through the specific mechanical energy input (to 2000 kJ/kg) and temperature increase (to 80 °C). Above 50 °C, specific mechanical energy highly increases the complex modulus. The aggregation of proteins, as evidenced by size-exclusion chromatography measurements, occurs later as the dough temperature reaches 70 °C. The nature of network interactions and the respective influence of hydrophobic and disulphide contribution is discussed. A general expression is proposed for describing the viscous behaviour of a gluten/glycerol mix, which could seem simplistic for such a complex rheological behaviour, but would remain sufficient for modelling the flow behaviour in a twin screw extruder.

Macroscopic thermodynamics of flowing polymeric liquids

Abstract: The thermodynamics and mechanics of non-isothermal polymeric fluids are examined within the auspices of a new methodology wherein the laws of physics and principles of mechanics which are applicable to these thermodynamic systems are imbedded in a definite mathematical structure of a general, abstract equation. Such a concept allows new insight to be obtained concerning some aspects of non-isothermal flows of polymeric fluids, and permits a consistent expression and interpretation of other thermodynamic theories for these systems which have been developed over the past forty years. A major portion of this article is devoted to demonstrating the above statements, and in so doing some common misconceptions occurring in a significant fraction of the literature regarding this subject are exposed. The definite mathematical structure of the new methodology permits the thermodynamically consistent generalization of isothermal, incompressible models of polymeric fluids to non-isothermal, compressible conditions. Doing thus reproduces, corrects, and extends non-isothermal models which have been developed over the years, and also allows for simpler (but equivalent) representations of these models in terms of alternate variables with a clearer connection to the microstructure of the material than the stress tensor and heat flux vector fields. Furthermore, a generalization of the GENERIC structure is proposed that accommodates interactions between phenomena of differing parities, which impose antisymmetry upon the corresponding elements of the dissipative operator matrix.

Manifestation of phase separation processes in oscillatory shear: droplet-matrix systems versus co-continuous morphologies

Abstract: Phase separation processes in mixtures of poly-α-methylstyrene-co-acrylonitrile (PαMSAN) and poly-methylmethacrylate (PMMA) with lower critical solution temperature (LCST) behavior have been studied, focusing on the manifestation of the interface in oscillatory shear measurements. By using blends of different composition, systems with a droplet-matrix morphology or a co-continuous structure are generated during the phase separation process. The feasibility of probing this morphology development by rheological measurements has been investigated. The development of a disperse droplet phase leads to an increase in the elasticity of the blend at low frequency, showing up as a shoulder in the plot of storage modulus versus frequency. Here, the droplet growth is unaffected by the shear amplitude up to strains of 0.2; therefore the resulting dynamic data are suitable for quantitative analysis. In contrast, for blends in which phase separation leads to a co-continuous structure, the storage modulus shows a power law behavior at low frequency and its value decreases as time proceeds. For the latter systems, effects of the dynamic measurement on the morphology development have been observed, even for strain amplitudes as low as 0.01. To probe the kinetics of morphology evolution in droplet-matrix systems, measurements of the time dependence of the dynamic moduli at fixed frequency should be performed (for a whole series of frequencies). Only from such measurements, curves of the frequency dependence of the moduli at a well defined residence time can be constructed. From fitting these curves to the emulsion model of Palierne, the droplet diameter distribution at that particular stage in the phase separation and growth process can be obtained. It is not appropriate to use a simplified version of the Palierne model containing only the average droplet size, because a morphology with too broad a size distribution is generated.

Edge fracture in cone-plate and parallel plate flows

Abstract: Edge fracture is an instability of cone-plate and parallel plate flows of viscoelastic liquids and suspensions, characterised by the formation of a `crack' or indentation at a critical shear rate on the free surface of the liquid. A study is undertaken of the theoretical, experimental and computational aspects of edge fracture. The Tanner-Keentok theory of edge fracture in second-order liquids is re-examined and is approximately extended to cover the Criminale-Ericksen-Filbey (CEF) model. The second-order theory shows that the stress distribution on the semi-circular crack is not constant, requiring an average to be taken of the stress; this affects the proportionality constant, K in the edge fracture equation −N 2c = KΓ/a, where N 2c is the critical second normal stress difference, Γ is the surface tension coefficient and a is the fracture diameter. When the minimum stress is used, K = 2/3 as found by Tanner and Keentok (1983). Consideration is given to the sources of experimental error, including secondary flow and slip (wall effect). The effect of inertia on edge fracture is derived. A video camera was used to record the inception and development of edge fracture in four viscoelastic liquids and two suspensions. The recorded image was then measured to obtain the fracture diameter. The edge fracture phenomenon was examined to find its dependence on the physical dimensions of the flow (i.e. parallel plate gap or cone angle), on the surface tension coefficient, on the critical shear rate and on the critical second normal stress difference. The critical second normal stress difference was found to depend on the surface tension coefficient and the fracture diameter, as shown by the theory of Tanner and Keentok (1983); however, the experimental data were best fitted by the equation −N 2c = 1.095Γ/a. It was found that edge fracture in viscoelastic liquids depends on the Reynolds number, which is in good agreement with the inertial theory of edge fracture. Edge fracture in lubricating grease and toothpaste is broadly consistent with the CEF model of edge fracture. A finite volume method program was used to simulate the flow of a viscoelastic liquid, obeying the modified Phan-Thien-Tanner model, to obtain the velocity and stress distribution in parallel plate flow in three dimensions. Stress concentrations of the second normal stress difference (N 2) were found in the plane of the crack; the velocity distribution shows a secondary flow tending to aid crack formation if N 2 is negative, and a secondary flow tending to suppress crack formation if N 2 is positive.

The rheological and microstructural characterisation of the non-linear flow behaviour of concentrated oil-in-water emulsions

Abstract: This paper reports experimental observations on the rheology and microstructure of concentrated oil-in-water emulsions stabilised by macromolecular and low-molecular-weight emulsifiers. From the four different samples that were tested, certain general trends were identified and the measured linear viscoelastic and non-linear viscoelastic properties were compared using a phenomenological factored integral constitutive equation with a continuous relaxation spectrum. The self-consistency of the model was quite good in two cases (vegetable protein and polyoxyethylene glycol non-ionic surfactant emulsifiers) with the general exception of low steady shear rate data where the model overpredicted experimental stress measurements. It is shown that the fitting of the experimental data is sensitive to a wide range of inter-relating factors. In addition, optical observations of the sheared materials consistently showed low shear rate surface slip and this observation was correlated with the rheology miss match. For some systems the optical microstructure studies reveal a range of behaviour for the emulsions dependent on emulsifier composition. Wall slip, microdomain movement, chaining and changes in droplet size distribution were all observed under different conditions and in some cases it has been possible to correlate these microstructure observations with the sample rheology.

Creep recovery behavior of metallocene linear low-density polyethylenes

Abstract: The rheological behavior of two metallocene linear low-density polyethylenes (mLLDPE) is investigated in shear creep recovery measurements using a magnetic bearing torsional creep apparatus of high accuracy. The two mLLDPE used are homogeneous with respect to the comonomer distribution. The most interesting feature of the two mLLDPE is that their molecular mass distributions are alike. Therefore, as one of the mLLDPE contains long-chain branches, the influence of long-chain branching on the elastic properties of polyethylene melts could be investigated. It was found that long-chain branches increase the elasticity of the melt characterized by the steady-state recoverable compliance. The long-chain branched mLLDPE has a flow activation energy of 45 kJ/mol which is distinctly higher than that of the other mLLDPE. The shear thinning behavior is much more pronounced for the long-chain branched mLLDPE. A discrepancy between the weight average molecular mass Mw calculated from size exclusion chromatography measurements by the universal calibration method and the zero shear viscosities of the two mLLDPE was observed. These observations are discussed with reference to the molecular architecture of the long-chain branched mLLDPE. The rheological properties of the long-chain branched mLLDPE are compared with those of a classical long-chain branched LDPE. It is surprisingly found that the rheological behavior is very much the same for these two products although their molecular mass distributions and presumedly the branching structures differ largely.

A constitutive theory of fluid saturated granular materials and its application in gravitational flows

Abstract: A continuum theory of fluid-saturated granular materials is presented. The microstructural effects are accounted for by additional balances of equilibrated forces. A set of constitutive equations for a viscous solid-fluid mixture with microstructure is derived by use of the Muller-Liu thermodynamic approach. This theory is applied for the description of the steady gravitational flow of a solid-fluid mixture down an inclined plate. The resulting boundary value problem is solved numerically and results are presented for various values of parameters and boundary conditions. Solutions of this problem demonstrate many of the characteristics normally assumed in the other treatments of solid-fluid mixtures. Typically, in the vicinity of the bottom, a layer of high shear rate occurs with high dilatancy, whose thickness is nearly several grain diameters. Above this layer a plug-like region develops in which the velocity is almost constant.

Shear banding in reaction-diffusion models

Abstract: Shear banding occurs in the flow of complex fluids: various types of shear thinning and shear thickening micelle solutions and liquid crystals. In order to cope with the strongly inhomogeneous interface between the bands, constitutive models used in standard rheology must be supplemented by non-local terms. This leads rather generally to non-linear partial differential equations of the reaction-diffusion type. We use this formalism in order to explain some observed experimental features and as a guide for future research in this field.

Effect of interfacial tension on linear viscoelastic behavior of immiscible polymer blends

Abstract: When interfacial tension is increased from zero to infinity, the storage dynamic modulus predicted by Palierne's model varies in a nearly Gaussian fashion with almost equal asymptotic values at the limits of low and high interfacial tension. We report a simple physical discussion of such an effect.

Diffusion effects on the interfacial tension of immiscible polymer blends

Abstract: Most methods of measuring the interfacial tension between two immiscible polymers are based on the analysis of the shape that a drop of one polymer immersed in the other one exhibits under the action of flow or gravity. In such a situation, the small, yet nonzero mutual solubility between the two polymers acts toward mass transfer between the drop and the surrounding fluid. In this work, diffusion effects on the interfacial tension of the pair polyisobutylene/polydimethylsiloxane have been investigated by drop deformation under shear flow. When the drop was made of polyisobutylene, drop size decreased with time due to diffusion. Drop shrinkage was associated with a significant increase in interfacial tension, until an apparent plateau value was reached. The effect was attributed to a selective migration of molecular weights, which would act to enrich the drop with higher molar mass material. To support such an interpretation, drop viscosity was evaluated by drop shape analysis and it was actually found to increase with time. In some cases, the ratio between drop and continuous phase viscosity became higher than the critical value for drop breakup in shear flow. Upon inverting the phases (i.e., when the drop was made of polydimethylsiloxane), no significant transient effects were observed. In the light of these results, the problem of what are the correct values of interfacial tension and viscosity ratio for a polymer blend of a certain composition will also be discussed.

A new constitutive model for monodispersed suspensions of spheres at high concentrations

Abstract: We describe a constitutive model for monodispersed concentrated suspensions of spheres at high volume fractions. In this model the motion of a pair of generic spheres is represented by that of a pair of force-free and torque-free spheres tumbling along with the flow. The interaction with the surrounding spheres is modelled by an anisotropic diffusion process. Viscometric and elongational properties of the model are obtained by a Brownian dynamic simulation.

Rheo-optical investigations of lyotropic mesophases of polymeric surfactants

Abstract: The shear orientation of hexagonal and lamellar liquid crystalline phases of polymeric surfactants was investigated by rheo-optical techniques (flow birefringence (Δn), small-angle light scattering) as well as by nuclear magnetic resonance and optical microscopy. The evolution of birefringence in the hexagonal phase is discussed for simple and oscillatory shear, and an alignment of rodlike micelles along the flow direction was found. A shear induced formation of vesicles (“onions”) is observed with the lamellar phase. They displayed a characteristic four-lobe pattern in depolarized light scattering. Above a critical shear stress vesicles were degraded and perpendicularly aligned lamellae (i.e. with their normal along the vorticity direction) were obtained. A comparison of experiments performed at constant stress and constant rate revealed that the vesicle to planar lamellae transition occurred above a critical shear stress. The behavior of the polysoap lyotropic mesophases under shear, i.e. the strain dependent alignment in the hexagonal phase, the shear induced formation of vesicles, and a transition to planar lamellae in the lamellar phase, is very similar to the behavior of lyotropic mesophases formed by low molar mass surfactants or amphiphilic block copolymers. The geometrical constraints that are introduced when amphiphilic side groups are fixed to a polymer backbone do not significantly alter the response of the mesophase to a shear deformation.

Rheological and molecular characterization of linear backbone flexible polymers with the Cole-Cole model relaxation spectrum

Abstract: The empirical Cole-Cole distribution is an analytical three parameter model of the relaxation spectra that provides accurate fits to experimental dynamic viscosity data for many systems of commercial linear backbone flexible polymers. We demonstrate that for disparate systems of polyethylenes, the three Cole-Cole model parameters have simple power law relationships to moments of the molecular weight distribution enabling direct molecular interpretation of the mechanical relaxation spectrum. A simple relationship between the Cole-Cole distribution and the Cross model for the non-linear flow curve can be deduced utilizing the empirical Cox-Merz rule. Accurately representing the linear viscoelastic material functions with empirical analytical relaxation spectra containing relatively few fitting parameters that can be readily interpreted is a major advance in polymer characterization. The three Cole-Cole parameters effectively replace single point material characterizations such as melt flow index. Development of higher resolution polymer characterization methods is imperative with the advent of metallocene catalyst technology, which enables the molecular weight and backbone architecture to be carefully controlled.

Elastic recovery of immiscible blends 1. Analysis after steady state shear flow

Abstract: Due to the interfacial tension, immiscible blends can show an elastic recovery that is substantially larger than that of their pure components. Here it is attempted to relate the elastic recovery after steady shear flow to the underlying morphology. On the one hand, the predictions of the Palierne and the Doi-Ohta models are calculated for the flow conditions during recoil. On the other hand, systematic recoil experiments after steady state shearing have been performed on a model blend. As the component polymers hardly show any recoil under the stresses applied in these tests, the measured recovery can be attributed completely to the action of the interface. Comparison of the model predictions with the experimental results shows that the recoverable strain can be derived quantitatively from the linear Palierne theory. Although the droplet deformation remained limited during the preshear, the retardation time predicted by this model has to be multiplied by the aspect ratio of the droplet phase to the power 2/3 to describe the experiments. For conditions in which the material does not show an intrinsic length scale, particular scaling relations as derived from the Doi-Ohta theory are found to apply also to recoil.

Rheological characterisation of a high-density polyethylene with a multi-mode differential viscoelastic model and numerical simulation of transient elongational recovery experiments

Abstract: The rheological characterisation of a high-density polyethylene is performed by means of measurements of the storage and loss moduli, the shear viscosity and the transient uniaxial elongational viscosity, the latter being obtained with the Meissner extensional rheometer. The rheological behaviour of the polymeric material is described by means of a multi-mode Phan Thien-Tanner fluid model, the parameters of which are successively fitted on the basis of the linear and non-linear properties. By using a semi-analytical technique and the finite element method, numerical investigations are performed for the shape recovery of the sample, and the predictions are compared with their experimental counterparts. Surface tension effects are also explored. We discuss the agreement between the experiments and the simulation results.

Application of the Casson model to thixotropic waxy crude oil

Abstract: The rheological behavior of a waxy crude oil was investigated using a coaxial cylinder viscometer. Experimental flow curves were fitted with the Casson equation. The Casson model was modified to interpret the hysteresis between upward and downward curves obtained in a series of consecutive runs. At the same shear rate, the mean axial ratio of the flow unit related to a down-curve (↓) is smaller than that related to an equilibrium up-curve (↑). This results in a decrease of the Casson yield stress τc↓ with respect to τc↑. A certain ξ coefficient describing departure from the equilibrium mean axial ratio was introduced into the model. Values of ξ calculated from the Casson yield stresses agreed satisfactorily with the theoretically predicted ones. Deviations from the Casson model at low shear rates were also explained.

The motion of long bubbles through viscoelastic fluids in capillary tubes

Abstract: The penetration of long gas bubble through a viscoelastic fluid in a capillary tube has been studied in order to investigate the influence of viscoelastic material properties on the hydrodynamic coating thickness and local flow kinematics. Experiments are conducted for three tailored ideal elastic (Boger) fluids, designed to exhibit similar steady shear properties but substantially different elastic material functions. This allows for the isolation of elastic and extensional material effects on the bubble penetration process. The shear and extensional rheology of the fluid is characterized using rotational and filament stretching rheometers (FSR). The fluids are designed such that the steady-state extensional viscosity measured by the FSR at a Deborah number (De) greater than 1 differs over three orders of magnitude (Trouton ratio = 103–106). The experiment set up to measure the hydrodynamic coating thickness is designed to provide accurate data over a wide range of capillary numbers (0.01 < Ca < 100). The results indicate that the coating thickness in this process increases with an increase in the extensionally thickening nature of the fluid. Experiments are also conducted using several different capillary tube diameters (0.1 < D < 1 cm), in order to compare responses at similar Ca but different flow De. Suitable scaling methods and nonlinear viscoelastic constitutive equations are explored to characterize the displacement process for polymeric fluids. Bubble tip shapes at different De are recorded using a CCD camera, and measured using an edge detection algorithm. The influence of the mixed flow field on the bubble tip shape is examined. Particle tracking velocimetry experiments are conducted to compare the influence of viscoelastic properties on the velocity field in the vicinity of the bubble tip. Local shear and extension rates are calculated in the vicinity of the bubble tip from the velocity data. The results provide quantitative information on the influence of elastic and extensional properties on the bubble penetration process in gas-assisted injection molding. The bubble shape and velocity field information provides a basis for evaluating the performance of constitutive equations in mixed flow.

Nonlinear rheology of concentrated spherical silica suspensions: 3. Concentration dependence

Abstract: Nonlinear rheology was examined for concentrated suspensions of spherical silica particles (with radius of 40 nm) in viscous media, 2.27/1 (wt/wt) ethylene glycol/glycerol mixture and pure ethylene glycol. The particles were randomly and isotropically dispersed in the media in the quiescent state, and their effective volume fraction φeff ranged from 0.36 to 0.59. For small strains, the particles exhibited linear relaxation of the Brownian stress σB due to their diffusion. For large step strains γ, the nonlinear relaxation modulus G(t,γ) exhibited strong damping and obeyed the time-strain separability. This damping was related to γ-insensitivity of strain-induced anisotropy in the particle distribution that resulted in decreases of σB/γ. The damping became stronger for larger φeff. This φeff dependence was related to a hard-core volume effect, i.e., strain-induced collision of the particles that is enhanced for larger φeff. Under steady/transient shear flow, the particles exhibited thinning and thickening at low and high γ˙, respectively. The thinning behavior was well described by a BKZ constitutive equation using the G(t,γ) data and attributable to decreases of a Brownian contribution, σB/γ˙. The thickening behavior, not described by this equation, was related to dynamic clustering of the particles and corresponding enhancement of the hydrodynamic stress at high γ˙. In this thickening regime, the viscosity growth η+ after start-up of flow was scaled with a strain γ˙t. Specifically, critical strains γd and γs for the onset of thickening and achievement of the steadily thickened state were independent of γ˙ but decreased with increasing φeff. This φeff dependence was again related to the hard-core volume effect, flow-induced collision of the particles enhanced for larger φeff.

Pressure influences upon shear thickening of poly(acrylamide) solutions

Abstract: This paper provides experimental data, measured with a Bohlin VOR viscometer and a Haake Searle-type high temperature and high pressure viscometer, which describe the shear thickening behaviour of a poly(acrylamide) in various glycerol-water mixtures. The influence of the glycerol content, the polymer solute concentration, the presence of salts and also the variation of the temperature and the pressure upon the shear thickening properties and associated descriptive parameters are reported. A proposed mechanism for the observed shear thickening behaviour, due to the formation of transient networks between the oriented and stretched polymer chains, under the action of the high shear forces is tentatively presented. The influence of the above variables upon the formation of a proposed interconnected network is discussed and the influence upon the rheological response is considered.

Characterization of the flow properties of sodium carboxymethylcellulose via mechanical and optical techniques

Abstract: Sodium carboxymethylcellulose (NaCMC) in solution represents a complex rheological system, since it forms aggregates and associations and hence higher-level structures and, depending on the synthesis, is only found in a molecularly dispersed form in exceptional cases. Rheo-mechanical investigations of the viscoelasticity showed that the Cox-Merz rule is not fulfilled. The aim was therefore to examine whether rheo-optics could be employed to provide more detailed conclusions about the parameters that influence the flow behavior of NaCMC than has hitherto been available with mechanical methods. The flow birefringence, Δn′, rises as the degree of polymerization increases, and exhibits the same dependence on molar mass as does the viscosity: Δn′∝Mw3.4. As the degree of polymerization increases while the shear rate remains constant, the polymer segments become more distinctly aligned in the direction of shear. Hence increasing the degree of polymerization also affects the solution structure, i.e. the interaction of the molecules with one another. The stress-optical rule only applies to a limited extent for this system. The stress-optical coefficient, C, is almost independent of the shear rate, but is strongly influenced by the concentration and attains a limiting value of 3 × 10−8 Pa−1. C was determined for a polymer in dilute solution and the curve obtained also enabled transitions in the solution structure to be recognized.

1H NMR spectroscopy of polymers under shear and extensional flow

Abstract: We discuss the potential insights gained from 1H nuclear magnetic resonance (NMR) spectroscopy experiments on polymeric systems under both shear and extension, and we show in particular that 1H spin-spin relaxation is sensitive to both molecular conformation and to molecular interactions. Rheo-NMR 1H spectroscopy studies on semi-dilute solutions of polyacrylamide demonstrate that the chain protons exhibit a marked T2 reduction under shear and that the recovery on shear cessation is indicative of slow reorganisational dynamics. Studies of the wheat flour protein, gluten, indicate marked spectroscopic changes in the vicinity of the amidic resonances associated with glutamine residues, an effect we attribute to the disruption of hydrogen bonding.

Rheological properties of polymer blends with sphere-in-sphere morphology

Abstract: The linear viscoelastic behavior of polystyrene (PS) and poly(methylmethacrylate) (PMMA) blends with PS as the matrix and amounts of PMMA in the range 10–30 wt% was investigated. Transmission electron microscopy (TEM) revealed a complex morphology which was characterized by the existence of composite particles; the PMMA particles which are enclosed in the PS matrix themselves carry PS inclusions. In order to explain the G* data of these blends a model is presented which consists of a Palierne model for the composite particles and a Palierne model for the whole blend, taking into account composite and neat particles. Simulations show the principal relevance of the assumptions made. Moreover, it is shown that the measurements agree well with the model for the whole measured frequency region and that the fit parameters, the size of the composite particles and the concentration and size of interior particles are in reasonable agreement with data available from TEM.

Shear viscosity of suspensions of aligned non-Brownian fibres

Abstract: We report on the steady-state shear viscosity of suspensions of fibres dispersed in Newtonian fluids, in a wide range of volume fractions throughout the dilute and semi-dilute regimes. We show that the apparent shear-thinning behaviour, which is sometimes observed in the semi-dilute regime at intermediate shear rates, is an experimental artefact due to the presence of transient clusters of entangled fibres in the suspensions. At high shear rates, the fibres are aligned and the suspensions exhibit Newtonian behaviour. In this regime, the viscosity is a function of volume fraction and fibre aspect ratio only. The data can be rescaled onto a universal curve using a variable that accounts for the average contribution of the particles to the bulk stress. All these results are discussed in relation to recent theories.

Suspension of layered particles: an optimum electrorheological fluid for d.c. applications

Abstract: A comparison is made between two types of solid particles used in electrorheological fluids: particles with homogeneous electrical properties versus layered particles with a semi-conducting core surrounded by an outer layer of lower conductivity. Rheological measurements of these suspensions under steady shear and d.c. electric field show that the layered particle system produces the same yield stress but with a substantially reduced electric current. X-ray spectroscopic analysis confirms that these particles have a thin layer of SiOx on the outer surface which causes the reduction in conductivity. Measurement of the dielectric permittivity followed by analysis using the Maxwell-Wagner model of polarization indicates that the conductivity of the outer layer is about 0.62 times that of the core region.

Flow birefringence study of sharkskin and stress relaxation in polybutadiene melts

Abstract: In this paper we report rheo-optical and rheological observations made through a transparent slit die attached to a capillary rheometer. We find that the flow birefringence signal oscillates periodically near the die exit when sharkskin-like extrudate distortion is present. In contrast, steady behavior is observed in the die inland region. Specifically, the flow birefringence varies at the die exit with a period identical to that measured directly from the sharkskin extrudate. We also show that the exit flow instability leading to sharkskin can be observed directly through cross-polarizers in terms of the temporal change of the retardation order. We demonstrate that the same kind of interfacial flow instability can occur at a boundary discontinuity within the die land where the upper portion of a clean die wall meets the lower portion of a polysiloxane-coated die wall. Finally, stress relaxation upon the cessation of the slit die flow of two polybutadiene melts is studied through time-dependent flow birefringence measurements. The stress relaxation is then correlated with sharkskin time scales to describe the role of relaxation in sharkskin ridge formation.

Flow-aligning and tumbling in small-molecule liquid crystals: pure components and mixtures

Abstract: The results of an experimental study to measure the tumbling parameter, λ, for various small-molecule liquid crystals and their mixtures are presented. The methods used include textural observations (twist walls), a direct method, a rheological method, and the oscillatory method developed by Mather, Pearson, and Burghardt in 1995. The single-component results are compared with a molecular theory derived in 1995 by Archer and Larson as well as Kroger and Sellers, which predicts the temperature dependence of λ, while the results from the binary mixtures are compared to a continuum theory derived by Rey in 1996, giving the concentration dependence of λ. The results from the four experimental methods agree with each other for single-component liquid crystals, but not for mixtures. This suggests a failure of the single director Leslie-Ericksen theory to describe the rheology of liquid crystal mixtures.