Dispersion of multi-walled carbon nanotubes in PDMS/PB blend

In this study, the sequential dispersion of multi-walled carbon nanotubes (CNTs) in PDMS/PB (polydimethylsiloxane/polybutene) blends and the change of blend morphology by the dispersion of CNTs were investigated by rheological and morphological observations. The dispersion of CNTs into PDMS/PB blend was accomplished by the dilution of the CNT master (2?wt.% CNT in PDMS) in PDMS/PB blend using an extensional mixer. The morphological study shows that under the extensional flow, CNTs in the dispersed CNT master phase are mainly broken up by tip-streaming and the continuous pinching-off of PDMS drops during morphology evolution enhances the dispersion of CNT. It has been shown that CNTs can be disentangled as in the case of dispersing CNTs in a Boger fluid. Rheological data and TEM observations show that it is not simply a mixing of two phases and the CNTs in the master phase can be dispersed in the single CNT level.     

Specific rheology – morphology relationships for some blends containing LCPs

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

Stress relaxation after steady shear flow in immiscible model polymer blends

Stress relaxation in immiscible blends is studied for a well defined shear history, i.e. after prolonged steady state shearing. Model systems are used that consist of quasi-Newtonian liquid polymers. Hence the relaxation is dominated by changes in the morphology of the interface. Both shear stress and the first normal stress are considered. The measurements cover the entire concentration range. For dilute blends the interfacial contribution to the stress relaxation compares well with model predictions. Deviations occur when the matrix phase is slightly elastic. In that case the similarity between the relaxation of shear and normal stresses is also lost. The latter is attributed to a wider drop size distribution.Increasing the concentration of the disperse phase results in a complex evolution of the characteristic relaxation times. The normal stresses relax systematically slower than the shear stresses and the concentration curve includes two maxima. Even for equiviscous components the concentration curves are not symmetrical. It is concluded that even a slight degree of elasticity in the matrix phase drastically affects the morphology and the interfacial relaxation of such blends.     

A generalized equation for rheology of emulsions and suspensions of deformable particles subjected to simple shear at low Reynolds number

We present analyses to provide a generalized rheological equation for suspensions and emulsions of non-Brownian particles. These multiparticle systems are subjected to a steady straining flow at low Reynolds number. We first consider the effect of a single deformable fluid particle on the ambient velocity and stress fields to constrain the rheological behavior of dilute mixtures. In the homogenization process, we introduce a first volume correction by considering a finite domain for the incompressible matrix. We then extend the solution for the rheology of concentrated system using an incremental differential method operating in a fixed and finite volume, where we account for the effective volume of particles through a crowding factor. This approach provides a self-consistent method to approximate hydrodynamic interactions between bubbles, droplets, or solid particles in concentrated systems. The resultant non-linear model predicts the relative viscosity over particle volume fractions ranging from dilute to the the random close packing in the limit of small deformation (capillary or Weissenberg numbers) for any viscosity ratio between the dispersed and continuous phases. The predictions from our model are tested against published datasets and other constitutive equations over different ranges of viscosity ratio, volume fraction, and shear rate. These comparisons show that our model, is in excellent agreement with published datasets. Moreover, comparisons with experimental data show that the model performs very well when extrapolated to high capillary numbers (C a?1). We also predict the existence of two dimensionless numbers; a critical viscosity ratio and critical capillary numbers that characterize transitions in the macroscopic rheological behavior of emulsions. Finally, we present a regime diagram in terms of the viscosity ratio and capillary number that constrains conditions where emulsions behave like Newtonian or Non-Newtonian fluids.     

A simple extensional viscometer

An extensional viscometer is described in which the liquid filament leaving a capillary is subjected to a stretching deformation. In order to keep the flow rate through the capillary unaltered upon inception of stretching, the pressure head at the capillary entrance has to be reduced by an amount equal to the extensional viscoelastic stress at the capillary exit. This affords a simple means of measuring small fluid forces such as those that occur in the stretching of dilute polymer solutions. Since stretch rates can be obtained from a knowledge of the mass flow rate and the filament diameter profile, extensional viscosities can be computed. The efficacy of the technique is demonstrated by obtaining the anticipated results for Newtonian liquids.     

Morphology development in polystyrene/polyethylene blends during uniaxial elongational flow

The deformation of linear low-density and low-density polyethylene particles dispersed in a polystyrene matrix was studied during defined uniaxial elongational flow conditions for different capillarity numbers and different temperatures. The morphology of the elongated samples was analysed by quenching the specimens in liquid nitrogen directly after the deformation. Furthermore, morphology development after recovery was investigated. By measuring the transient elongational viscosity of the blend matrix the true hydrodynamic stress during the flow process was calculated. Using a modified critical capillarity number, the fibril formation of the dispersed phase could be described at all test conditions. Virtually no break-up processes were observed. This finding could be explained by calculating the characteristic time of fibril break-up due to Rayleigh instabilities. By annealing the elongated samples a spherical shape of the dispersed droplets was regained. Compared with the initial sample morphology a pronounced increase of the particle sizes due to coalescence processes during elongation was observed.     

Non-linear behaviour of asphalts in steady and transient shear flow

Steady-state and transient shear stress and normal stress data were obtained for four asphalts with a modified Weissenberg Rheogoniometer. Interest was specially related to non-linear behaviour at high shear-rates. The time-temperature superposition principle was found to hold in non-linear behaviour. Moreover, steady-state and transient data could be plotted as master curves irrespective of the nature of the asphalts. In particular, the master curve of steady-state viscosity could be extended to results published in the literature. In the nonlinear region the shear stress relaxation after cessation of a steady shear rate becomes a function of t only and is related to the primary normal-stress coefficient, as predicted by the Yamamoto equation. In the shear stress growth experiment an overshoot is obtained at a constant strain close to 1.5, independent of the rate of strain.     

Influence of Viscous Fingering on Dynamic Saturation–Pressure Curves in Porous Media

We report on results from primary drainage experiments on quasi-two-dimensional porous models. The models are transparent, allowing the displacement process and structure to be monitored in space and time during primary drainage experiments carried out at various speeds. By combining detailed information on the displacement structure with global measurements of pressure, saturation and the capillary number Ca, we obtain a scaling relation relating pressure, saturation, system size and capillary number. This scaling relation allows pressure–saturation curves for a wide range of capillary numbers to be collapsed on the same master curve. We also show that in the case of primary drainage, the dynamic effect in the capillary pressure–saturation relationship observed on partially water saturated soil samples might be explained by the combined effect of capillary pressure along the invasion front of the gaseous phase, and pressure changes caused by viscous effects in the wetting fluid phase.     

Mechanical energy balances for a capillary viscometer

The entrance and exit flow processes for a cylindrical geometry are analyzed by writing macroscopic mechanical energy balances for a capillary viscometer. These equations can be used to compute the entrance and exit excess dissipation integrals from measured pressure differences if viscometric normal stress data are available for the material of interest. Upper and lower bounds are derived for these integrals for cases when high shear rate normal stress data are not available. The utilization of macroscopic mechanical energy balances in the interpretation of capillary viscometer results is illustrated using numerical solutions for a Maxwell fluid and experimental pressure drop data for high density polythylene.     

Uniaxial deformation and relaxation of polymer blends: relationship between flow and morphology development

Uniaxial elongational flow followed by stress relaxation of a dilute mixture of polystyrene/polymethylmethacrylate) PS/PMMA with PS (5 wt%) as a dispersed phase was investigated. The behavior of the blend was found to be dominated by the PMMA matrix during elongation and by the interface during the relaxation at long time. Such a behavior was related to drop deformation and shape recovery during the relaxation process as was confirmed by morphological analyses on samples quenched within the rheometer just after elongation and at various times during the relaxation process. The morphology and the rheological material functions variation were compared to the Yu model (Yu W, Bousmina M, Grmela M, Palierne JF, Zhou C (2002) Quantitative relationship between rheology and morphology in emulsions. J Rheol 46(6):1381–1399).     

Processing the capillary viscometry data of fluids with yield stress

The capillary viscometer is used to measure the shear stress-shear rate relationship of a wide range of purely viscous fluids. It is however not considered as an appropriate instrument for obtaining the yield stress and the post-yield behaviour of fluids that have a yield stress. This is partly because conventional methods of processing the capillary viscometry data of purely viscous fluids cannot be applied to similar data of fluids with yield stress. The unavoidable experimental noise in the capillary data, particularly at low shear rates, also makes it difficult to obtain a reliable estimate of the yield stress from capillary data. In this investigation the problem of converting the capillary viscometry data of yield stress fluids into a shear stress-shear rate curve and a yield stress is formulated as a Volterra integral equation of the first kind. This is an ill-posed problem i.e. noise in the data will be amplified by inappropriate methods of data processing. A method, based on Tikhonov regularisation that takes into account the ill-posed nature of the problem, is then developed to solve this problem for fluids with yield stress. The performance of this method is assessed by applying it to a set of “synthetic” capillary viscometry data with added random noise and to a set of experimental data for a concentrated suspension of TiO₂ taken from the literature. In both cases Tikhonov regularisation was able to extract the complete shear properties of these fluids from capillary viscometry data alone. Received: 22 November 1999/Accepted: 17 December 1999     

Rheograms for asphalt from single viscosity measurement

Asphalt materials are used in a variety of applications such as road paving, waterproofing, roofing membranes, adhesive binders, rust proofing and water resistant coatings. There are available in a number of grades distinguished in terms of their softening point and flow resistance. The selection of the proper grade of asphalt for a particular application is governed by the desired flow behaviour. A knowledge of the complete flow curve depicting the variation of melt viscosity with shear rate at the relevant temperatures is necessary not only for proper grade selection, but also for specifying processing conditions for aggregate mixing and spraying. The rheological data are also useful in assessing end use performance. The scientific techniques for generating the rheological data involve the use of expensive, sophisticated instruments. Generation of the necessary flow data using these instruments is beyond the financial and technical means of most processors of asphalt materials. The engineering techniques involving the use of inexpensive vacuum viscometers are relatively easy, but provide a single point viscosity measurement at low shear rate. In the present work, a method is proposed for unifying the viscosity versus shear rate a data at various temperatures for a number of asphalt grades. A master curve has been generated that is independent of the grade of asphalt and the temperature of viscosity measurement. The master curve can be used to generate rheograms at desired temperatures for the asphalt grade of interest, knowing its zero-shear viscosity at that temperature.NCL Communication Number 2914.     

Effects of coalescence and breakup on the steady-state morphology of an immiscible polymer blend in shear flow

The steady-state morphology of an immiscible polymer blend in shear flow has been investigated by optical microscopy techniques. The blend is composed by poly-isobutylene (PIB) and poly-dimethylsiloxane (PDMS) of comparable viscosity. Experiments were performed by means of a home-made transparent parallel plate device. The two plates can be independently counterrotated, so that sheared droplets of the dispersed phase can be kept fixed with respect to the microscope point of view, and observed for long times. The distribution of drops and their average size were measured directly during flow at different shear rates and for different blend compositions. It was found that the average drop size in steady-state conditions is a decreasing function of the applied shear rate, and does not depend on blend composition for volume fractions up to 10%. Experiments have proved that, in the shear rate range which could be investigated, the stationary morphology is controlled only by coalescence phenomena, droplet breakup playing no role in determining the size of the dispersed phase. More generally, it has been shown that the steady-state morphology is a function not only of the physical parameters of the blend and of the shear rate, but also of the initial conditions applied to the blend. The steady-state results reported in this paper constitute the first direct experimental confirmation of theoretical models which describe the mechanisms of shear-induced drop coalescence.     

Rheology of a suspension of particles in viscoelastic fluids

In this paper we study the bulk stress of a suspension of rigid particles in viscoelastic fluids. We first apply the theoretical framework provided by Batchelor [J. Fluid Mech. 41 (1970) 545] to derive an analytical expression for the bulk stress of a suspension of rigid particles in a second-order fluid under the limit of dilute and creeping flow conditions. The application of the suspension balance model using this analytical expression leads to the prediction of the migration of particles towards the centerline of the channel in pressure-driven flows. This is in agreement with experimental observations. We next examine the effects of inertia (or flow Reynolds number) on the rheology of dilute suspensions in Oldroyd-B fluids by two-dimensional direct numerical simulations. Simulation results are verified by comparing them with the analytical expression in the creeping flow limit. It is seen that the particle contribution to the first normal stress difference is positive and increases with the elasticity of the fluid and the Reynolds number. The ratio of the first normal stress coefficient of the suspension and the suspending fluid decreases as the Reynolds number is increased. The effective viscosity of the suspension shows a shear-thinning behavior (in spite of a non-shear-thinning suspending fluid) which becomes more pronounced as the fluid elasticity increases.     

On the pressure correction of capillary melt rheology data

In this paper, the importance of a pressure correction of viscosity data obtained in capillary melt rheology is demonstrated. A linear polycarbonate has been chosen as a highly pressure-sensitive material for which data obtained by rotational rheometry does not overlap with capillary data. This apparent problem with the Cox–Merz relation is attributed to the existence of a mean pressure inside the capillary which is significantly different from atmospheric conditions. Different methods to determine the pressure coefficient of polycarbonate have been evaluated based on experiments performed with a capillary rheometer equipped with a pressure chamber. It is demonstrated that the pressure coefficient obtained at constant shear stress and the pressure coefficient obtained by the superposition method represent accurate pressure coefficient values. Two approaches are proposed to correct the original capillary data. In the direct methodology, the pressure coefficient is used to rescale the mean pressure inside the capillary to atmospheric conditions. The indirect approach consists of first constructing a mastercurve at a certain reference pressure using capillary data obtained with a pressure chamber. The resulting mastercurve can then be rescaled to atmospheric conditions. It is shown that both methods lead to viscosity curves on which both rotational and capillary data overlap, hence confirming the Cox–Merz relationship for polycarbonate. The indirect method is proven to be advantageous since it opens the possibility to significantly extend the shear rate window in which viscosities can be measured.     

Shear-induced crystallization of PB-1 up to processing-relevant shear rates

Two experimental methods to study shear-induced crystallization of poly(butene-1) (PB-1) in the high shear rate region are presented: one using a concentric cylinder rheometer and the other a capillary rheometer equipped with a cylindrical die. The crystallization onset time (t _on) is used as the parameter to monitor crystallization progress through the output signal from each device. By combining the new data with the results from a previous paper (2005) in which a plate–plate rheometer was used, onset time data covering a shear rate range from 10^-4 to 500 s^-1 at temperatures 99–107°C are obtained. In this range, a decrease in onset time spanning five decades is observed. The onset times obtained from the capillary rheometer are larger compared to those from the other two methods, which can be explained from the different type of flow. The data also confirm the procedure to construct a temperature-invariant curve, which can be extended to high shear rates for three PB-1 samples having different molecular weight distributions. The slope of the fitted curve for all three cases is −1, which suggests that a critical value is required for shear-induced crystallization. The morphology of the formed crystals (spherulitic or rod-like) depends on the molecular weight, but this does not affect the validity of the T-invariant curve. Above the melting point, it is shown that the amount of long chains influences the temperature limit where shear-induced crystallization can still take place.The paper was presented at AERC 2005, Grenoble, with the title “Shear-Induced Crystallization of Polybutene-1 Covering a Wide Shear Rate Range.”An erratum to this article can be found at     

Microstructure and rheological properties of triblock copolymers under extrusion conditions

Triblock copolymers with different microstructures were subjected to macroscopic deformations under extrusion using a miniaturized high pressure capillary rheometer. The rheological properties of the triblock copolymers investigated depend strongly on composition and configuration of the building units, which are microphase separated into complex morphologies. Under extrusion conditions they organize to stretched layer systems, which are perpendicular oriented in respect to the direction of the shear plane and the orientation decreases again at high shear rates. The macroscopic order leads to integral values of the order parameter from two-dimensional small X-ray scattering and form birefringence, which show a good correlation in the relevant shear rate range. Furthermore, a master curve of the form birefringence can be obtained.     

Capillary Pressures by Fluid Saturation Profile Measurements During Centrifuge Rotation

A novel centrifuge technique to obtain the capillary pressure curve by measuring the local fluid distribution in a spinning core is presented. The Nuclear Tracer Imaging Centrifuge (NTIC) method measures the fluid saturation profile along the length of the core to directly obtain the capillary pressure curve. The proposed method is superior to conventional centrifuge techniques because (1) the capillary pressure curve is obtained at one rotational speed, (2) core plugs are not removed from the spinning centrifuge for imaging, and (3) no mathematical solution is needed to calculate the capillary pressure curve. The literature states that the various mathematical solutions used in conventional centrifuge tests are the greatest source of error, not the uncertainty in the experimental data. By eliminating the dependence of such solutions, the NTIC represents an alternative to conventional centrifuge tests, and may be used to validate the various mathematical procedures applied in conventional centrifuge capillary pressure tests. NTIC may also confirm the applicability of other imaging techniques that rely on core plug removal for saturation imaging, by verifying if there is no fluid re-distribution at static conditions.     

Rheology of polymer blends with matrix-phase viscoelasticity and a narrow droplet size distribution

A Hamiltonian framework of non-equilibrium thermodynamics is adopted to construct a set of dynamical continuum equations for a polymer blend with matrix viscoelasticity and a narrow droplet size distribution that is assumed to obey a Weibull distribution function. The microstructure of the matrix is described in terms of a conformation tensor. The variable droplet distribution is described in terms of two thermodynamic variables: the droplet shape tensor and the number density of representative droplets. A Hamiltonian functional in terms of the thermodynamic variables is introduced and a set of time evolution equations for the system variables is derived. Sample calculations for homogenous flows and constant droplet distribution are compared with data of a PIB/PDMS blend and a HPC/PDMS blend with high viscoelastic contrast. For the PIB/PDMS blend, satisfactory predictions of the flow curves are obtained. Sample calculations for a blend with variable droplet distribution are performed and the effect of flow on the rheology, droplet morphology, and on the droplet distribution are discussed. It is found that deformation can increase or decrease the dispersity of the droplet morphology for the flows investigated herein.