Rheology of immiscible blends with particle-induced drop clusters

We consider the effects of 2.7-μm-diameter hydrophobic silica particles added to droplet–matrix blends of polyethylene oxide (PEO) and polyisobutylene (PIB). The particles adsorb on the surface of the PEO drops but protrude considerably into the PIB phase. Hence, it is possible for a single particle to adsorb onto two PEO drops simultaneously. Such particles are called “bridging” particles, and they the glue drops into noncoalescing clusters. Flow visualization studies show that shearing the sample promotes bridging-induced clustering of drops and that the structure of the clusters depends on the shear rate. Rheologically, the most significant consequence of bridging-induced drop clustering appears to be a plateau in G′ at low frequencies characteristic of gel-like behavior. The gel-like behavior develops fully after shearing the sample, and the kinetics of gel formation are faster with increasing shear stress or increasing drop volume fraction. The gel-like behavior suggests that the bridging-induced drop clusters form a weak network. Apart from particle bridging, optical microscopy also reveals that particles can organize into a hexagonal lattice on the drops’ surfaces, a phenomenon that has only been noted in aqueous systems previously. Finally, rheology and flow visualization both suggest that particles promote coalescence of drops. This is surprising in light of much past research that shows that particles that are preferentially wetted by the continuous phase generally hinder coalescence in droplet–matrix systems.     

Effect of fumed silica nanoparticles on the morphology and rheology of immiscible polymer blends

We examined the effect of interfacially active particles on the morphology and rheology of droplet/matrix blends of two immiscible homopolymers. Experiments were conducted on polybutadiene/polydimethylsiloxane (10/90) blend and the inverse system. The effects of fumed silica nanoparticles, at low particle loadings (0.1–2.0 wt%), were examined by direct flow visualization and by rheology. Fumed silica nanoparticles were found to significantly affect the morphology of polymer blends, inducing droplet cluster structure and decreasing the droplet size, regardless of which phase wets the particles preferentially. This is surprising in light of much past research that shows that particles are capable of bridging and thus induce droplet cluster structure in droplet/matrix systems only when they are preferentially wetted by the continuous phase. Therefore, there should exist other possible mechanisms responsible for these droplet cluster structures except for the bridging mechanism. We proposed a particle-flocculating mechanism based on the fact that fumed silica particles readily flocculate due to their high aspect ratio, fractal-like shape, or interparticle attractions. Optical microscopy also reveals that the clustering structure becomes more extensive, and the droplet sizes in the clusters become smaller when the particle loading is increased. Rheologically, the chief effect of particles is to change the flow behavior from a liquid-like rheology to gel-like behavior. This gel-like behavior can be attributed to droplet clustering. Moreover, it should be emphasized that such gel-like behavior can be seen in the blends regardless of which phase wets the particles preferentially, suggesting that, once again, bridging is not the only cause of droplet clustering.     

Rheology and structure of precipitated silica and poly(dimethyl siloxane) system

The reinforcing capability of precipitated silica in poly(dimethyl siloxane: PDMS) was characterized by means of bound rubber formation, solvent swelling, yield stress, rheological and dynamic properties. Volume concentration of precipitated silica in PDMS was varied from 0 to 0.16. The homogeneity of the compounds after mixing was confirmed by studying a uniformity of dispersion of silica particles in PDMS via SEM morphology of vulcanizates. Bound rubber measurements of the compounds and solvent swelling studies of vulcanizates showed that the precipitated silica exhibited much stronger interaction with PDMS than that of typical carbon black with rubbers but less than that of fumed silica with PDMS. At high volume concentrations of silica (0.128 and 0.160), a yield behavior was evident from the storage modulus measurements. The network formation due to an interaction between the precipitated silica and PDMS was visualized via dynamic property measurements.     

Coalescence suppression in model immiscible polymer blends by nano-sized colloidal particles

The effect of nanometer sized silica particles (R16 nm) on the flow-induced morphology of immiscible polymer blends is studied. Polydimethylsiloxane (PDMS) and polyisobutylene (PIB) are chosen as model components. A stable droplet/matrix microstructure is obtained for blends of 30% PIB in 70% PDMS or vice versa. Rheological measurements are used to show that the silica particles alter the sensitivity of the of dispersed phase/matrix microstructure to shear flow. Coalescence is suppressed or at least slowed down on a practical time scale, especially when PDMS is the matrix phase. The effect of mixing conditions, pre-shear rate and particle concentration on the blend morphology are studied. Cryo-SEM is used to observe the accumulation of the particles at the interface. Blends stabilized by solid particles could provide an interesting alternative to blends compatibilized by block-copolymers.This paper was presented at the first Annual European Rheology Conference (AERC) held in Guimarães, Portugal, September 11-13, 2003.     

Particle-stabilized polymer blends

The effect of low-volume fractions of nanoparticles on the morphological processes and the rheological properties of immiscible blends are dis cussed. For blends of poly-isobutylene and poly-dimethylsiloxane stabilized by silica particles, particles help to suppress coalescence. Yet, particle bridging of different droplets has also been reported and leads to a slow build up of a gel-like structure, which could interfere with the morphology evolution under flow. We first investigated the importance of this effect under relevant conditions. To further assess the relative importance of the different processes in technically relevant polymer–polymer blends, the effect of carbon black particles on morphological processes—coalescence and break-up—in polyamide and ethylene–ethylene–metylacrylate copolymers will be studied using rheological methods. It will be shown that particles affect coalescence and break-up, suggesting that the effect of particles is linked to their effect on interfacial dynamics.     

Non-linear viscoelastic behavior of fumed silica suspensions

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. Received: 9 March 1998 Accepted: 17 November 1998     

A thermodynamic approach to the rheology of highly interactive filler-polymer mixtures. Part II. Comparison with polystyrene/nanosilica mixtures

The dynamic properties as a function of frequency and strain amplitude, steady-state viscosity as a function of shear rate, and transient shear stresses at startup and cessation of shear flow of polystyrene (PS)/fumed silica mixtures of various concentrations were investigated. An abrupt change in the viscoelastic properties was noticed at a concentration above 1% by volume. Observations by means of scanning electron microscopy (SEM) indicate the presence of a three-dimensional network through the bridging of filler particles by the adsorbed polymer. The viscoelastic behavior is simulated utilizing a theory proposed in Part I (Havet and Isayev 2001) based on a double network created by the entangled polymer matrix and the adsorbed polymer with filler concentration taken into account through the bridging density of polymer-filler interactions and a hydrodynamic reinforcement. The steps taken for determining the model parameters required to carry out the simulation are described. The major features of the rheological behavior of highly interactive polymer-filler mixtures are captured qualitatively and in some cases, quantitatively predicted.     

A model system for thixotropy studies

Many constitutive equations have been proposed for thixotropic materials but the supporting experimental evidence has usually been rather fragmentary. To a large extent this is due to the difficulties involved in measuring thixotropic systems. These systems normally display various phenomena that result in poor accuracy and poor reproducibility of the measurements. Therefore, it has been attempted here to formulate a robust thixotropic system that allows accurate measurements and that would be suitable for detailed studies of thixotropy. The system that has been developed is based on a matrix liquid that consists of a high boiling paraffin oil and a low molecular weight poly(isobutylene). A suitable type of fumed silica is used as the dispersed phase. The various rheological parameters of the material can be altered by varying the concentration of the components and, if necessary, the molecular weight of the polymer. The relative humidity around the sample turns out to be an important factor in controlling the yield stress, and its effect is shown to be reversible. The selected system can be measured accurately over a wide range of measurement conditions. These include stress jump measurements, which can be used to separate viscous and elastic contributions. The highest possible shear rate is limited by the occurrence of a peculiar phenomenon that shows up in the normal stresses.     

Understanding droplet coalescence and its use to estimate interfacial tension

The study of coalescence of polymer droplets is presented in the viscosity ratio range (p) going from 0.1 to 10. It is shown that the determination of the characteristic time of coalescence is a good way to estimate the interfacial tension. Polydimethylsiloxane (PDMS) is mixed with polyisobutylene (PIB) and the temperature change provides a way to modify the interfacial tension of the PDMS/PIB system significantly, as measured using a pendant drop apparatus. We obtain a dependence of the reduced coalescence time as a function of p^-1/2 which gives access to the interfacial tension. This technique can be an interesting choice for estimating interfacial tension without requiring sophisticated techniques. In a further attempt to correlate these observations with a theoretical model (Verdier C (2001) Polymer 42), the flow field inside and outside the droplets is investigated. PIV measurements are carried out where the evidence of elongational regimes is demonstrated. Such experiments are also interesting for future comparisons with numerical results.     

Interfacially active particles in droplet/matrix blends of model immiscible homopolymers: Particles can increase or decrease drop size

Particles have been shown to adsorb at the interface between immiscible homopolymer melts and to affect the morphology of blends of those homopolymers. We examined the effect of such interfacially active particles on the morphology of droplet/matrix blends of model immiscible homopolymers. Experiments were conducted on blends of polydimethylsiloxane and 1,4-polyisoprene blended in either a 20:80 or 80:20 weight ratio. The effects of three different particle types, fluoropolymer particles, iron particles, and iron oxyhydroxide particles, all at a loading of 0.5 vol.%, were examined by rheology and by direct flow visualization. Particles were found to significantly affect the strain recovery behavior of polymer blends, increasing or decreasing the ultimate recovery, slowing down or accelerating the recovery kinetics, and changing the dependence of these parameters on the applied stress prior to cessation of shear. These rheological observations were found to correlate reasonably well with particle-induced changes in drop size. The particles can both increase as well as decrease the drop size, depending on the particle type, as well as on which phase is continuous. The cases in which particles cause a decrease in drop size are analogous to the particle stabilization of “Pickering emulsions” well-known from the literature on oil/water systems. We hypothesize that cases in which particles increase drop size are analogous to the “bridging–dewetting” mechanism known in the aqueous foam literature.     

Droplet retraction in the presence of nanoparticles with different surface modifications

We studied the influence of nanoparticles with different surface modifications on the interfacial tension and relaxation of model polymer blend after cessation of different strains. The droplet retraction experiments were carried out on a model system composed of polydimethylsiloxane (PDMS) as the suspending fluid and polyisobutylene (PIB) as droplet at room temperature in the presence of hydrophobic and hydrophilic nanosilica. Different weight fractions of particles were dispersed in the PIB droplet before forming a dispersed droplet by using a microsyringe in shear cell. We found that applied strain, nanoparticle concentration and their thermodynamically preferred localization affect both nominal interfacial tension and droplet retraction process. By addition of nanoparticles at a concentration as low as 0.2%wt, the nominal interfacial tension decreases from 3.12?±?0.15 mN/m for neat PIB-PDMS interface depending on the surface characteristics of nanosilica. Hydrophilic nanosilica has the most effect on nominal interfacial tension and decreases it as low as 0.2?±?0.21 mN/m at 1 wt.% loading under a strain of 7. The results show that the retraction process in this system is mainly controlled by interfacial phenomena rather than bulk rheological properties. Additionally, the shape evolution of droplets changes and the retraction rate slows down in the presence of nanoparticles.     

Role of droplet bridging on the stability of particle-containing immiscible polymer blends

The effect of micron-sized hydrophobic calcium carbonate particles on the stabilization of polydimethylsiloxane (PDMS)/polyisobutylene (PIB) immiscible model blends is investigated in this study. The analytical splitting of bulk and liquid–liquid interface contributions from the droplet bridging one is successfully performed due to the negligible contribution of hydrophobic microparticles to the bulk rheology of phases. The presence of particles at the fluid–fluid interface is supported by wetting parameter calculation and verified by optical microscopy observations. Moreover, direct visualizations shows that particles are able to form clusters of droplets by simultaneously adsorbing at two fluid–fluid interfaces and glue-dispersed droplets together, probably due to the patchy interactions induced by heterogeneous distribution of particles along the interface. Rheological studies show that the flow-induced coalescence is slowed down upon addition of particles and almost suppressed with the addition of 4 wt% particles. The linear viscoelastic response is modeled to estimate interfacial tension by considering the contribution of particle-induced droplet aggregation in addition to bulk and droplet deformation ones. From linear and nonlinear viscoelastic responses, the improved stability of filled polymer blends is attributed to the interfacial rheology and/or the bridged structure of droplets, even though the interfacial area is not fully covered by particles. Furthermore, Doi–Ohta scaling relations are investigated by employing stress growth response upon step-up of shear flow.     

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.     

Capillary-driven percolating networks in ternary blends of immiscible polymers and silica particles

We investigate the structure and rheology of a melt-blended ternary system composed of a continuous polymer phase, silica particles in the few-micron size range, and a small amount of a second immiscible polymer phase which preferentially wets the particles. The morphology of the ternary system is found to consist of a volume-spanning “pendular network” of particles bridged by menisci of the wetting polymer, as well as “capillary aggregates” which are large compact particle aggregates saturated by the wetting polymer. The ternary blends have strongly non-Newtonian melt rheology due to the pendular network. The relative extent of capillary aggregation depends on the melt-blending history, and the rheological properties can be used to track the changes in the blend structure. The pendular network is seen at a particle loading of only 10 vol.%, demonstrating that capillary bridging lowers the percolation threshold of a particle-filled polymer.      

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.     

Effect of polymer bridging on rheological properties of dispersions of charged silica particles in the presence of low-molecular-weight physically adsorbed poly(ethylene oxide)

 The effect of a low-molecular-weight physically adsorbed poly(ethylene oxide) on the rheological behavior of aqueous dispersions of silica particles (as a model system) has been investigated. Particular attention is given to the evolution of the rheological behavior with increasing polymer concentration in the system at different volume fractions of the particles. Experiments were performed in the absence of salt and just the pH of the dispersion was adjusted to 9.5, a condition at which the system is electrostatically stable and electrostatic repulsive forces are long range in nature. It was observed that the shear viscosity and the linear viscoelastic functions of the dispersion at 55 vol% increase initially through the addition of polymer, reach a maximum, and then decrease to a minimum with further addition of polymer to the system. At higher polymer concentrations, there may be an increase in the viscosity of the dispersion owing to an increase in the concentration of free polymer chains in the medium causing depletion flocculation in the system. The increase in the rheological behavior of the dispersion at low polymer coverage is attributed to polymer bridging flocculation caused by a low-molecular-weight poly(ethylene oxide) in the system. Comparison of the data given here with the results of earlier studies on the viscosity behavior of the system in the presence of salt (0.01 M) indicates that the range of the electrostatic repulsion has a significant role in the rheological behavior of the system. Received: 7 February 2001 Accepted: 18 October 2001     

Capture of small drops by large drops in an electric field

In the investigation of the process of the breakdown of emulsions by the coalescence of drops, up to the present time, use has been made of the theory of the coagulation of colloids (for example, [1]). However, there is a considerable difference between colloids and emulsions. Forces of attraction, bringing about the coalescence of two colloidal particles, become predominant at distances much greater than the particle size, so that, in a hydrodynamic sense, it can be assumed that colloidal particles do not interact. On the contrary, the disperse phase in emulsions consists of molecularly smooth spherical drops with a size from a few tenths of a micron or more and, with approach of the drops, forces of hydrodynamic interaction, inhibiting coalescence, become substantial. As a rule, the drops can be regarded as rigid undeformed spheres since their surface is stabilized by surface-active substances. With the approach of such spheres, the layer of liquid between them generates a braking force proportional to the rate of approach of the drops and inversely proportional to the distance between their surfaces. As a result, the approach of drops under the action of a finite force takes place over an infinite time. It follows from this that the process of the coalescence of drops requires the presence of a force of attraction, rising to infinity with approach of the drops, and any theory of coalescence must take simultaneous account of the forces of attraction of the drops and of the hydrodynamic forces.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 5, pp. 61–68, September–October, 1973.     

Dynamic rheological properties of a fumed silica grease

The thermo-rheological characteristics of a fumed silica lubricating grease in linear and nonlinear oscillatory experiments have been investigated. The material rheological behavior represents a soft solid being thermo-rheologically complex. There is an abnormal temperature dependency in the range of ??10 to 10 °C which is related to the phase transition of the base oil. The dynamic moduli data in linear viscoelastic envelop (LVE) have been modeled using mode-coupling theory (MCT) in the whole temperature range. Two main relaxation mechanisms can be identified through linear and nonlinear viscoelastic properties related to interaction of the primary particle and its neighbor particles as well as a slow relaxation process which represents the escape of this particle from its “cage”. Finally, it is demonstrated that the dominant yielding process in large amplitude oscillatory experiments can be explained based on either particle cage rupture (consistent with MCT framework) or particle “hopping” out of its cage proposed in soft glassy rheology (SGR) model. It will be discussed that the governing mechanism depends on the applied frequency.     

A phenomenological modification of rheological models for concentrated two-phase systems: application to a thermoplastic/thermoset blend

This paper considers an improvement of the emulsion models to take into account concentrated emulsions with no coalescence but with significant interaction between particles. For this purpose, a term proportional to the volume fraction of material in excess to the percolation threshold is added to the dynamic modulus. Its usefulness was tested to model the viscoelastic behavior in oscillatory shear flow of concentrated and diluted blends of a thermoplastic polystyrene with an epoxy-amine thermoset. These blends experience phase separation upon polymerization and the volume fraction of separated phase varies continuously with time. At low volume fraction of dispersed phase, the behavior could be described with a simple emulsion model that takes into account the plastisizing, dilution, and phase separation mechanisms. However, for concentration in excess to the percolation threshold, the modification can cope with a larger increase in the modulus related to the mechanical percolation of the dispersed particles.