Brownian dynamics simulation of multiphase suspension of disc-like particles and polymers

A computational model is proposed for simulating the flow of polymer nanocomposites. This model is based on a multiphase suspension of disc-like particles and polymers. The particles are represented by oblate spheroid particles that interact with each other via the Gay-Berne (GB) potential, and the polymers are modeled by finitely extensible nonlinear elastic (FENE) chains that interact with each other via the repulsive Lennard-Jones potential. The interaction between an oblate spheroid particle and a FENE chain is also considered using a modified GB potential. A Brownian dynamics simulation of the shear flows of this system was conducted to investigate the orientation behavior of disc-like particles and the rheological properties of this system. The orientation of disc-like particles was affected by polymers, and the particles in a suspension were well aligned in flows because of the flow orientation property of polymers. The predicted shear viscosity exhibited shear thinning, and the normal stress differences agree qualitatively with experimental measurements of polymer/clay nanocomposites. The simulation results suggest that the present model has the potential to be used as a computational model for polymer nanocomposites.     

Micron-scale origin of the shear-induced structure in Laponite–poly(ethylene oxide) dispersions

We study the transient response to simple shear of aqueous dispersions of Laponite clay particles and poly(ethylene oxide) at concentrations for which shear induces structure in the form of a network of polymer–clay bonds. We examine the effects of shear on the structure at the micrometer length scale. Bulk rheometric measurements give the material’s response to step changes in shear rate. We find that a critical value of the shear rate separates two regions with different rheological behaviors. Static small-angle light scattering shows a corresponding qualitative change in the anisotropy of the dispersion under shear at the micron scale. We interpret our results in terms of the effects of shear on the interactions between clay particles and polymer chains and on the aggregation mechanisms in the dispersion.     

Effects of anionic additives on the rheological behavior of aqueous calcium montmorillonite suspensions

Three different experimental measurements, namely, rheology, particle sizing, and x-ray diffraction (XRD), were used to study the effect of anionic additives on the properties of bentonite suspensions. The three additives were sodium carboxymethylcellulose, xanthan gum, and sodium dodecyl sulfate. Flow curves were obtained from shear stress–shear rate measurements, and the viscoelastic properties were determined from oscillatory and transient measurements. Mineralogical data were evaluated by XRD and the particle size analysis performed by light scattering technique. The presence of the surfactant modifies the face-to-face interactions and yields changes of the mixtures rheological behavior at low deformation rates. Polymers act by coating each clay particle and prevent their agglomeration. Therefore, the additives are responsible for the mechanisms of destructuration and structure reorganization as well as the mixtures viscous and viscoelastic behavior.     

Shear behaviour of biopolymer suspensions with spheroidal and cylindrical particles

The rheological behaviour of suspensions is influenced by many parameters, one of which is the particle shape. For rigid particle suspensions a number of studies demonstrate the effects of the particle aspect ratio. Indeed, fibres are widely used as rheology modifiers in different materials such as synthetic polymers. This work is concerned with testing the hypothesis that regularly shaped particles with aspect ratios larger than one that are made of gelled biopolymers could be used as rheology modifiers for biopolymer solutions. Biopolymers, and mixtures thereof are a widely used ingredient in foods and other products with structure functionality. Tailoring rheology modifiers by morphology offers an alternative to using different biopolymers. It is demonstrated how biopolymer suspensions with regular spheroidal, or cylindrical particle shapes can be produced by gelling the droplet phase of a liquid two phase biopolymer mixture in a shear field. Biopolymers were chosen such that gelation is initiated by cooling. Shear-cooling at constant stresses leads to the formation of ellipsoidal particles. Cylindrical particles can be generated by stepping up the shear stress prior to gelation, i.e., stretching the droplet phase into fibrils, and trapping the shape prior to break-up through gelation. Morphologies and steady shear rheological data for suspensions of the two biopolymers gellan and κ-carrageenan with an internal phase volume of 0.2 are reported. The influence of particle shape on relative viscosity is pronounced. At high shear stresses particle orientation leads to decreased viscosity with increasing particle aspect ratio. In the low shear region, higher aspect ratio suspensions show higher viscosities. Additionally, the material properties, including the interfacial tension, which influence the suspension morphology are reported. Received: 3 March 2000 Accepted: 22 August 2000     

Simple Shear Flow of Suspensions of Elastic Capsules

The simple shear flow of homogeneous suspensions of two-dimensional capsules enclosed by elastic membranes is studied in the limit of vanishing Reynolds number, in the special case where the viscosity of the fluid enclosed by the capsules is equal to the viscosity of the ambient fluid. The deformation of capsules with circular, elliptical, and biconcave unstressed shapes, and the rheological and statistical properties of their infinitely dilute and moderately dense suspensions are investigated by dynamical simulation using the method of interfacial dynamics for Stokes flow. In a preliminary investigation, the behavior of solitary capsules suspended in an infinite fluid is studied as a function of the dimensionless membrane elasticity number expressing the capsule deformability or the strength of the shear flow. It is found that a critical elasticity number above which a capsule exhibits continued elongation does not exist, and an equilibrium configuration is reached no matter how large the shear rate, in agreement with previous results for three-dimensional flow. A correspondence is established between the elasticity numbers for two- and three-dimensional flow at which the capsules undergo the same degree of deformation. Simulations of pairwise capsule interceptions reveal behavior similar to that exhibited by liquid drops with uniform surface tension. Because of strong hydrodynamic interactions in two-dimensional Stokes flow, the concept of hydrodynamic diffusivity in the limit of infinite dilution is ill-defined in the absence of fluid inertia. Dynamical simulations of doubly periodic monodisperse suspensions with up to 50 capsules distributed in each periodic cell at areal fractions of 0.25 and 0.40 provide information on the effective rheological properties of the suspension and on the nature of the statistical properties of the particle motion. The character of the flow is found to be intermediate between that of liquid drops and rigid particles, and this is attributed to the membrane deformability and to the ability of the interfaces to perform tank-treading motion. The results are compared with rheological measurements of blood flow with good agreement. Received 26 April 1999 and accepted 5 October 1999     

Shear-dependent thermal conductivity of alumina nanofluids

The thermal conductivities (k) of aqueous alumina nanofluids of various particle shapes (rods, bricks, blades) were measured at the dynamic state for the first time. The dynamic k was measured under torsional flows by using a homemade parallel-plate system. The homemade system was validated by numerical simulations and experiments with homogeneous liquids. All the nanofluids tested here showed decreasing k with increasing shear rate. This newly observed phenomenon was named ‘shear-reducing thermal conductivity.’ The dispersion characteristics were characterized by the dynamic light scattering (DLS) and rheological techniques. From the rheological properties of nanofluids it was inferred that the alumina nanofluids should have network structures and these microstructures should be destroyed or deformed by shearing. But not all the networks were destroyed by shearing. The DLS data revealed that some nanoparticles in nanofluids should exist as individual particles. The effective medium theory cannot explain the shear-reducing characteristics of nanofluids at the dynamic state. The rheological data imply that the heat percolation through the network may not be the sole reason for heat transfer enhancement in nanofluids. It is suggested that the Brownian motion of the primary particles cannot be excluded in heat conduction through nanofluids.     

Dispersion state and rheology of hectorite particles in water over a broad range of salt and particle concentrations

The relationship between the rheological properties of deionized aqueous suspensions of hectorite particles and the dispersion states of the particles has been studied with a broad range of salt and particle concentrations. The shear viscosity of the hectorite suspensions decreases drastically after exhaustively deionizing the suspensions with ion-exchange resins. By means of DLS measurements, it is clarified that the average size of the flocs of hectorite particles decreases and reaches the Stokes diameter of the individual particle as the degree of deionization advances. This fact strongly supports the idea that the electrical double layer around the hectorite particles expands significantly in the exhaustively deionized state and the particles are well-dispersed individually and do not form a three-dimensional network structure composed of particles, whereas such a network structure forms in the presence of a large amount of salt. In the case of exhaustively deionized state, the suspension forms a glassy state, at high particle fractions. The results show the importance of the electrical double layer that causes a strong repulsive force among the particles on the particle dispersion state, especially in the exhaustive deionization area below 10^− 4 M, and on the rheological properties; the hectorite suspension can be considered a Newtonian liquid in the deionized state, but it becomes elastic-solid in the presence of salt above a certain concentration confirmed by normal stress measurements.     

Linear and non-linear viscoelastic properties of ethylene vinyl acetate/nano-crystalline cellulose composites

This paper reports on the melt rheological properties of ethylene vinyl acetate containing between 0 and 10 wt.% of nano-crystalline cellulose (NCC). A complete set of rheological tests including frequency sweeps, shear transients, and uniaxial elongations was performed. Frequency sweeps showed that at low frequencies, a pseudo solid-like behavior was obtained for NCC concentrations higher than 5%. This behavior was related to hydrogen bonding between NCC particles and the creation of particle networks as the result of particle–particle interactions. For transient shear tests, all compositions presented a stress overshoot at high shear rates before reaching a steady state. It was found that the amplitude of this overshoot depends on both NCC content and shear rate. On the other hand, the time to reach the maximum was found to be highly shear rate dependent but concentration dependence was rather weak. For uniaxial extensional flow, higher extensional viscosity was observed with increasing NCC content. On the other hand, strain hardening was found to decrease with increasing NCC content.     

The effect of pH,ionic strength,and temperature on the rheology and stability of aqueous clay suspensions

The effect of pH level, ionic strength, and temperature on the theology and stability of aqueous suspensions of attapulgite clay was systematically investigated. A Rheometrics Mechanical Spectrometer with cone and plate fixtures was used to measure the steady shear viscosity of the system. The edge charges of the clay particles can be adjusted by changing the pH level of the suspending medium so as to influence the flocculation state and, consequently, the rheological behavior of the suspension. This pH effect may be counteracted by the ionic strength effect at both very high and very low pH levels where the ionic strength is high enough to cause flocculation of the electrostatically stabilized suspension. The temperature effect study indicates that the relative contribution of Brownian motion and shear flow to the viscosity is dependent on the flocculation state of the suspension.     

Experiments on transport of hydrophobic particles and gas bubbles in porous media

Adhesion of hydrophobic colloids (clay minerals) on the surface of bubbles of air and the transport of the composite units formed by bubbles and mineral particles were observed in a glass micro model.When a clay mineral suspension flowed in a porous medium that contained bubbles of air trapped in small pores, particles accumulated preferentially on the upstream portion of the bubbles, and quasi-stable bubble-mineral particle units were formed. With an increase in the flow velocity, the particles moved along the interface between the bubble and the liquid and accumulated on the downstream portion of the bubbles. A large stress could mobilize the units which, occasionally, accumulated in larger voids.The mechanism suggested is adhesion of the particles on the surface of the bubble due to compression of their diffuse electrical double layer. The adsorbed particles can be moved by shear stresses which act in the region of water molecules between the well-organized layers of water on the surfaces of the bubble and the clay particles. A large enough shear stress causes the bubbles to become more streamlined, allowing them to move in the channel system. If in contact, the common lamina of the bubbles can withdraw and rupture.Bubbles transport from 20 to 50 times more particles than can be transported by average suspension.     

Rheological studies in the bulk and at the interface of Pickering oil/water emulsions

The rheological behavior and interfacial properties of olive oil–water emulsions stabilized by surfactant and clay particles (smectite) were studied to evaluate the effect of particles and surfactant distribution both in the bulk phase and at the oil–water interface. The temperature sweep of surfactant solutions and emulsions with and without clay particles showed the critical effect of the solid particles on the viscosity change. The mechanism of adsorption of surfactant molecules onto clay particles has a direct impact on the micellization and gelling temperatures. Indeed, the presence of clay particles caused a slight decrease in the micellization temperature and a total cancellation of the gelling phenomenon. Dynamic interfacial tension values demonstrated that clay particles would not compete with the surfactant for adsorption at the interface. However, the significant increase in the elastic properties of the interface that was observed accounts for their accumulation in the vicinity of the interface, probably at the level of surfactant polar head groups. Thus, the clay particles would form a mechanical barrier, preventing coalescence of emulsion droplets.     

A rheological criterion to determine the percolation threshold in polymer nano-composites

In this work, the effect of multi-walled carbon nanotube (CNT) and montmorillonite nanoclay on polymer chain dynamics is investigated around the percolation concentration for systems based on ethylene vinyl acetate (EVA) copolymer. Then, the results obtained are compared with literature data to determine if, regardless of particle characteristics, a universal rheological behavior can be detected at percolation. To do so, rheological analyses are performed under small amplitude oscillatory shear (SAOS), large amplitude oscillatory shear (LAOS), and transient shear step. SAOS data showed that, while the dynamics related to the Rouse relaxation time (τ _R) were not significantly influenced, the reptation relaxation time (τ _D) was strongly increased by the presence of nanoparticles. In step shear transient tests, the critical shear rate \( \left({\dot{\upgamma}}_{\mathrm{cr}}\right) \) for overshoot appearance was decreased due to chain confinement, and the formation of particle network strongly increased the level of stress overshoot. Particle networks increased significantly the nonlinear parameters (I ₃/I ₁ and Q ₀) obtained under LAOS and quantified by FT-rheology. In all measurements, due to the higher surface area associated to its size and density as well as hollow structure, CNT showed stronger effects compared to clay. Moreover, while the percolation concentration was different for CNT and clay, both systems showed similar behavior at percolation: a 0.5 scaling for G′ indicating a Rouse-dominated behavior.     

Rheological characterization of bimodal colloidal dispersions

In order to investigate the effect of the particle size distribution on the rheological properties of concentrated colloidal dispersions both steady-state shear and oscillatory measurements have been performed on well-characterized bimodal dispersions of sterically stabilized PMMA particles. Replacing a minor amount of large particles by small ones in a concentrated dispersion, keeping the total effective volume fraction constant, decreases the viscosity quite drastically. On the other hand, replacing a small amount of small particles by big ones hardly effects the viscosity at all. This behavior can be attributed to the deformability of the stabilizing polymer layer. A procedure is proposed to calculate the limiting viscosities in a bimodal colloidal dispersion starting from the characteristics of the monodisperse systems. A good agreement has been obtained between the calculated values and the experimental results. The linear viscoelastic properties of the concentrated dispersions have been investigated by means of oscillatory measurements. The plateau values of the storage modulus for the bimodal dispersions decrease with an increasing fraction of the coarse particles. By substituting the bimodal dispersion by an equivalent monodisperse system the storage modulus can be superimposed on the values for the monodisperse suspensions when plotted as a function of the mean interparticle distance.     

Shear-induced changes of electrical conductivity in suspensions

The effect of shear on electrical conductivity (rheo-conduction) is studied to give information about particle behaviour in suspensions. Past work is reviewed, and expressions are derived for the rheo-conduction of a suspension of nonconducting spheroids in a conducting matrix for current flow, parallel and normal to the suspension flow direction. A simple apparatus to study rheo-conduction in pipe flow is described, and measurements of steady and time-dependent effects are reported for various suspensions of colloidal particles. Suspensions of anisometric rod- and platelike particles at low concentrations showed rheo-conductive changes of sign, magnitude and relaxation that were consistent with the particle shape, concentration and interactions. The rheo-conductive response decreased with increasing volume fraction for platelike kaolinite particles, attributed to orientational jamming. Spherical latex particles gave unexpected rheo-conductive changes consistent with shear disruption of a conductive network of particles. It is concluded that rheo-conduction measurements are a useful adjunct to conventional rheometry.     

Rheological properties and percolation in suspensions of multiwalled carbon nanotubes in polycarbonate

This paper is concerned with several issues related to the rheological behavior of polycarbonate/multiwalled carbon nanotube nanocomposites. The composites were prepared by diluting a masterbatch of 15 wt.% nanotubes using melt-mixing method, and the dispersion was analyzed by SEM, TEM, and AFM techniques. To understand the percolated structure, the nanocomposites were characterized via a set of rheological, electrical, and thermal conductivity measurements. The rheological measurements revealed that the structure and properties were temperature dependent; the percolation threshold was significantly lower at higher temperature suggesting stronger nanotube interactions. The nanotube networks were also sensitive to the steady shear deformation particularly at high temperature. Following preshearing, the elastic modulus decreased markedly suggesting that the nanotubes became more rigid. These results were analyzed using simple models for suspensions of rod-like particles. Finally, the rheological, electrical, and thermal conductivity percolation thresholds were compared. As expected, the rheological threshold was smaller than the thermal and electrical threshold.     

Effect of viscoelasticity on the rotation of a sphere in shear flow

When particles are dispersed in viscoelastic rather than Newtonian media, the hydrodynamics will be changed entailing differences in suspension rheology. The disturbance velocity profiles and stress distributions around the particle will depend on the viscoelastic material functions. Even in inertialess flows, changes in particle rotation and migration will occur. The problem of the rotation of a single spherical particle in simple shear flow in viscoelastic fluids was recently studied to understand the effects of changes in the rheological properties with both numerical simulations [D’Avino et al., J. Rheol. 52 (2008) 1331–1346] and experiments [Snijkers et al., J. Rheol. 53 (2009) 459–480]. In the simulations, different constitutive models were used to demonstrate the effects of different rheological behavior. In the experiments, fluids with different constitutive properties were chosen. In both studies a slowing down of the rotation speed of the particles was found, when compared to the Newtonian case, as elasticity increases. Surprisingly, the extent of the slowing down of the rotation rate did not depend strongly on the details of the fluid rheology, but primarily on the Weissenberg number defined as the ratio between the first normal stress difference and the shear stress.In the present work, a quantitative comparison between the experimental measurements and novel simulation results is made by considering more realistic constitutive equations as compared to the model fluids used in previous numerical simulations [D’Avino et al., J. Rheol. 52 (2008) 1331–1346]. A multimode Giesekus model with Newtonian solvent as constitutive equation is fitted to the experimentally obtained linear and nonlinear fluid properties and used to simulate the rotation of a torque-free sphere in a range of Weissenberg numbers similar to those in the experiments. A good agreement between the experimental and numerical results is obtained. The local torque and pressure distributions on the particle surface calculated by simulations are shown.     

Influence of particle shape on the microstructure evolution and the mechanical properties of granular materials

In order to study the influence of particle shape on the microstructure evolution and the mechanical properties of granular materials, a two-dimensional DEM analysis of samples with three particle shapes, including circular particles, triangular particles, and elongated particles, is proposed here to simulate the direct shear tests of coarse-grained soils. For the numerical test results, analyses are conducted in terms of particle rotations, fabric evolution, and average path length evolution. A modified Rowe's stress–dilatancy equation is also proposed and successfully fitted onto simulation data.     

A self-similar behavior for the relative viscosity of concentrated suspensions of rigid spheroids

A viscosity model for suspensions of rigid particles with predictive capability over a wide range of particle volume fraction and shear conditions is of interest to quantify the transport of suspensions in fluid flow models. We study the shear viscosity of suspensions and focus on the effect of particle aspect ratio and shear conditions on the rheological behavior of suspensions of rigid bi-axially symmetric ellipsoids (spheroids). We propose a framework that forms the basis to microscopically parameterize the evolution of the suspension microstructures and its effect on the shear viscosity of suspensions. We find that two state variables, the intrinsic viscosity in concentrated limit and the self-crowding factor, control the state of dispersion of the suspension. A combination of these two variables is shown to be invariant with the imposed shear stress (or shear rate) and depends only on the particle aspect ratio. This self-similar behavior, tested against available experimental and numerical data, allows us to derive a predictive model for the relative viscosity of concentrated suspensions of spheroids subjected to low (near zero) strain rates. At higher imposed strain rates, one needs to constrain one of the state variables independently to constrain the state of dispersion of the suspension and its shear dynamic viscosity. Alternatively, the obtained self-similar behavior provides the means to estimate the state variables from the viscosity measurements made in the laboratory, and to relate them to microstructure rearrangements and evolution occurring during deformation.     

Assessment of assembly shape and geometric effects on amplification of shear waves using discrete element method

The discrete element method (DEM) is a capable tool used to simulate shear wave propagation in granular assemblies for many years. Researchers have studied assembly shapes such as rectangles (in 2D simulations) or cylinders and cubes (in 3D simulations). This paper aimed to qualify the effect of assembly shape on the shear wave propagation and maximum amplification in the vertical plane (horizontal and vertical directions) caused by this propagation. To this end, shear wave propagations in different assembly shapes such as rectangle, trapezium, and triangle with rigid boundary conditions were simulated. A sine wave pulse was applied with a point source by moving a particle as the transmitter particle. To evaluate the shear wave velocity of the assemblies, the transmitter and receiver particles were simulated. All the simulations were performed with 2D DEM which is a useful tool to determine the amount and location of the maximum amplification factor of the assembly in both horizontal and vertical directions. An advantage of this study was assessing the effect of parameters such as input wave frequency, assembly height, shape, and aspect ratios on the amplification of the input waves.     

Effects of particle softness on the rheology and yielding of colloidal glasses

We studied the linear and nonlinear rheology of colloidal glasses consisting of hard spheres and soft core-shell particles at several volume fractions to explore the effects of particle softness on the mechanical properties and yielding. Creep and recovery and oscillatory shear measurements were used to determine the shear elastic modulus and the yield strain. Both hard and soft sphere glasses exhibited ‘entropic cage elasticity’ below random close packing, whereas for compressed soft spheres at higher effective volume fractions, the yield strain was determined by shell elasticity. The shear modulus followed a strong increase with volume fraction for hard spheres and a much weaker one for soft particles reflecting their interparticle potential. Nonlinear effects, revealed as strong distortions of the stress signal during yielding, were analyzed via Fourier transform rheology and Lissajous plots. The significant contribution of the nonlinearities was analyzed in terms of strain softening and hardening mechanisms within a cycle of oscillation and discussed in relation to particle softness.