Large amplitude oscillatory shear of pseudoplastic and elastoviscoplastic materials

We explore the utility of strain-controlled large amplitude oscillatory shear (LAOS) deformation for identifying and characterizing apparent yield stress responses in elastoviscoplastic materials. Our approach emphasizes the visual representation of the LAOS stress response within the framework of Lissajous curves with strain, strain rate, and stress as the coordinate axes, in conjunction with quantitative analysis of the corresponding limit cycle behavior. This approach enables us to explore how the material properties characterizing the yielding response depend on both strain amplitude and frequency of deformation. Canonical constitutive models (including the purely viscous Carreau model and the elastic Bingham model) are used to illustrate the characteristic features of pseudoplastic and elastoplastic material responses under large amplitude oscillatory shear. A new parameter, the perfect plastic dissipation ratio, is introduced for uniquely identifying plastic behavior. Experimental results are presented for two complex fluids, a pseudoplastic shear-thinning xanthan gum solution and an elastoviscoplastic invert-emulsion drilling fluid. The LAOS test protocols and the associated material measures provide a rheological fingerprint of the yielding behavior of a complex fluid that can be compactly represented within the domain of a Pipkin diagram defined by the amplitude and timescale of deformation.     

Large amplitude oscillatory shear behavior of PEO-PPO-PEO triblock copolymer solutions

Rheological properties of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer solution in both linear and nonlinear regions have been investigated. PEO-PPO-PEO triblock copolymer solution shows a dramatic change in mechanical properties as temperature changes. PEO-PPO-PEO triblock copolymer undergoes a transition from sol to gel with increase of temperature. During this transition the copolymer solution passes through three different stages, namely sol, soft gel, and hard gel. In our previous research (Hyun et al. in J Non-Newtonian Fluid Mech 55:51–65, 2002), large amplitude oscillatory shear (LAOS) behavior was found to be very sensitive to the generated microstructures. In this study, we investigated the relationship between the LAOS type and the microdomain structure. Newtonian behavior is observed in sol region, while there appear two kinds of LAOS types in the soft gel region. One is type I (G′, G′′ decreasing) and the other is a combination of type I and type IV (G′, G′′ increasing followed by decreasing). Type III (G′ decreasing, G′′ increasing followed by decreasing) is observed in the hard gel region. We compared the shape of stress curves, Lissajous pattern, and Fourier transform (FT) rheology of hard gel and soft gel under LAOS, and tried to relate the complex LAOS behavior with the microstructural change. From these investigations, it was found that the LAOS behavior and the stress pattern at large strain are closely related to the microdomain structure of PEO-PPO-PEO triblock copolymer, and provide a lot of useful information on the microstructures induced by large deformation.     

Large amplitude oscillatory shear behavior of graphene derivative/polydimethylsiloxane nanocomposites

Rheological properties of three different nanocomposites, consisting of graphene oxide (GO), reduced graphene oxide (rGO), and polyhedral oligomeric silsesquioxane grafted reduced graphene oxide (rGO-POSS) as nanofillers and polydimethylsiloxane (PDMS), were investigated by large amplitude oscillatory shear (LAOS). The viscoelastic nonlinearity of the three nanofluids groups was studied by Lissajous curves, local nonlinear viscoelastic moduli of an oscillatory shear cycle, and Fourier transform rheology as a function of filler concentration and increasing and decreasing strain magnitude. The nonlinear behavior of the nanofluids was compared to understand the variation of internal microstructures. Firstly, GO/PDMS composites behave with higher moduli and smaller linear viscoelastic range comparing to that of other two composites. Secondly, the elastic stress Lissajous curves of these composites changed from elliptic to rectangular with round the corner with increasing the filler level and strain amplitude. Thirdly, all these three nanofluids exhibited intra-cycle strain stiffening with increasing strains and shear thickening at intermediate strain and then shearing thinning with increasing strain further. Fourthly, higher harmonic intensity of rGO/PDMS increased with increasing strain and came to a plateau, while that of other two nanofluids reached a maximum and then decreased. It suggested that different surface functionalization of nanoparticles will present different rheological behavior due to formed different network and LAOS could be used as a potential helpful method to characterize rheological properties of nanocomposites, especially at higher shear strain.     

A classical problem revisited: rheology of nematic polymer monodomains in small amplitude oscillatory shear

We revisit the classical problem of the viscoelastic response of nematic (liquid crystal) polymers to small amplitude oscillatory shear. A multiple time scale perturbation analysis is applied to the Doi–Hess mesoscopic orientation tensor model to describe key features observed of longtime experiments, both physical (Moldenaers and Mewis, J Rheol, 30:567–584, 1986; Larson and Mead, J Rheol, 33:1251–1281, 1989b) and numerical (herein). First, there is a very slow time scale drift in the envelope of oscillations of the major director; we characterize the mean director angle and the envelope of oscillation. Second, there are bistable asymptotic orientational states, distinguished in that they are precisely the zero-stress orientational distributions noted in Larson and Mead (J Rheol, 33:185–206, 1989a). Third, the drift dynamics and asymptotic mean director angle are determined by the initial orientation of the director, not by material properties; we characterize the domain of attraction of each bistable state. Finally, the director drift leads to a predicted longtime decrease in the storage and loss moduli, consistent with experimental observations.

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Large amplitude oscillatory elongation flow

A filament stretching rheometer (FSR) was used for measuring the elongation flow with a large amplitude oscillative elongation imposed upon the flow. The large amplitude oscillation imposed upon the elongational flow as a function of the time t was defined as where ε is the Hencky strain, is a constant elongational rate for the base elongational flow, Λ the strain amplitude (Λ ≥ 0), and Ω the strain frequency. A narrow molecular mass distribution linear polystyrene with a molecular weight of 145 kg/mol was subjected to the oscillative flow. The onset of the steady periodic regime is reached at the same Hencky strain as the onset of the steady elongational viscosity ( Λ = 0). The integral molecular stress function formulation within the ‘interchain pressure’ concept agrees qualitatively with the experiments.     

Fluid inertia in large amplitude oscillatory shear

Homogeneous shearing is required in sliding plate flow experiments with one plate fixed and the other oscillating. However, when fluid inertia becomes significant, the velocity gradient and the stress will not be uniform. MacDonald et al. (1969) and Schrag (1977) investigated this effect for a linear viscoelastic fluid. However, linear viscoelasticity does not describe the behavior of melts in large amplitude oscillatory shear (LAOS). Jeyaseelan et al. (1993) have shown that the Berkeley kinetic network model does accurately describe the LAOS behavior of polymer melts. In this work, the Berkeley model is solved for LAOS in sliding plate flow with fluid inertia, by numerical integration of spatially discretized forms of the governing equations. Nonlinear viscoelasticity is predicted to aggravate the effects of fluid inertia in LAOS and experiments confirm this. Specifically, fluid inertia amplifies the first harmonic and produces no even harmonics. Operating limits are presented graphically for minimizing inertial effects in LAOS experiments. Received: 2 January 1998 Accepted: 27 April 1998     

Large amplitude oscillatory extension of soft polymeric networks

Using a filament stretching rheometer surrounded by a thermostatic chamber and equipped with a micrometric laser, it is possible to measure large amplitude oscillatory elongation (LAOE) on elastomeric based networks with no base flow as in the LAOE method for polymer melts. Poly(dimethylsiloxane)-based networks, considered as a model system for studying the development of soft elasticity, are mechanically characterised through reversed LAOE deformation, applying oscillatory measurements with several amplitudes and frequencies.     

Steady shear rheology of dilute polystyrene particle gels

This paper describes an experimental study on dispersions of monodisperse polystyrene (PS) spheres with a typical radius of 1 μm, dispersed in an electrolyte at high ionic strength, screening the electrostatic repulsion. These suspensions gelate at rest even at low volume fractions of PS particles. The density of the particles is matched with the solvent by using deuterium oxide for volume fractions φ≤0.117. Steady-state flow curves, viscosity as a function of shear rate, are measured and reported for 0.014<φ<0.322. The measured flow curves are analyzed on the basis of two models: 1. In the giant floc model (van Diemen and Stein 1983, 1984; Schreuder et al. 1986, 1987; Laven et al. 1988), at low shear rates, the shear is not distributed homogeneously but is limited to certain shear planes; the energy dissipation during steady flow is due primarily to overcoming the viscous drag on the suspended particles during motion caused by encounters of particles in the shear planes. Though this model was developed for higher solid volume fractions (0.35–0.425), we found that it also describes the rheology of dilute particle gels for 0.15≤φ≤0.3, using the same values for the parameters in the model as in the high solid volume fraction region. For φ<0.15, the model also describes the data if the fraction of distance by which a moving particle entrains its neighbors, is assumed to increase in this φ region. 2. The model of de Rooij (de Rooij et al. 1993, 1994) considers aggregates in shear flow to be monodisperse impermeable spheres with a fractal structure. The permeability is taken into account by considering a hydrodynamic radius smaller than the gyration radius in the Krieger-Dougherty expression for the hydrodynamic contribution to the viscosity. Through the use of a yield criterion the aggregate radius is modeled as a function of shear rate. We found that the model describes our experimental results, with a combination of parameter values used already by de Rooij, but only for φ<0.15. Received: 7 May 1998 Accepted: 22 December 1998     

Numerical simulation of a drop undergoing large amplitude oscillatory shear

Direct numerical simulations are conducted for a Newtonian drop in a Newtonian matrix subjected to large amplitude oscillatory shear flows. In the experimental study of Guido et al. (in Rheol Acta 43:575–583, 2004), the drop shape is found to oscillate at higher harmonics of the forcing frequency when the capillary number is increased. Their phenomenological model requires a much smaller capillary number for predicting the harmonic nature of the experimental data. In this paper, computational results on the evolution of drop length and inclination angle are obtained at the same fluid and flow properties as the experiments, and are shown to reasonably reproduce the experimental data. In particular, the computed velocity fields around the drop are shown to elucidate the over-rotation, which is a mechanism for the experimentally observed harmonics.     

Prediction of normal stresses under large amplitude oscillatory shear flow

The dynamic response of viscoelastic fluids under large amplitude oscillatory shear (LAOS) has been a subject of long history. In the LAOS flow, the analysis has been mostly focused on shear stress, possibly due to the lack of accurate measurement of normal stress. However, the normal stress may become larger than shear stress at high-strain amplitudes, and thus it is important that we have a good understanding of the normal stress behavior. Furthermore, with the advancement in the instrumentation, it has become possible to get more reliable data. The purpose of this paper is to develop a research platform to analyze and to understand the normal stress behavior of complex fluids under LAOS flow. In this study, we utilized the Giesekus model as a representative constitutive model, and investigated its diverse responses. We defined the dynamic properties corresponding to normal stress, in a similar way to define dynamic moduli from shear stress, and examine their behavior with various analyzing tools. Experimental data were also compared with model predictions. Despite the fact that it is not yet possible to compare all of the predictions because of instrumental limitation, the prediction has been found to fit well with the experimental data. This study is expected to provide a useful framework for further understanding the nonlinear behavior of complex fluids at large deformation.     

Obtaining Fourier series graphically from large amplitude oscillatory shear loops

Large amplitude oscillatory shear (LAOS) flow has been used to characterize the nonlinear viscoelasticity of polymer melts and solutions. Results are frequently reported with shear stress versus strain loops, or with shear stress versus shear rate loops. A Fourier analysis of the stress response to LAOS is often desired for comparison with theory, or for quantitative comparison between resins. A method is presented which employs the discrete Fourier transform to obtain the Fourier series coefficients from LAOS loops.     

High sensitivity measurements of normal force under large amplitude oscillatory shear

The two aims of this publication are to introduce a new and rheometer-independent rheometric tool for measuring the axial normal force in oscillatory shear rheology and to study the normal forces of polyolefin melts under large amplitude oscillatory shear (LAOS). A new plate geometry with an incorporated highly sensitive piezoelectric normal force sensor was designed for a rotational rheometer. The new geometry was used to investigate normal forces of polyethylene (PE) melts under LAOS. The resulting stress and normal force data was compared with the data from measurements in commercial high performance rotational rheometers. The stress and the normal force response were Fourier-transformed and their resulting spectra were analysed. The non-linear contributions to the FT-magnitude spectra (i.e. the intensities of the higher harmonics) were analysed using the framework of the Q-parameter, \(Q=I_{3/1}/{\gamma ^{2}_{0}}\) for both the stress spectrum and the normal force spectrum, resulting in the strain-dependent \(Q\left (\gamma _{0}\right )\) and \(Q_{NF}\left (\gamma _{0}\right )\), respectively. The newly designed normal force geometry had a sensitivity in the measurement starting from \(5\times 10^{-5}\) N up to 20 N, and respectively a signal-to-noise ratio (SNR) of \(1:\) 16.000, which is about a factor of 1.8 times better than the best performing commercial rheometers. The new geometry was used to determine \(Q\left (\gamma _{0}\right )\) and \(Q_{NF}\left (\gamma _{0}\right )\), to characterize the shear rheological behaviour of the PE melts. Even rather simple rheometers, those without normal force detection, can be extended utilizing the here presented tools for high sensitive FT-rheology analysing the normal forces.     

Rheological behavior of fiber-filled polymers under large amplitude oscillatory shear flow

Small and large amplitude oscillatory shear measurements (SAOS and LAOS) were used to investigate the rheological behavior of short glass fibers suspended in polybutene and molten polypropylene. Raw torque and normal force signals obtained from a strain-controlled instrument (ARES rheometer) were digitized using an analog to digital converter (ADC) card to allow more precise data analysis. The fiber concentration did not affect the torque signal in the SAOS mode, except for its magnitude, whereas the normal force signal was too low to be measurable. With increasing strain amplitude, the magnitude of the torque became a function of time. Depending on the applied frequency and strain rate, the stress in the filled polybutene increased with time, whereas for reinforced polypropylene (viscoelastic matrix), the behavior was opposite, i.e. the stress decreased with time. These effects were more pronounced at high fiber content. In addition the primary normal stress differences were no longer negligible at large deformation amplitude and exhibited a non-sinusoidal periodic response. Fast Fourier transform (FFT) analysis was performed and the resulting spectra, along with Lissajous figures of the shear stress and the primary normal stress differences, are explained in terms of fiber orientation. The experimental results for the suspensions in polybutene are well predicted by the Folgar-Tucker-Lipscomb (FTL) model.     

Comparison of stress-controlled and strain-controlled rheometers for large amplitude oscillatory shear

In linear viscoelastic region, it is well known that dynamic modulus and dynamic compliance can be converted to each other. However, it is questionable whether there exists an interconversion between large amplitude oscillatory shear (LAOS) data measured from different types of rheometers—stress-controlled and strain-controlled rheometers. Hence, we tried to prove the existence by use of polyethylene oxide (PEO) aqueous solutions with well-developed entanglements. From this experiment, we can conclude that a stress-controlled rheometer can simulate LAOS behavior measured from a strain-controlled rheometer under the conditions where inertia effect is not significant. Furthermore, it is investigated whether the LAOS data of the stress-controlled rheometer obey stress–frequency superposition as the strain–frequency superposition found by Cho et al. (J Rheol 54:27–63, 2010) from LAOS data measured by the strain-controlled rheometer. This scaling relation shows that the dimensionless stress amplitude is a function of zeta which is the product of the stress amplitude and linear viscoelastic function J′(ω). The plot shows that all of the data are superposed in a single curve without regard to frequency, molecular weight, and concentration of PEO aqueous solutions.     

Extensional rheology of a shear-thickening cornstarch and water suspension

A filament-stretching rheometer is used to measure the extensional viscosity of a shear-thickening suspension of cornstarch in water. The experiments are performed at a concentration of 55 wt.%. The shear rheology of these suspensions demonstrates a strong shear-thickening behavior. The extensional rheology of the suspensions demonstrates a Newtonian response at low extension rates. At moderate strain rates, the fluid strain hardens. The speed of the strain hardening and the extensional viscosity achieved increase quickly with increasing extension rate. Above a critical extension rate, the extensional viscosity goes through a maximum and the fluid filaments fail through a brittle fracture at a constant tensile stress. The glassy response of the suspension is likely the result of jamming of particles or clusters of particles at these high extension rates. This same mechanism is responsible for the shear thickening of these suspensions. In capillary breakup extensional rheometry, measurement of these suspensions demonstrates a divergence in the extensional viscosity as the fluid stops draining after a modest strain is accumulated.     

Rheo-PIV of a shear-banding wormlike micellar solution under large amplitude oscillatory shear

We explore the behavior of a wormlike micellar solution under both steady and large amplitude oscillatory shear (LAOS) in a cone–plate geometry through simultaneous bulk rheometry and localized velocimetric measurements. First, particle image velocimetry is used to show that the shear-banded profiles observed in steady shear are in qualitative agreement with previous results for flow in the cone–plate geometry. Then under LAOS, we observe the onset of shear-banded flow in the fluid as it is progressively deformed into the non-linear regime—this onset closely coincides with the appearance of higher harmonics in the periodic stress signal measured by the rheometer. These harmonics are quantified using the higher-order elastic and viscous Chebyshev coefficients e _n and v _n , which are shown to grow as the banding behavior becomes more pronounced. The high resolution of the velocimetric imaging system enables spatiotemporal variations in the structure of the banded flow to be observed in great detail. Specifically, we observe that at large strain amplitudes (γ ₀ ≥ 1), the fluid exhibits a three-banded velocity profile with a high shear rate band located in-between two lower shear rate bands adjacent to each wall. This band persists over the full cycle of the oscillation, resulting in no phase lag being observed between the appearance of the band and the driving strain amplitude. In addition to the kinematic measurements of shear banding, the methods used to prevent wall slip and edge irregularities are discussed in detail, and these methods are shown to have a measurable effect on the stability boundaries of the shear-banded flow.     

The rheology of pigment dispersions

Summary A kinetic model is developed to relate the measured shear stress in a dispersion with the rate of deformation, and with the level of structure caused by the competing effects of flocculation and deflocculation.The model parameters are determined from experimental data obtained from equilibrium and transient oscillatory shear, using dispersions of a pigment in three different oil-based media. It is found that the model can successfully describe the flow behaviour of the dispersions under all three types of deformation, and account for different concentrations and temperatures.

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Zusammenfassung Es wird ein kinetisches Modell entwickelt, das die in einer Dispersion gemessene Schubspannung mit der Deformationsgeschwindigkeit in Beziehung setzt unter Berücksichtigung der im Wettbewerb stehenden Flokkulations-und Deflokkulationseffekte.Die Modellparameter werden mit Hilfe experimenteller Daten bestimmt, die zu stationären und oszillatorischen Scherströmungen unter Einbeziehung wechselnder Beanspruchungsarten erhalten wurden. Dabei wurden Pigment-Dispersionen in drei verschiedenen Medien auf Öl-Basis verwendet. Man findet, daß das Modell das Fließverhalten der Dispersionen unter allen betrachteten Deformationstypen sowie bei den verschiedenen angewandten Konzentrationen und Temperaturen erfolgreich zu beschreiben vermag.

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a, b experimental constants - c dispersion concentration by weight - d ₃ mean volume to surface diameter of a floc. - f (·,·) function defined by eq. [20] - g(·) a function of volume fraction - k Boltzmann's constant - n _s number of floccules containings flocs, per unit volume - ratio of the number of floccules containings flocs, per unit volume, to the total number of flocs per unit volume - t present time - B, D derived constants - E ₀,E ₁ activation energies for viscous flow of a dispersion at low and high shear rates - E _m activation energy for viscous flow of the medium - E _f ,E _d activation energies for flocculation and deflocculation of a dispersion - G shear rate - K ₁,K ₂ model constants - M parameter related to the total number of flow units - N number of flocs per unit volume - R, R ₀ the ratio of the rate function for deflocculation to the rate function for flocculation, and its value in the absence of shear - T absolute temperature - ₀, ₀ constants - (·,·),(·) rate functions for flocculation and deflocculation - , , v model parameters - , ₀, ₁ viscosity of a dispersion, and its value at low and high shear rates - _r the viscosity of a dispersion of floccules each containingr flocs - dynamic viscosity of a dispersion - µ, µ ₀ viscosity of a medium at temperatureT, and in the limit of high temperature - _p , _f , _F volume fraction of pigment, of flocs, of floccules - measured shear stress - non-dimensional time - a characteristic time for flocculation With 8 figures and 7 tables     

Filling the gap between transient and steady shear rheology of aqueous graphene oxide dispersions

Even though the rheological behavior of aqueous graphene oxide (G-O) dispersions has been shown to be strongly time-dependent, only few transient measurements have been reported in the literature. In this work, we attempt to fill the gap between transient and steady shear rheological characterizations of aqueous G-O dispersions in the concentration range of 0.004 < ? <?3.5 wt%, by conducting comprehensive rheological measurements, including oscillatory shear flow, transient shear flow, and steady shear flow. Steady shear measurements have been performed after the evaluation of transient properties of the G-O dispersions, to assure steady-state conditions. We identify the critical concentration ? _c =?0.08 wt% (where G-O sheets start to interact) from oscillatory shear experiments. We find that the rheology of G-O dispersions strongly depends on the G-O concentration ?. Transient measurements of shear viscosity and first normal stress difference suggest that G-O dispersions behave like nematic polymeric liquid crystals at ?/? _c =?25, in agreement with other work reported in the literature. G-O dispersions also display a transition from negative to positive values of the first normal stress difference with increasing shear rates. Experimental findings of aqueous graphene oxide dispersions are compared and discussed with models and experiments reported for nematic polymeric liquid crystals, laponite, and organoclay dispersions.