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     

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.     

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.     

TTS in LAOS: validation of time-temperature superposition under large amplitude oscillatory shear

The validation of time-temperature superposition of non-linear parameters obtained from large amplitude oscillatory shear is investigated for a model viscoelastic fluid. Oscillatory time sweeps were performed on a 11?wt.% solution of high molecular weight polyisobutylene in pristane as a function of temperature and frequency and for a broad range of strain amplitudes varying from the linear to the highly non-linear regime. Lissajous curves show that this reference material displays strong non-linear behaviour when the strain amplitude is exceeding a critical value. Elastic and viscous Chebyshev coefficients and alternative non-linear parameters were obtained based on the framework of Ewoldt et al. (J Rheol 52(6):1427?C1458, 2008) as a function of temperature, frequency and strain amplitude. For each strain amplitude, temperature shift factors a _T (T) were calculated for the first order elastic and viscous Chebyshev coefficients simultaneously, so that master curves at a certain reference temperature T _ref were obtained. It is shown that the expected independency of these shift factors on strain amplitude holds even in the non-linear regime. The shift factors a _T (T) can be used to also superpose the higher order elastic and viscous Chebyshev coefficients and the alternative moduli and viscosities onto master curves. It was shown that the Rutgers-Delaware rule also holds for a viscoelastic solution at large strain amplitudes.     

A note on start-up and large amplitude oscillatory shear flow of multimode viscoelastic fluids

Start up of plane Couette flow and large amplitude oscillatory shear flow of single and multimode Maxwell fluids as well as Oldroyd-B fluids have been analyzed by analytical or semi-analytical procedures. The result of our analysis indicates that if a single or a multimode Maxwell fluid has a relaxation time comparable or smaller than the rate of change of force imparted on the fluid, then the fluid response is not singular as Elasticity Number (E ). However, if this is not the case, as E , perturbations of single and multimode Maxwell fluids give rise to highly oscillatory velocity and stress fields. Hence, their behavior is singular in this limit. Moreover, we have observed that transients in velocity and stresses that are caused by propagation of shear waves in Maxwell fluids are damped much more quickly in the presence of faster and faster relaxing modes. In addition, we have shown that the Oldroyd-B model gives rise to results quantitatively similar to multimode Maxwell fluids at times larger than the fastest relaxation time of the multimode Maxwell fluid. This suggests that the effect of fast relaxing modes is equivalent to viscous effects at times larger than the fastest relaxation time of the fluid. Moreover, the analysis of shear wave propagation in multimode Maxwell fluids clearly show that the dynamics of wave propagation are governed by an effective relaxation and viscosity spectra. Finally, no quasi-periodic or chaotic flows were observed as a result of interaction of shear waves in large amplitude oscillatory shear flows for any combination of frequency and amplitudes.     

Orientation behavior of AB and ABC block copolymers under large amplitude oscillatory shear flow

Flow alignment in a large amplitude oscillatory shear field (LAOS) of a lamellar AB and a lamellar ABC block copolymer (A,B are lamellae, C forms cylinders in B-lamellae) has been studied. 2D-small angle X-ray scattering (2D-SAXS) and scanning electron microscopy were used for morphological characterization, and flow birefringence and Fourier-Transform rheology were used to monitor the orientation. The diblock copolymer shows the known frequency-dependent orientation behavior, i.e., a perpendicular or a parallel orientation of the lamellae, while under all conditions for the ABC block copolymer only a perpendicular orientation after a long induction period was found. Due to the introduced third block C the AB lamellar structure with a high viscosity contrast between the A and B domains cannot adapt a parallel orientation of sliding phases. Dynamic mechanical analysis indicates shear induced improvement of the microphase separation of the short C block.     

Newtonian drop in a Newtonian matrix subjected to large amplitude oscillatory shear flows

The dynamics of a single Newtonian drop immersed in a Newtonian matrix subjected to large-amplitude oscillatory shear flow is investigated. The ratio of the drop and matrix viscosity is above criticality, and thus break-up is absent under constant shear flow. At small forcing amplitudes the drop shape follows a regular oscillation. As the forcing amplitude increases, multipeaked oscillations of drop shape and orientation are observed. Experimental results are compared with predictions obtained with a phenomenological model. Model predictions are in qualitative good agreement with experimental data. The model suggests that the appearance of higher harmonics in the drop response is mainly due to flow nonaffinity.     

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.     

Coupling between flow and diffusion at polymer/polymer interfaces: large amplitude oscillatory shear experiments

 Coupling between flow and diffusion at symmetric polymer/polymer interfaces has been investigated. Polystyrene/polystyrene sandwich assemblies were subjected to large-amplitude oscillatory shear (LAOS) using a sliding-plate rheometer (SPR) and the stress was monitored as a function of time. The results were treated using a new model combining Wagner's model with the theory of Doi and Edwards. The model explicitly expresses the influence of the strain and stress amplitudes frequency and time on the self-diffusion process. The apparent self-diffusion coefficient was found to increase with welding time, in agreement with our previous results obtained using small-amplitude oscillatory shear measurements. However, it was found in the present case that the self-diffusion coefficient depends strongly on the strain and stress amplitudes and frequency, and its steady state value was found to be larger than that determined from small-amplitude oscillatory shear measurements. It appears that the large strain oscillatory shear field continuously increases the density of chain ends at the interface and thus increases the flux of mass transport. Received: 30 January 2001 Accepted: 12 June 2001     

Numerical simulation of large amplitude oscillatory shear of a high-density polyethylene melt using the MSF model

We study the flow response in large amplitude oscillatory shear of the molecular stress function (MSF) model that has recently been proposed by Wagner et al. [M.H. Wagner, P. Rubio, H. Bastian, The molecular stress function model for polydisperse polymer melts with dissipative convective constraint release, J. Rheol. 45 (2001) 1387–1412]. The MSF model is derived from molecular theory and has only two parameters to describe the non-linear material response. The model predictions are analysed in both the frequency and time domain. It shows good agreement with experimental data for a linear high-density polyethylene melt. At low and medium strains, MSF model predictions are in excellent agreement with experimental data and predictions of a six-mode Giesekus model which has six parameters to describe the non-linear material response. At medium strains, the basic Doi–Edwards model, which has no non-linear parameters, already underpredicts the data. At high strains, the MSF model predictions agree slightly better with the experimental data than the Giesekus model. Surprisingly, however, it is the Doi–Edwards model that shows excellent agreement with experimental data at high strains. For the linear melt we consider, it outperforms the models that have non-linear parameters, both in the time and frequency domain.     

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.     

Free oscillatory shear measurements —an interesting application of constant stress rheometers in the creep mode

A constant stress rheometer in the creep mode was used to perform free oscillatory shear measurements on soft solids. The results obtained are in good to excellent agreement compared to forced oscillatory shear measurement data. Depending on the rheologic properties of the sample and the moment of inertia of the rotating device of the measurement system, free oscillations are suited to confirm or supplemented forced oscillatory measurement results.Dedicated to Professor W. Nitsch on the occasion of his 60^th birthday.     

Comparison of different shear rheometers with regard to creep and creep recovery measurements

The performance of two shear rheometers with regard to creep and creep recovery measurements is investigated. The first one is a commercially available stress-controlled rheometer that uses an air bearing, and the second one is a magnetic bearing torsional creep apparatus that was built at the Institute of Polymer Materials in Erlangen. The creep and creep recovery measurements were performed in the linear-viscoelastic regime of two polyethylene melts at a temperature of 150°C. The creep compliances of the polyethylenes measured by both rheometers are in excellent agreement. The recoverable compliances of both polyethylene melts, however, have lower values in the case of the commercial rheometer than in the case of the magnetic bearing rheometer. The experimental parameters of creep recovery experiments and the features of the two bearings that are responsible for the different results of the two rheometers are discussed. The influence of the level of the applied shear stress on the short time behavior is investigated as well as the residual torque of the bearings which influences the long time region of the recoverable compliances. Also addressed are the influence of the momentum of inertia of the rotor and the bearing friction which is different for the two rheometers.     

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.     

Large amplitude oscillatory shear rheology of three different shear-thickening particle dispersions

We present a large amplitude oscillatory shear rheology (LAOS) investigation of three different shear-thickening particle dispersions - fumed silica in polyethylene oxide (FLOC), fumed silica in polypropylene glycol (HydroC), and cornstarch in water (JAM). These systems shear-thicken by three different mechanisms - shear-induced formation of particle clusters flocculated by polymer bridging, hydrocluster formation, and jamming. The viscoelastic non-linearities of the three fluids were studied as a function of strain and strain-rate space through the use of Lissajous-Bowditch curves and local nonlinear viscoelastic moduli of an oscillatory shear cycle. The nonlinear behaviors of the three fluids were compared and contrasted to understand the nonlinear shear-thickening mechanism of each. Both HydroC and JAM dispersions were found to exhibit strong strain stiffening of the elastic moduli and strain thickening of the loss moduli behavior associated with possible hydrocluster formation and particle jamming. However, the FLOC dispersion, in contrast, showed strong strain softening and strain thinning behavior at large strain amplitudes associated with yielding of the microstructure. The expected thickening of the loss modulus of FLOC in LAOS with increasing strain was not observed even though viscosity of FLOC was found to shear-thicken in steady-shear measurements. This disagreement is likely due to very large strain amplitudes required for shear-thickening to occur by shear-induced polymer bridging mechanism. The hypothesis was confirmed through stress growth experiments. Conversely, the HydroC and JAM dispersions required relatively small applied strains for shear-thickening to occur by hydrocluster and jamming mechanism. The comparison of local intra-cycle nonlinearity through Lissajous-Bowditch plots and nonlinear viscoelastic parameters indicated that the elastic nonlinearities of all three systems are primarily driven by a strong dependence on the magnitude of the applied strain-rates within an oscillatory cycle rather than the amplitude of the applied strain. A close inspection of the LAOS data reveals strong differences in the viscoelastic nonlinearities of these three different shear-thickening dispersions which can be used to create a nonlinear rheological fingerprint for each and offers valuable new insights into the nonlinear dynamics associated with each of the shear-thickening mechanisms.