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Recent work modeling the rheological behavior of human blood indicates that blood has all the hallmark features of a complex material, including shear-thinning, viscoelastic behavior, yield stress, and thixotropy. There is renewed interest in the modeling of human blood with thixo-elasto-visco-plastic rheological models. Previous work [Armstrong and Tussing, Phys. Fluids 32, 094111 (2020)] has led to the development of the enhanced thixotropic viscoelastic model for blood (ethixo-mHAWB; called here, after a minor modification, ETV) that incorporates viscoelasticity to a thixotropic model for the stress contributed by the rouleaux aggregates, in addition to describing using a nonlinear viscoelastic model the stress contributed by the individual red blood cells deforming under the action of the flow. This model has shown superior performance in fitting human blood steady state and transient rheological data from a strain-controlled rheometer [Horner et al., J. Rheol. 62, 577–591 (2018); 63, 799–813 (2019)] as compared to other alternate models. In the present work, we first develop another variant of the ETV model, the enhanced structural stress thixotropic-viscoelastic (ESSTV) model, and the modification patterned following an elastoviscoplastic model developed recently [Varchanis et al., J. Rheol. 63, 609–639 (2019)]. We develop full tensorial stress formulations of the rouleaux stresses for both the above-mentioned models, resulting in the t-ETV and t-ESSTV models. We use steady state and step-ups, and step-downs in shear rate data to independently fit the parameters of all before-mentioned models. We compare predictions against experimental data obtained on small, large, and unidirectional large amplitude oscillatory shear conditions. We find that the full tensor stress formulations t-ETV and t-ESSTV significantly improved the predictive capability of the earlier ETV model. [ABSTRACT FROM AUTHOR]

In rheological experiments, the relationship between stress and strain is determined. In the transient regime, this relationship may depend on which of these properties is applied and which is measured. In general, data collected using one or the other as the control parameter are not necessarily equivalent. Moreover, the assumed steady state and the relaxation following this state might depend on whether stress or strain has been applied. We examined colloidal suspensions with concentrations around the glass transition and compared their response to stress and strain, in particular, their transient response after the start-up of shear, their steady state, and their relaxation after cessation of shear. After the start-up of shear, the transient behavior was found to significantly depend on whether the sample is exposed to a constant shear rate or a constant stress. Nevertheless, the transients lead to a rheological steady state that is independent of how it is reached, as long as yielding occurred and the corresponding shear rate or stress is applied. After cessation of shear, the relaxation under strain and stress control shows both similarities and differences. This is quantified based on, e.g., the hydrodynamic, Brownian, and residual stress as well as the recovered strain. In addition, the responses of the rheometers to the abrupt changes have been characterized. The corresponding technical data are presented and taken into account in the data interpretation. [ABSTRACT FROM AUTHOR]

We found an anomalous nonlinear behavior under large amplitude oscillatory shears, where the amplitude stress deviates strongly from the linear dependence of strain, while the time dependence of stress remains sinusoidal. This phenomenon is usually accompanied with the Payne effect of filled rubbers. In order to understand the molecular details regarding this unusual behavior, we examined a series of polybutadiene/tetradecane solutions filled with carbon black. Our results show that there is a previously unrecognized transition in the system as the matrix polymer concentration ϕ approaches and passes through a characteristic polymer concentration ϕc. Below ϕc, the system typically shows the classic nonlinearity, where the storage modulus G′ decreases as the strain amplitude γ0 increases and the resulting stress waveforms are distorted from sinusoidal waves. Above ϕc, the system displays an anomalous nonlinearity, where the stress responses at any given strain remain surprisingly sinusoidal regardless of the drop in the storage modulus G′. The critical concentration ϕc is about an order of magnitude greater than the entanglement polymer concentration ϕe. The degree of entanglement in the matrix apparently determines the occurrence of this unusual rheological event and plays a key role here. Increasing the polymer molecular weight enhances this transition. [ABSTRACT FROM AUTHOR]

We present results from a comprehensive investigation of the rheological responses of the gelled waxy crude oils during the yielding transition process by both stress-controlled and strain-controlled tests. If the deformation is within the linear viscoelastic region, G ′ increases slowly with increasing frequency following a power-law relationship. 80% of the total deformation accumulated during creeping is recoverable, and this recoverability remains largely independent of both imposed stress and testing time. The waxy gel relaxes the restored stress slowly with a time scale of ∼100 s. If the induced deformation exceeds the linear viscoelastic region, the elasticity of waxy structure starts to gradually decay with increasing creep stress and creep time, and the plastic contribution has come into play in the nonlinear region. A rapid reduction in the obtained time scale is observed with increasing applied strain. After the structure fractures, both G ′ and G ″ decrease with increasing strain following a power-law relationship. The ratio of the large amplitude shear-thinning exponents of G ′ and G ″ is around 2, indicating a more rapid decay of the elastic property than the viscous property. A brittleness index I is defined to quantitatively describe the brittleness of the waxy gel. The value of I for the waxy gel formed at lower temperatures is smaller, indicating that the waxy gel tends to have a more brittle fracture when yielding. The values of linear storage modulus G ′ ( γ 0 → 0 ) , critical linear strain γ 1 , critical linear stress σ 1 , and yield strain γ y obtained by different rheological testing methods are found to be well consistent. The yielding transition process is found to be strain determined rather than stress determined, and thereby γ 1 and γ y rather than yield stress are suggested to indicate the yielding transition. [ABSTRACT FROM AUTHOR]

A framework for determining the first nonlinear relaxation modulus of a viscoelastic fluid from a medium-amplitude oscillatory shear (MAOS) deformation is constructed. Knowledge of this "MAOS relaxation modulus" allows one to predict the weakly nonlinear stress response of a material under an arbitrary transient deformation via a memory integral expansion. Our framework is demonstrated by explicitly determining the MAOS relaxation modulus for a dilute suspension of Brownian spheroids subject to a dual-frequency oscillatory shear flow. Specifically, we first calculate the second normal stress difference for such a deformation from a corotational memory integral expansion. Second, the microstructural stress response of the model system of Brownian spheroids is determined via a regular perturbation expansion of the orientation distribution function at small dimensionless strain-rate amplitude, or Weissenberg number. An analytical expression for the MAOS relaxation modulus is resolved by comparing the second normal stress difference results of the memory integral expansion and microstructural stress calculation. Finally, using the MAOS relaxation modulus, we reconstruct the stress response of the model system for the start-up and cessation of simple shear and uniaxial extension. In summary, our work offers an approach to utilizing medium (and large) amplitude oscillatory shear results to predict stress dynamics of viscoelastic fluids in other transient, nonlinear flows. [ABSTRACT FROM AUTHOR]

We present unique nonlinear rheological data of well-defined symmetric Cayley-tree poly(methyl methacrylates) in shear and uniaxial extension. Earlier work has shown that their linear viscoelasticity is governed by the hierarchical relaxation of different generations, whereas the segments between branch points are responsible for their substantial strain hardening as compared to linear homopolymers of the same total molar mass at the same value of imposed stretch rate. Here, we extend that work in order to obtain further experimental evidence that will help understanding the molecular origin of the remarkable properties of these highly branched macromolecules. In particular, we address three questions pertinent to the specific molecular structure: (i) Is steady state attainable during uniaxial extension? (ii) What is the respective transient response in simple shear? and (iii) How does stress relax upon cessation of extension or shear? To accomplish our goal, we utilize state-of-the-art instrumentation, i.e., filament stretching rheometry and cone-partitioned plate shear rheometry for polymers with 3 and 4 generations, and complement it with state-of-the-art modeling predictions using the branch-on-branch (BoB) algorithm. The data indicate that the extensional viscosity reaches a steady state value, whose dependence on extensional rate is identical to that of entangled linear and other branched polymer melts. Nonlinear shear is characterized by transient stress overshoots and the validity of the Cox-Merz rule. Remarkably, nonlinear stress relaxation is much broader and slower in extension compared to shear. It is also slower at higher generation, and rateindependent for rates below the Rouse rate of the outer segment. For extension, the relaxation time is longer than that of the linear stress relaxation, suggesting a strong "elastic memory" of the material. These results are described by BoB semiquantitatively, both in linear and nonlinear shear and extensional regimes. Given the fact that the segments between branch points are less than three entanglements long, this is a very promising outcome that gives confidence in using BoB for understanding the key features. Moreover, the response of the segments between generations controls the rheology of the Cayley trees. Their substantial stretching in uniaxial extension appears responsible for strain hardening, whereas coupling of stretches of different parts of the polymer appears to be the origin of the slower subsequent relaxation of extensional stress. Concerning the latter effect, for which predictions are not available, it is hoped that the present experimental findings and proposed framework of analysis will motivate further developments in the direction of molecular constitutive models for branched and hyperbranched polymers. [ABSTRACT FROM AUTHOR]

Rheologists have expectations for signatures of linear viscoelastic properties, such as shapes of G'(ω) and G?(ω). Medium amplitude (or asymptotically-nonlinear) oscillatory shear (MAOS) provides additional nonlinear rheological information with low dimensional, well-defined material functions [Ewoldt and Bharadwaj, Rheol. Acta 52, 201-209 (2013)]. Here, we develop expectations of signatures (or fingerprints) for the four asymptotically-nonlinear material functions associated with MAOS, [e1](ω), [e3](ω), [v1](ω), [v3](ω). Although the linear fingerprints may be identical for different models, the asymptotically-nonlinear fingerprints may be different in magnitude, frequency-scaling, curve shapes, and sign changes. To perform the analysis, we collect/translate a library of available analytical strain-controlled MAOS fingerprints for seven different constitutive models. Using this library, we identify general trends and highlight key differences of asymptotic-nonlinear viscoelasticity. Asymptotic nonlinearities for all models considered here obey the terminal regime inter-relations and frequency scaling predicted by Bharadwaj and Ewoldt [J. Rheol. 58, 891-910 (2014)]. Unlike the positive linear viscoelastic measures, at least one of the four asymptotic nonlinearities changes signs with Deborah number (De). Following sign interpretations of Ewoldt and Bharadwaj [Rheol. Acta 52, 201-209 (2013)], we show that nonlinearities tend to be driven by strain-rates at small De, and by strains at large De, a trend observed for nearly all the constitutive models studied here, the exception being the model for dilute rigid dumbbell suspensions of Bird et al. [J. Chem. Phys. 140, 074904 (2014)]. Some constitutive models exhibit multiple sign changes at intermediate De and there may be no universal behavior of asymptotically-nonlinear fingerprints in this regime. Therefore, frequency-dependent signatures can be material-specific. This will allow inverse problems to infer structure, select models, and fit model parameters using asymptotically-nonlinear signatures. To illustrate this aspect, we demonstrate a fingerprint matching exercise with experimental measurements on a transiently cross-linked hydrogel system. We find that currently available model fingerprints can match the qualitative magnitudes and frequency dependence, but not the signs of the experimental transient network response. [ABSTRACT FROM AUTHOR]

We propose, in this paper, a model for predicting the rheological response of both vibrated and sheared 3D granular suspensions in stationary and nonstationary conditions. The major assumption of this model is the inherent bimodal behavior of chain forces in granular packings. The model is set up from a kinetic equation describing the dynamic exchange between a population of strongly correlated caged particles and a population of slightly correlated free particles. To compare the predictions of the model to experimental results, the kinetic equation is transformed into a differential constitutive equation, relating stress to strain, by including the effect of the interstitial fluid on the suspension. With only four adjustable parameters intrinsic to the system (i.e., independent of the type of rheological test used), the model is in very close agreement with experiments. Despite the fact that our approach remains at a mean-field level, it is able to predict and describe several rheological behaviors, in stationary, nonstationary conditions, linear and nonlinear regimes, including Newtonian and frictional Coulombian regimes, as well as elastic Hookean and viscoelastic Maxwellian behaviors. It then appears that this two-state approach allows capturing both the viscoelastic behavior of dry granular materials and granular suspensions. Vibrated dense suspensions and granular media are thus unified under a common framework. [ABSTRACT FROM AUTHOR]

The dynamic response of a viscoelastic suspension of spheres under small and large amplitude oscillatory shear is investigated by three-dimensional direct numerical simulations. A sliding triperiodic domain is implemented whereby the computational domain is regarded as the bulk of an infinite suspension. A fictitious domain method is used to manage the particle motion. After the stress field is computed, the bulk properties are recovered by an averaging procedure. The numerical method is validated by comparing the computed linear viscoelastic response of Newtonian and non-Newtonian suspensions with previous theories and simulations. The numerical predictions are in very good quantitative agreement with experimental data for the Newtonian case, whereas deviations are found with respect to some sets of experiments for semidilute and concentrated viscoelastic suspensions. To investigate on such discrepancies, the effect of aggregates in the bulk of the suspension is examined. The simulations show that the presence of structures significantly alters the loss modulus. Such an effect is more pronounced as the volume fraction increases. In this light, the above mentioned disagreement between simulations and data (and among experimental data themselves) can be rationalized, as its origin can be attributed to inhomogeneous particle configurations. For increasing strain amplitudes, both loss and storage moduli depart from the linear viscoelastic values. Although the deviations are qualitatively similar to the large amplitude response of the unfilled suspending matrix, our results for dilute and semidilute suspensions show that the decrease of the moduli is more and more pronounced as the volume fraction is higher. Furthermore, a higher concentration of solid particles reduces the value of strain amplitude such that the nonlinear behavior is observed. Simulations at higher frequencies also correctly capture the overshoot in the loss modulus for intermediate strain amplitudes. Finally, the effect of fluid elasticity on the particle motion is analyzed. The particles are found to move away from their starting positions and the average distance, computed at the beginning of each cycle with respect to the initial configuration, linearly increases with the number of cycles. The change in the microstructure is attributed to the long-range hydrodynamic interactions mediated by fluid viscoelasticity. [ABSTRACT FROM AUTHOR]

Characterizing elongational behavior of polymer melts in constant elongation rate or constant tensile stress experiments is hampered by the onset of 'necking' instabilities according to the Considère criterion: For an elastic filament, homogeneous uniaxial extension is not guaranteed for strains larger than the strain at which a maximum occurs in the force versus extension curve. Although simulations and experiments seem to indicate that in viscoelastic fluids viscosity effects delay the onset of necking to higher strains, integral measurements of elongational viscosities in Meissner- or Münstedt-type elongational rheometers are often affected by inhomogeneous deformations. A simple means of avoiding the consequences of the Considère criterion consists in operating at constant tensile force, but little attention has been paid so far to constant force elongational rheometry since the pioneering work of Raible et al. [J. Non-Newtonian Fluid Mech. 11, 239 (1982)]. Constant force elongation is also of great industrial relevance, since it is the correct analog of steady fiber spinning, as, e.g., exemplified by the so-called Rheotens test. We present experimental data for two long-chain branched polyethylene melts obtained in constant elongation rate and constant tensile force modes by use of a Sentmanat extensional rheometer in combination with an Anton Paar MCR301 rotational rheometer. The accessible experimental window and experimental limitations are discussed. Constant force elongation can be subdivided into three distinct deformation regimes: At small deformations (regime 1), constant force elongation is equivalent to creep at constant tensile stress. This is followed by regime 2, which is characterized by a steep increase in tensile stress at roughly constant strain rate, while regime 3 corresponds to elongation of a viscous power-law fluid. All three regimes can be modelled quantitatively by a single integral constitutive equation, and a constitutive analysis reveals substantial underestimation of the effective strain-hardening effect observed in constant strain-rate elongation in comparison to constant tensile force extension, which may be indicative of the effect of necking under constant elongation-rate conditions. [ABSTRACT FROM AUTHOR]

Fractional Viscoelasticity is referred to materials, whose constitutive law involves fractional derivatives of order β∈R such that 0≤β≤1. In this paper, two mechanical models with stress-strain relation exactly restituting fractional operators, respectively, in ranges 0≤β≤1/2 and 1/2≤β≤1 are presented. It is shown that, in the former case, the mechanical model is described by an ideal indefinite massless viscous fluid resting on a bed of independent springs (Winkler model), while, in the latter case it is a shear-type indefinite cantilever resting on a bed of independent viscous dashpots. The law of variation of all mechanical characteristics is of power-law type, strictly related to the order of the fractional derivative. Because the critical value 1/2 separates two different behaviors with different mechanical models, we propose to distinguish such different behavior as elasto-viscous case with 0≤β≤1/2 and visco-elastic case for 1/2≤β≤1. The motivations for this different definitions as well as the comparison with other existing mechanical models available in the literature are presented in the paper. [ABSTRACT FROM AUTHOR]

It has recently been shown that the dynamics of complex interfaces can be treated by hyperelastic finite deformation, and the Cauchy stress tensor can be written as a tensor derivative of the interfacial energy. In the present study, the analytical nature of this tensor derivative was further explored, resulting in a more useful constitutive relation between the stress tensor and the Finger strain tensor. To accommodate the interfacial relaxation effects, an energy balance principle was adopted in developing a nonlinear relaxation model which was then used in a visco-hyperelastic formulation for stress determination. Case studies on this visco-hyperelastic model were performed, and validations against known results were attempted. While at small deformation rates, the new model agrees with the linear viscoelastic calculations, as well as Doi and Ohta's scaling predictions, high nonlinearity was observed at large deformation rates. [ABSTRACT FROM AUTHOR]

The main aim of this work is to study the flow, failure, and rupture dynamics of a benchmark low-density polyethylene (BASF Lupolen 1840H) in true tensile creep conditions in both the viscoelastic and elastic deformation regimes. For this, we used a novel extensional rheometer that for the first time allows real controlled-stress conditions to be applied to the materials (as opposed to nominally controlled-stress) until physical rupture occurs (as opposed to being limited by maximum Hencky strain). We observed that constant strain rate was achieved for all flow conditions, and depending on the level of applied tensile stress, one or two states were obtained. In the former case, the observed mode of rupture was ductile, or liquid-like, and in the latter was cohesive, or elastic-like. The coupling at the molecular level between these flow and rupture mechanisms is not yet fully understood, although some recent studies in the literature may be able to offer at least partial explanations. [ABSTRACT FROM AUTHOR]

Non-linear correlations are found between the melt strength and fundamental shear flow properties such as low frequency loss tangent, crossover frequency, and zero-shear-rate viscosity for a series of polypropylene (PP) melts. The very good non-linear correlations suggest rheotens as a reliable rheological test to characterize extensional rheology relevant to fabrication, despite its non-homogeneous and non-isothermal flow kinematics. The rheotens model of Doufas [J. Rheol. 50, 749-769 (2006)] with a modified Giesekus (MG) viscoelastic constitutive equation is expanded to the case of PP melts. A single set of molecular parameters per material predicts the rheotens force curves very well over a wide range of processing conditions. The rheotens model is proposed as a tool for determination of rheological parameters of constitutive equations applicable to the simulation of complex polymer processes. Molecular considerations and predictions of the rheotens model are extensively discussed. A multi-mode MG model predicts the non-linear steady shear data (shear and first normal stresses) very favorably satisfying linear viscoelasticity. The oscillatory shear data and model predictions satisfy both the Cox-Merz [J. Polym. Sci. 28, 619-621 (1958)] and Laun [J. Rheol. 30, 459-501 (1986)] rules. The model exhibits stable numerical behavior without singularities or turning points in the prediction of steady shear viscosity even at quite high shear rates (e.g., on the order of 20 000 s-1), problems that have been reported for other constitutive equations. [ABSTRACT FROM AUTHOR]

Failure of polymer liquids under flow has been the subject of a relatively strong computational, theoretical, and experimental effort over the years, despite which a clear picture of the phenomenon is still nonexistent. For example, there are still arguments in the literature whether the maximum in engineering stress, also known as the Considère limit for failure, is a point of true yielding of the polymer network or simply a purely elastic mechanical instability and if this onset of yielding also corresponds to the true onset of non-homogeneous deformation, as expressed for example by necking. The main objective of the present work is to contribute to the ongoing discussion on this matter by studying a linear polyisobutylene melt in terms of its failure and rupture behavior in both the viscoelastic and purely elastic deformation regimes of deformation showing that homogeneous flow still occurs after the maximum in engineering stress and quantifying this deviation. This is ultimately connected with the observation of a limiting stress at rupture in the rubbery (elastic) regime. From the results, it is apparent that, for this particular polydisperse melt and in the viscoelastic regime, the Considère criterion underestimates by approximately 60% the point of onset of non-homogeneous deformation, i.e., necking. The calculated true onset of failure, on the other hand, agrees almost exactly with the visually determined onset. However, it is clear that a general working criterion for failure of entangled polymer melts, especially in the all-important viscoelastic deformation regime, is still lacking. [ABSTRACT FROM AUTHOR]

We have studied stress overshoot behavior in startup shear of four monodisperse polymer melts with a range of chain entanglement from Z=24 to 160 entanglement points per chain. In the elastic deformation regime defined by γτR>1, where τR is the Rouse relaxation time, (i) the peak shear stress σmax scales with the time tmax at the peak to -1/2 power, in contrast to an exponent of -1/4 in the viscoelastic regime (for γτR<1), (ii) σmax changes linearly with the elapsed strain at the stress peak γmax, which scales with the applied shear rate as γ1/3, (iii) a supermaster curve collapses time-dependent shear stress growth curves up to the stress maximum at all shear rates for all the four styrene-butadiene rubber samples. [ABSTRACT FROM AUTHOR]

A new method for measurement of the viscoelastic properties of the liquid with the torsion resonator on forced resonance is presented in this paper. Both theoretical analysis and experiments of different glycerol-water mixtures with our homemade torsion pendulum apparatus demonstrate that this new method avoids the restriction of the common method that the resonator should have the high quality factor both in air and in liquid sample and has the prominent advantage of measuring the concentrated and large-viscous liquid in the low frequency range (≤100 Hz) with a better precision, which is usually unavailable by the common method. Employment of the new method can thus extend the accessible ranges of viscosity and frequency of the torsion resonator apparatus and close the gaps between conventional rheometers and the torsion resonators. [ABSTRACT FROM AUTHOR]

Two-step reversing flows are severe tests of constitutive equations for polymer melts and have attracted interest for testing the response of branched polymers. Here we report on single-step and three types (types B, C, and D) of reversing torsional flows on branched and linear polyethylenes (PEs). The responses were analyzed using Kaye–Bernstein–Kearsley–Zapas (K-BKZ) theory. Comparisons between data and theory in type B and C flows for the two branched PEs (LD 103 and LD 146) and a linear HDPE are presented. For the LD 146 material and to strains higher than previously examined, the results agree with prior studies, i.e., the K-BKZ theory provides a good description of the response of branched polymers in reversing flows while the opposite is the case for the linear polymers. Surprisingly, it is found that the other branched polymer (LD 103) behaves more like a linear polymer and not a branched polymer in that it does not follow the K-BKZ theory. In the type D flow, one which was not previously investigated, the K-BKZ theory describes the normal force (NF) responses for branched LD 146 but not for the linear PE. Also, isochronal derivatives of the strain potential function (W1 and W2) were calculated from torque (T) and NF responses in single-step tests. The damping function fits to a modified sigmoidal formula and is close to the BKZ limit as reported by Wagner (2004a) for branched polystyrenes. The normal stress difference ratio and damping function were extracted from W1 and W2. Finally, the Cox–Merz rule was examined for one of the branched PEs. [ABSTRACT FROM AUTHOR]

A recent, nonlinear viscoelastic theory for predicting the thermomechanical response of glassy polymers has been shown to predict behaviors from enthalpy relaxation to temperature-dependent mechanical yield in various modes of deformation quite well. The foundation of this theory rests on a “material clock” that depends on the potential energy of the system. The molecular basis for the clock and the Rational Mechanics framework for the constitutive equation are briefly reviewed. The theory is then used to predict and explain much more complicated behavior of glassy polymers: the change in compressive yield stress during physical aging at different temperatures, the peculiar enthalpic response of glassy polymers previously compressed to different strains, “volumetric implosion” on samples subjected to tensile strains, and the dependence of the shift factor on aging time and applied stress. [ABSTRACT FROM AUTHOR]

The creep compliance and relaxation functions used in characterizing the mechanical response of linear viscoelastic solids are traditionally found by conducting two separate experiments. Alternatively, one of the functions may be determined from a single experiment while the other is obtained through interconversion. All direct interconversion methods, however, require the solution of an ill-posed problem. The goal of this paper is to present the theoretical framework for developing a new apparatus, based on “spring loading,” which facilitates the determination of both creep and relaxation functions from a single experiment. There is no need for interconversion. Questions of stability with respect to the measured data are discussed and a stable numerical algorithm is presented. [ABSTRACT FROM AUTHOR]