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We present a systematic experimental study of the shear rheology of metallosupramolecular assemblies based on entangled telechelic star polymers comprising one (single dynamic network) or two (double dynamics network) types of physical bonds with the aim to unravel the role of concentration and strength of these bonds on the nonlinear response. Model dynamic networks functionalized with terpyridine ligands were formed by adding different metal ions with increasing bonding strength, zinc, copper, and cobalt. The dynamics are driven by entanglement/disentanglement processes and a ligand exchange mechanism. Steady-state viscosities of single and double dynamics networks collapse onto a universal curve over a wide range of Weissenberg numbers based on terminal time (up to about 300 for single and 1000 for double), exhibiting stronger shear thinning (with an exponent of −0.76) compared to entangled neutral star polymers. Double dynamics networks consisting of two different metal ions (with different lifetimes) exhibit stronger mechanical coherence (rate-dependent fractional viscosity overshoot) and accumulate larger strain at steady-state flow compared to single-ion counterparts. The shear stress growth function signals exhibit weak, albeit unambiguous shear strain hardening, which becomes more pronounced for stronger associations. They also exhibit double overshoot, which reflects the interplay of association strength and chain deformation. Increasing the strength of associations leads to the failure of the Cox–Merz rule, which is more severe for single dynamic networks. The markedly different behavior of double dynamics networks is attributed to the fact that at sufficiently high ion content, the weaker bond acts as a sacrificial component, which provides local energy dissipation and enhances the overall deformability. This bears analogies with their linear viscoelastic response, which has revealed that the arm disentanglement (delayed due to the reversible bonds) effectively interpolates between the two single dynamic network components, depending on composition. Our results suggest ways to tailor the mechanical properties of this class of materials by judicious choice of the type and content of the ion.

Dynamic mechanical oscillatory shear measurements with torsional rectangular geometry are widely carried out in order to determine the mechanical properties of soft solid materials in a quick and practical way. This technique has the advantage of avoiding slip effects, thus being particularly attractive for testing stiff elastomers such as vulcanized rubber compounds. However, one of its drawbacks is the clamping system required to keep the specimen edges in place. Since it imposes a constraint to warping deformations (i.e., out-of-plane cross-section distortions about the torsional axis), a certain increase of dynamic moduli with respect to their values in simple shear is observed and considered as an experimental artifact (i.e., de Saint-Venant's assumption of primary torsion of the specimen is no longer valid). The increase of dynamic moduli in torsion depends on the specimen's cross-section geometry and relative dimensions. We test here the capability of different torsion models to describe the constrained warping effect for an industrial rubber with rectangular specimen cross section using a wide range of different geometric parameters (length-to-width p ratio and width-to-thickness u ratio). We compare two theoretical models (Vlasov's model and Timoshenko's approach) and a phenomenological model (based on finite element simulations by Diani and Gilormini) with our experimental data set. We propose a slight modification of Vlasov's model to obtain realistic predictions of torsion over a wider parameter range. It is shown to be particularly useful in soft rubber testing, and the limitations in the choice of specimen geometry to obtain sufficient torque signal are overcome.

We present a comprehensive experimental rheological dataset for purified entangled ring polystyrenes and their blends with linear chains in nonlinear shear and elongation. In particular, data for the shear stress growth coefficient, steady-state shear viscosity, and first and second normal stress differences are obtained and discussed as functions of the shear rate, as well as molecular parameters (molar mass, blend composition, and decreasing molar mass of linear component in the blend). Over the extended parameter range investigated, rings do not exhibit clear transient undershoot in shear, in contrast to their linear counterparts and ring-linear blends. For the latter, the size of the undershoot and respective strain appear to increase with the shear rate. The universal scaling of the strain at overshoot and fractional overshoot (the ratio of the maximum to the steady-state shear stress growth coefficient) indicates subtle differences in the shear-rate dependence between rings and linear polymers or their blends. The shear thinning behavior of pure rings yields a slope nearly identical to predictions (−4/7) of a recent shear slit model and molecular dynamics simulations. Data for the second normal stress difference are reported for rings and ring-linear blends. While N2 is negative and its absolute value stays below that of N1, as for linear polymers, the ratio –N2/N1 is unambiguously larger for rings compared to linear polymer solutions with the same number of entanglements (almost by a factor of 2), in agreement with recent nonequilibrium molecular dynamics simulations. Furthermore, –N2 exhibits slightly weaker shear rate dependence compared to N1 at high rates, and the respective power-law exponents can be rationalized in view of the slit model (3/7) and simulations (0.6), although further work is needed to unravel the molecular original of the observed behavior. The comparison of shear and elongational stress growth coefficients for blends reflects the effect of ring-linear threading, which leads to significant viscosity enhancement in elongation. Along the same lines, the elongational stress is much larger than the first normal stress in shear, and their ratio is much larger for rings and ring-linear blends compared to linear polymers. This confirms the interlocking scenario of rings and their important role in mechanically reinforcing linear matrices.

We report upon the characterization of the steady-state shear stresses and first normal stress differences as a function of shear rate using mechanical rheometry (both with a standard cone and plate and with a cone partitioned plate) and optical rheometry (with a flow-birefringence setup) of an entangled solution of asymmetric exact combs. The combs are polybutadienes (1,4-addition) consisting of an H-skeleton with an additional off-center branch on the backbone. We chose to investigate a solution in order to obtain reliable nonlinear shear data in overlapping dynamic regions with the two different techniques. The transient measurements obtained by cone partitioned plate indicated the appearance of overshoots in both the shear stress and the first normal stress difference during start-up shear flow. Interestingly, the overshoots in the start-up normal stress difference started to occur only at rates above the inverse stretch time of the backbone, when the stretch time of the backbone was estimated in analogy with linear chains including the effects of dynamic dilution of the branches but neglecting the effects of branch point friction, in excellent agreement with the situation for linear polymers. Flow-birefringence measurements were performed in a Couette geometry, and the extracted steady-state shear and first normal stress differences were found to agree well with the mechanical data, but were limited to relatively low rates below the inverse stretch time of the backbone. Finally, the steady-state properties were found to be in good agreement with model predictions based on a nonlinear multimode tube model developed for linear polymers when the branches are treated as solvent.

Thermodynamic or kinetic state transitions of six polymeric systems were probed using rheology in isothermal and nonisothermal isochronal experiments. The polymeric systems were representative of three different types of transitions: Gelation, macrophase separation, and order-disorder transitions. A phenomenological dimensionless parameter termed the relative elasticity, R, was found to be particularly sensitive to these transitions and was finitely bound by the viscous limit and the elastic limit with values of zero and one, respectively. In addition, the (time or temperature) derivative of R and tan δ (with δ being the phase angle) proved to be more sensitive to transitions as compared to the respective pure values. When compared to other methods found in literature, these new phenomenological protocols are found to be robust while providing a convenient and precise means of detecting transitions. Hence, they may complement existing methods, whereas they are beneficial to industrial or other systems exh...

Whereas mixtures of colloids and nonadsorbing polymers have been studied in great detail in the last two decades, binary colloidal mixtures have not received much attention. Yet, fragmental evidence from asymmetric mixtures of hard spheres indicates a wide-ranging, complex behavior from liquid to crystal to single glass and to double glass, and respective rich rheology. Recently, we addressed the question of softness by investigating a mixture of soft and virtually hard colloidal spheres. We found an unprecedented wealth of states including repulsive single glass (RG), liquid, arrested phase separation (APS), and double glass (DG). This is a consequence of the coupling of softness and osmotic forces due to the hard component. We now report on the rheology of the different states with emphasis on the nonlinear response during startup of stress at constant rate, its relaxation upon flow cessation, and large amplitude oscillatory shearing. Distinct features are identified, whereas comparison with single-colloid (soft or hard) glasses reveals some phenomenological universalities in yielding, residual stresses and periodic intracycle stress response. In brief, the DG exhibits much larger yield and residual stresses as compared to the RG and APS, whereas the yield strain is the same for all states. Two-step yielding is unambiguously evidenced for the APS whereas both yield stress and strain exhibit a weak dependence on Peclet number. Large amplitude oscillatory tests reveal large value of the intrinsic nonlinear parameters, reflecting the role of colloidal interactions. Moreover, RG exhibits intracycle stress overshoots, a feature that characterizes most of the soft glassy materials formed by interpenetrable particles and that vanishes as hard (nearly impenetrable) colloids are added in the mixtures. These results demonstrate the sensitivity of linear and nonlinear rheology to colloidal state transitions and, more importantly, the power of entropic mixing as a means to tailor the flow properties, hence performance and handling of soft composites.Whereas mixtures of colloids and nonadsorbing polymers have been studied in great detail in the last two decades, binary colloidal mixtures have not received much attention. Yet, fragmental evidence from asymmetric mixtures of hard spheres indicates a wide-ranging, complex behavior from liquid to crystal to single glass and to double glass, and respective rich rheology. Recently, we addressed the question of softness by investigating a mixture of soft and virtually hard colloidal spheres. We found an unprecedented wealth of states including repulsive single glass (RG), liquid, arrested phase separation (APS), and double glass (DG). This is a consequence of the coupling of softness and osmotic forces due to the hard component. We now report on the rheology of the different states with emphasis on the nonlinear response during startup of stress at constant rate, its relaxation upon flow cessation, and large amplitude oscillatory shearing. Distinct features are identified, whereas comparison with single-coll...

In analogy with the pom-pom model, we introduce a simple model for comb polymers with multiple side-arms attached to a linear backbone by considering a set of coupled equations describing the stretch in the individual interbranch backbone segments. The stretch equations predict a sudden onset of backbone stretch as the flow rate is increased. Drag-strain coupling smooths this transition to some extent. For a series of well characterized polyisoprene and polystyrene combs, we find good agreement with the experimentally determined transient stress growth coefficients in uniaxial extension.

International audience; Upon addition of small nonadsorbing linear polymers, colloidal glasses composed of large hard spheres melt and eventually revitrify into the so-called attractive glass regime. We show that, when replacing the hard spheres by star polymers representing model soft particles, a reentrant gel is formed. This is the result of compression and depletion of the stars due to the action of the osmotic pressure from the linear homopolymers. The viscoelastic properties of the soft dense gel were studied with emphasis on the shear-induced yielding process, which involved localized breaking of elements with a size of the order of the correlation length. Based on these results, a phenomenological attempt was made at describing the universal rheological features of colloid/nonadsorbing polymer mixtures of varying softness. The star gel was found to undergo thermoreversible melting, despite the fact that conventional hard-sphere depletion gels are invariant to heating. This phenomenon is attributed to the hybrid internal microstructure of the stars, akin to a dry-to-wet brush transition, and is characterized by slow kinetics, on the time scale of the osmotic gel formation process. These results may be useful in finding generic features in colloidal gelation, as well as in the molecular design of new soft composite materials.

We report on the shear flow start-up and the relaxation upon flow cessation of anionically synthesized comb polymers of different chemistries. The experimental data, obtained with a cone partitioned-plate geometry in order to avoid artifacts, showed that the start-up shear flow of combs exhibits systematic dependencies on the branching structure. They were interpreted by invoking dynamic dilution and hierarchical relaxation, which are known to control the linear viscoelastic response. For all combs studied here, the backbones remained entangled after dynamic dilution due to branch relaxation. We combined the important molecular parameters (i.e., the number and molar mass of the branches) into a single parameter, the number of entanglements of the dynamically diluted backbone, ZBBDIL., which we found to be the main scaling parameter for the observed nonlinear flow behavior. The steady viscosities as function of Weissenberg number were less shear-thinning compared to linear analogues, and the higher the amo...

We present a detailed systematic investigation of the transient uniaxial extensional response of a series of well-characterized, anionically synthesized comb polystyrenes and polyisoprenes. The comb architecture consists of a linear chain backbone with multiple branches of equal molar mass, and represents an excellent model branched polymer. The linear viscoelastic response has been studied already in great detail. Our results indicate that the strain hardening becomes more important as the Hencky strain rate is increased. In general, the larger the number of entanglements of the segments between branches and/or of the branches, the stronger the strain hardening and the smaller the characteristic rate for its onset. The key molecular parameter appears to be the number of entanglements per branch. By varying it, one can tailor the amount and onset of strain hardening. This can be rationalized by accounting for the combined effect of backbone tube dilation and extra friction, brought about by the branches. In fact, we define an effective “stretch time” of the comb as the timescale for stretch relaxation along the dilated backbone tube when accounting for the large friction that comes from the branches and suggest that extension hardening occurs at rates equal to or greater than its inverse. The good comparison of this prediction to experimental data is a promising guide toward a universal framework for understanding the effects of branches on extensional rheology, and hence providing some insight into the behavior of long-chain branched polyolefins.

A cone-partitioned-plate fixture for the ARES rheometer (TA instruments, DE) has been designed, implemented, and validated. This geometry allows measuring the nonlinear shear flow properties of samples, which display edge fracture in regular cone-and-plate geometries, such as polymer melts and concentrated solutions. Reliable bulk shear flow data can be obtained with these systems at high rates and strains, using very small sample quantities. Measurements can be performed at temperatures ranging from at least − 50 °C up to over 200 °C in a controlled nitrogen environment. An extensive set of start-up shear measurements on moderately entangled linear monodisperse polyisoprene (60 kg/mol) and polystyrene (182 kg/mol) melts to validate the design are presented and discussed with focus on the Cox–Merz rule and the characteristics of the stress overshoot. With this new geometry, the range of artifact-free data is extended by a decade in Weissenberg number (WiD). It is shown that the obtained results compared w...

We investigate the response of a well-characterized colloidal star glass to large-amplitude oscillatory stress and strain fields. By combining these measurements with dynamic time sweeps we demonstrate the importance of probing both strain- and stress-induced nonlinear rheology of such complex fluids in order to elucidate the yielding and fluidization behavior. We also show that, due to the strong time dependence, it is essential to perform dynamic time sweeps at different strain and stress amplitudes, which result in different departures of the glass cage from its quiescent quasiequilibrium structure. This allows for steady-state responses to be reached and for nonlinear oscillatory responses to be treated properly while also suggesting that yielding is a gradual process. Further, we use a recently published framework for analyzing nonlinear responses to large-amplitude oscillatory shear [Rogers et al., J. Rheol. 55, 435 (2011)], based on the analysis of the whole stress waveforms as a sequence of physic...

Several attempts have been made recently to develop universal analysis techniques for the stress response to large-amplitude oscillatory shear (LAOS) in a variety of materials from viscous and viscoelastic to viscoplastic. All previous attempts have assumed, tacitly or otherwise, that such responses display a minimum number of symmetries in stress/strain. We present the stress response to LAOS of a glassy suspension of multiarm star polymers, which exhibits a complete lack of any type of symmetry during the 10 000 s experimental window. We also present new physical interpretations of previously defined parameters and conjecture that the lack of symmetry observed in the stress response is a consequence of the aging process, which can be viewed as slow cage rearrangement and evolution of heterogeneities.

We investigate the complex flow behavior of a well-characterized colloidal star glass using linear and nonlinear rheology. The results are integrated into a generic state diagram which specifies the states of the glass for different initial conditions and mechanical histories: viscoelastic liquid and solid, homogeneous shear-thinned solution, and shear-banded material. Aging takes different forms which can be interpreted as kinetic pathways through the state diagram. Shear-banding appears to be an intrinsic mechanical instability which occurs when the solid state of the glass is shear-melted. Our results provide a straightforward methodology to fingerprint the material behavior of soft glassy materials undergoing rheological transitions which can be used as predictive tool to design systems with a desired rheological response.

We probed the viscoelastic behavior of polydisperse star/linear polymer blends with varying composition and average arm length. The linear viscoelastic behavior has been investigated over a wide range of frequencies using both oscillatory and long creep/recovery experiments. A method was developed for splitting the molar mass distributions of the blends into the contributions of different architectures. These results were used to implement a time-marching algorithm based on a parameter-free tube model for predicting the linear viscoelastic behavior. The model predictions were successfully validated with the experimental data, opening the route for designing blends with desired rheological properties.

We investigated the rheology of a series of anionically synthesized, model symmetric Cayley tree poly(methylmethacrylates) having from 1 to 4 generations of identical molar mass. The hierarchical relaxation of the different generations was assessed from the linear data by accounting for both the plateau modulus and the characteristic relaxation times. Using a tube-model time-marching analysis based on the concept of hierarchy of motion, we described quantitatively the frequency spectra without adjustable parameters. We also performed uniaxial extensional measurements using the Sentmanat extensional rheometer fixture. The samples tested exhibited significant strain hardening compared to their linear analogs at lower and intermediate Hencky strain rates. This hardening was more pronounced with increasing number of generations, hence branch points. The extracted effective steady extensional viscosity was found to scale with the extensional rate with a power exponent of about -0.5, in agreement with earlier findings with linear polystyrenes. We also extended the time-marching-algorithm to predict the extensional behavior of these polymers using the conceptual framework developed recently for pom-pom and Cayley-tree polymers. Comparison between theoretical and experimental results was satisfactory when the maximum stretch which can be supported by the molecule was estimated by accounting for the recently proposed inter-chain pressure effects. (C) 2010 The Society of Rheology. [DOI: 10.1122/1.3368724]

A strain-rate frequency superposition (SRFS) technique, recently proposed to analyze the low-frequency behavior of soft materials, is evaluated. The application of SRFS to an emulsion and multiarm star polymer solution produces master curves that, while promising in appearance, do not match the anticipated linear response as they seem inconsistent with dynamic frequency sweep data and the Kramers–Kronig relation. While the raw unscaled frequency sweep data are well described using the generalized Maxwell model, strong discrepancies appear when the same procedure is applied to SRFS data. These inconsistencies appear to be generic and are observed in other materials as well. An examination of Lissajous curves obtained from large amplitude oscillatory strain shows that nonlinear contributions, such as solvent-mediated convective flow, strongly affect SRFS master curves. Based on these findings, SRFS should be approached with caution when applied to soft materials.

We measure the stress relaxation of linear comb polymer solutions, after a large amplitude step shear strain. We apply the time-temperature superposition principle in order to construct stress relaxation master curves that span many orders of magnitude in time and cover the entire comb relaxation from early branch retraction to backbone reptation. We find evidence of distinct relaxation processes and dynamic tube dilation that can be attributed to the architectural features of the polymer.

We report a number of experiments, mainly rheological measurements, examining the yielding behavior of colloidal glasses with hard-sphere interaction plus a short-range attraction. The system is a suspension of nearly hard-sphere colloidal particles and non-adsorbing linear polymer which induces an adjustable depletion attraction between the particles. The pure hard-sphere glass shows a simple yielding process at a strain corresponding to the maximum distortion of the cage of nearest neighbors—the structural arrest length scale. However, the attraction-dominated glasses show a two-step yielding process at different ranges of strain. We suggest that the first step at low yield strain corresponds to the breaking of attractive bonds between particles. The other at larger strain corresponds to the cage breaking process.

We investigated the linear melt viscoelasticity and the crystallization kinetics of a series of model poly(ethylene oxide) stars with different functionalities (f=4-32 arms) and moderately entangled arms (their molecular masses ranging from 5.5 to 12 kg/mol). The limited data in the homogeneous state indicated that the zero-shear viscosity eta(0) was adequately described by the Milner-McLeish model for functionalities f < 32, where the core effect is insignificant; a similar behavior was observed for the recoverable compliance J(e)(0) which depended on both the molecular weight and the number of the arms. Below the melting point, the isothermal crystallization was measured with differential scanning calorimetry and rheology, and analyzed in terms of the Avrami theory, expanding over a wide range of temperatures. The results were supported by additional polarizing optical microscopy data and indicated a slower crystallization kinetics of the stars compared to their linear analogues. They showed a strong dependence of the crystallization rate on the arm molecular weight, whereas the available experimental evidence is suggestive of some functionality dependence as well. (c) 2007 The Society of Rheology. Journal of Rheology

Dispersions of multiarm star polymers in an athermal solvent are studied as a model system to explore the effects of soft colloidal interactions on the dynamics of colloidal glasses. Linear viscoelastic measurements in the glassy state are congruent with Mode Coupling Theory predictions for hard sphere glasses at moderate frequencies, indicating similarities in the relaxation processes of hard and soft colloidal glasses near equilibrium. On the other hand, distinct features of the star relaxation (related to arm disengagement) are observed to affect the nonlinear behavior associated with shear melting of the glass, which exhibits transitions previously unreported for hard sphere systems. Whereas a single maximum in G″(γ) is evident under large amplitude oscillatory shear at frequencies near the beta relaxation, secondary transitions between yielding and the onset of macroscopic flow are observed at higher and lower frequencies. The latter are annealed out upon complete fluidization of the star polymer sus...

We explore the nonlinear rheological response of a soft gel formed by a crowded colloidal star polymer and focus on the occurrence of a stress plateau, marked hysteresis, and yield stress in its flow curve. With the aid of nuclear magnetic resonance velocimetry we find evidence for fluctuations in the flow behavior across the gap of the concentric cylindrical Couette device, in association with a degree of apparent slip at the inner wall. The time scale of the these fluctuations appears rapid (with respect to the measurement time per shear rate in the flow curve), on the order of tens to hundreds of milliseconds, with the speed of fluctuations associated with the flow history of the sample. Our velocity profile analysis suggests a qualitative model in which intermittent changes due to jamming/unjamming transitions occur, analogous to cage dynamics in colloidal glasses.

We present experimental results on the linear rheology of multiarm star/linear polymer mixtures, the latter having molecular weight much smaller than the star arm molecular weight. In such a case the linear chains act as ideal macromolecular solvents, which dilute entanglements of the arms. Using different star polymers we show that it is possible to account for this dilution and describe the linear rheology of the mixtures using the Milner–McLeish theory for arm relaxation, complemented by the longitudinal modes of stress relaxation and high frequency Rouse modes. A universal description of the isofrictional arm relaxation time as a function of the number of entanglements is obtained for stars of any functionality and degree of dilution. The slow structural mode, related to the diluted star’s colloidal core, also depends on the number of entanglements, but in a more complex way.

We explore the dynamic response of a marginally entangled poly(dimethyl siloxane)/poly(ethyl methyl siloxane) blend in simple shear flow using rheology and small angle light scattering in situ. Data are collected in both the flow/gradient and flow/vorticity planes. We find that for this model binary blend, exhibiting upper critical solution temperature behavior, shear suppresses the large pretransitional concentration fluctuations and eventually yields homogenization. The simple modified Cahn–Hilliard–Cook phenomenological model of Lai and Fuller [J. Polym. Sci. Part B: Polym. Phys. 32, 2461–2474 (1994)] describes semiquantitatively the time evolution of the structure factor and orientation angle well, supporting the experimental observations of enhanced orientation with flow. In the phase separated region, when the late stages of spinodal decomposition are reached, the shear-induced anisotropic distortion of the spinodal ring, orienting in the flow direction, and its relaxation upon flow cessation are pr...

We investigate the thermorheological properties of a partially miscible polymer blend exhibiting lower critical solution temperature phase diagram and having high glass transition and molecular weight constituents, namely poly(styrene-co-maleic anhydride)/poly(methyl methacrylate), SMA/PMMA, in the nonlinear regime. By using parallel plate, sliding plate, and capillary rheometry, with the knowledge of the blend’s phase behavior, we address the following aspects of its dynamic response: (i) the sensitivity of nonlinear viscoelastic properties to the phase behavior, which is reflected in the observed thermorheological complexity and a dual-peak stress response in large amplitude oscillatory shear; (ii) the effects of shear history on the morphological and rheological properties, which corroborate the picture of shear-induced fibrilar-type growth of the SMA-rich inclusions in the phase separated regime; and (iii) the evolution of shear and normal stresses and the relevant morphological changes in the phase s...

The response of macromolecular binary mixtures to shear flow is rather complex. Experimental evidence suggests that both shear-induced mixing and shear-induced demixing, observed as suppression or enhancement of concentration fluctuations, respectively, can occur (Hobbie et al, 1994; Larson, 1992; Takebe et al, 1989), depending on the amount of shearing and the molecular characteristics of the polymers (molecular weights, glass transition temperature, Tg). Some of the important open problems on the field are: (i) what happens with real industrial blends; (ii) what is the effect of very high shear rates (200 S−1 and above); (iii) how does the presence of glassy components and their large viscosity difference interplay with the shear influences on the phase characteristics.

Metallocene catalysts are known to produce homogeneous random polyolefin copolymers with narrow molecular weight distribution and controlled long/short-chain branching. Two such linear low-density polyethylenes were studied by using both constant-stress and capillary rheometry, in order to assess their rheological and processing behavior, as well as to identify critical conditions for the onset of flow instabilities. It was found that these polymers are thermorheologically complex liquids, apparently due to the presence of long-chain branching. Compared with conventional linear low-density polyethylenes, these metallocene polyethylenes exhibit quite unusual behavior in capillary flow, not previously reported to our knowledge. Specifically, we have encountered long transients in start-up of capillary experiments, and in some cases, the capillary reservoir had to be loaded several times before a steady-state pressure was obtained. In addition, we found that these polymers slip at shear stresses higher than about 0.05 MPa. This critical value is much smaller than the critical value of 0.10 MPa reported for other conventional polyethylenes. A simple qualitative model is proposed to rationalize these findings. It suggests that the molecular mechanism of slip is dominated by a competition between flow-induced chain detachment from the wall and disentanglement of the chains in the bulk from those attached to the wall.

Carefully prepared aqueous solutions of drag‐reducing polymers have been characterized by means of steady viscometric and molecular weight measurements. Solutions of anionic polyacrylamide (Cyanatrol‐750), 0.5–50 ppm, and nonionic poly (ethylene oxide) (Polyox WSR‐303), 100–1000 ppm, were investigated. Steady shear viscosity measurements, with a Rheometrics Stress Rheometer and a Contraves LS30 rheometer, reveal substantial shear thinning for Cyanatrol solutions above 2 ppm and Polyox solutions above 500 ppm, for the shear‐rate range investigated. Zero‐shear viscosity was accurately determined for all solutions. Intrinsic viscosity,hydrodynamic radius of gyration, and overlap concentration were also estimated. The Carreau and Carreau–Yasuda models successfully fit all shear viscosity data, and allow estimates of elasticity. Reduced variables were used for generalizing the shear viscosity data. Aging tests show that both polymers are stable. The molecular weight and polydispersity of Cyanatrol were measured using the technique of band sedimentation/low angle laser light scattering. The drag‐reducing capability of these polymers has been confirmed by pipe flow experiments.

Recently, large-amplitude oscillatory shear has been studied in great detail with emphasis on its impact on the material response. Here we present a conceptually different, robust methodology based on viewing the stress waveforms as representing a sequence of physical processes. This novel approach provides the viscous and elastic contributions while overcoming the problems with infinite series encountered by Fourier transformation. Application to a soft colloidal star glass leads to the unambiguous determination and quantification of rate-dependent static and dynamic yield stresses, the rationalization of the response to strain sweeps and the post-yield regime by introducing the apparent cage modulus, and a connection to the steady-shear stress, all from a single-amplitude experiment. We propose that this approach is generic, but focus in this contribution only on a yield stress material which exhibits repeating cycles of (i) elastic extension, (ii) yielding, (iii) flow, and (iv) reformation. We show tha...

Suspensions of multiarm star polymers are studied as models for soft colloidal glasses. Using an established pre-shearing protocol which ensures a reproducible initial state (the “rejuvenation” of the system), we report here the time evolution of the stress upon startup of simple shear flow for a range of shear rates. We show the existence of critical shear rates, γc(c) which are functions of the concentration, c. When the suspensions are sheared at rates below γc(c), the stress rises to a common value σc(c) which is also a function of the concentration. The system thus develops a yield stress. This behavior manifests itself as an evolution from a monotonic slightly shear-thinning flow curve to a flow curve dominated by a stress plateau. We relate this bulk evolution to spatially resolved velocity profiles. Hence, yield stress is linked to shear banding in this class of soft colloids.