Dimitris Vlassopoulos

Unexpected power-law stress relaxation of entangled ring polymers

After many years of intense research, most aspects of the motion of entangled polymers have been understood. Long linear and branched polymers have a characteristic entanglement plateau and their stress relaxes by chain reptation or branch retraction, respectively. In both mechanisms, the presence of chain ends is essential. But how do entangled polymers without ends relax their stress? Using properly purified high-molar-mass ring polymers, we demonstrate that these materials exhibit self-similar dynamics, yielding a power-law stress relaxation. However, trace amounts of linear chains at a concentration almost two decades below their overlap cause an enhanced mechanical response. An entanglement plateau is recovered at higher concentrations of linear chains. These results constitute an important step towards solving an outstanding problem of polymer science and are useful for manipulating properties of materials ranging from DNA to polycarbonate. They also provide possible directions for tuning the rheology of entangled polymers.

Yielding behavior of repulsion- and attraction-dominated colloidal glasses

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.

A sequence of physical processes determined and quantified in LAOS: Application to a yield stress fluid

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...

INTERFACIAL PHENOMENA IN THE CAPILLARY EXTRUSION OF METALLOCENE POLYETHYLENES

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 ...

Viscoelasticity and shear melting of colloidal star polymer glasses

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...

Asymmetric caging in soft colloidal mixtures

The long-standing observations that different amorphous materials exhibit a pronounced enhancement of viscosity and eventually vitrify on compression or cooling continue to fascinate and challenge scientists, on the ground of their physical origin and practical implications. Glass formation is a generic phenomenon, observed in physically quite distinct systems that encompass hard and soft particles. It is believed that a common underlying scenario, namely cage formation, drives dynamical arrest, especially at high concentrations. Here, we identify a novel, asymmetric glassy state in soft colloidal mixtures, which is characterized by strongly anisotropically distorted cages, bearing similarities to those of hard-sphere glasses under shear. The anisotropy is induced by the presence of soft additives. This phenomenon seems to be generic to soft colloids and its origins lie in the penetrability of the constituent particles. The resulting phase diagram for mixtures of soft particles is clearly distinct from that of hard-sphere mixtures and brings forward a rich variety of vitrified states that delineate an ergodic lake in the parameter space spanned by the size ratio between the two components and by the concentration of the additives. Thus, a new route opens for the rational design of soft particles with desired tunable rheological properties.

Probing Collective Motions of Terminally Anchored Polymers

Polymer chains attached by one end to an impenetrable surface at high coverage exemplify a tethered layer of mesoscopic dimensions. At equilibrium, thermal fluctuations of the segment density profile of the brushlike layer reflect the tethered chain dynamics; the probing of these fluctuations by evanescent-wave dynamic light scattering is reported. By utilizing a set of terminally attached layers with thicknesses (L0) from 45 to 130 nanometers, it was found that there is a preferred wavelength of order L0 of these fluctuations with a concurrent slowing down of their thermal decay rate. This technique could open the route for the investigation of the largely unexplored area of polymer surface dynamics.

Ageing and yield behaviour in model soft colloidal glasses

We use multi-arm star polymers as model soft colloids with tuneable interactions and explore their behaviour in the glassy state. In particular, we perform a systematic rheological study with a well-defined protocol and address aspects of ageing and shear melting of star glasses. Ageing proceeds in two distinct steps: a fast step of O(103 s) and a slow step of O(104 s). We focus on creep and recovery tests, which reveal a rich, albeit complex response. Although the waiting time, the time between pre-shear (rejuvenation) of the glassy sample and measurement, affects the material’s response, it does not play the same role as in other soft glasses. For stresses below the yield value, the creep curve is divided into three regimes with increasing time: viscoplastic, intermediate steady flow (associated with the first ageing step) and long-time evolving elastic solid. This behaviour reflects the interplay between ageing and shear rejuvenation. The yield behaviour, as investigated with the stress-dependent recoverable strain, indicates a highly nonlinear elastic response intermediate between a low-stress Hookean solid and a high-stress viscoelastic liquid, and exemplifies the distinct characteristics of this class of hairy colloids. It appears that a phenomenological classification of different colloidal glasses based on yielding performance may be possible.

Dynamics and rheology of colloidal star polymers

We attempt to elucidate the dynamics of multiarm star polymer solutions, which are representative of a large class of soft hairy colloids, over a wide range of concentrations. In addition to the usual β-relaxation (in-cage rattling) and α-relaxation (terminal cage escape), the relaxation of stars in the glassy state involves a mode associated with arm interpenetration. From linear and nonlinear rheological measurements, we establish a set of criteria for identifying the colloidal glass transition, including aging, yielding and elastic properties. Linear viscoelasticity and steady-shear measurements merge at low frequencies, indicating that terminal behavior is accessible, albeit at very long times. The transition from linear to nonlinear response is controlled by star elasticity and a balance between Brownian diffusion and flow advection. In the nonlinear regime, the flow curves collapse on a universal flow curve using a scaling that expresses a competition between solvent-mediated interactions and elastic forces. While applied to stars, our framework appears to be a generic tool for fingerprinting liquid-solid transitions in colloidal suspensions.

On the stability of the simple shear flow of a Johnson–Segalman fluid

We solve the time-dependent simple shear flow of a Johnson‐Segalman fluid with added Newtonian viscosity. We focus on the case where the steady-state shear stress:shear rate curve is not monotonic. We show that, in addition to the standard smooth linear solution for the velocity, there exists, in a certain range of the velocity of the moving plate, an uncountable infinity of steady-state solutions in which the velocity is piecewise linear, the shear stress is constant and the other stress components are characterized by jump discontinuities. The stability of the steady-state solutions is investigated numerically. In agreement with linear stability analysis, it is shown that steady-state solutions are unstable only if the slope of a linear velocity segment is in the negative-slope regime of the shear stress:shear rate curve. The time-dependent solutions are always bounded and converge to a stable steady state. The number of the discontinuity points and the final value of the shear stress depend on the initial perturbation. No regimes of self-sustained oscillations have been found.