Effect of die surface on the onset of stick-slip flow in polymer processing

International audienceIn this paper, we investigate the relationships between stick-slip defect and molecular slip at the wall for linear polymers. By considering Brochard-de Gennes slip model and molecular chain dynamics at the wall, we propose an expression for the critical shear stress at the onset of stick-slip as a function of the wettability of the polymer on the die surface or, more precisely, as a function of the apparent contact angle between polymer and die surface

Periodic "stick-slip" transition within a continuum model for entangled supramolecular polymers

We investigate shear flow instabilities using a recently-derived constitutive law, designed for describing the rheology of entangled telechelic polymers. The continuum model displays shear banding, often accompanied by a strong elastic recoil in the transient response, which appears as an "apparent'" wall slip. For certain parameters, the model also displays a novel "apparent" stick-slip behavior, giving rise to strong nonlinear oscillations in the stress response driven by a repeating cycle of elastic recoil followed by diffusive rehomogenization of the flow. We elucidate the detailed mechanism behind this oscillatory response, demonstrating that it arises from a competition between shear-induced breaking of sticky bonds, which leads to recoil and banding, and a diffusive rehomogenization of the flow. We discuss the relation between the apparent stick-slip in our continuum model with similar behavior in "true" wall slip

A fractional K-BKZ constitutive formulation for describing the nonlinear rheology of multiscale complex fluids

The relaxation processes of a wide variety of soft materials frequently contain one or more broad regions of power-law like or stretched exponential relaxation in time and frequency. Fractional constitutive equations have been shown to be excellent models for capturing the linear viscoelastic behavior of such materials, and their relaxation modulus can be quantitatively described very generally in terms of a Mittag–Leffler function. However, these fractional constitutive models cannot describe the nonlinear behavior of such power-law materials. We use the example of Xanthan gum to show how predictions of nonlinear viscometric properties, such as shear-thinning in the viscosity and in the first normal stress coefficient, can be quantitatively described in terms a nonlinear fractional constitutive model. We adopt an integral K-BKZ framework and suitably modify it for power-law materials exhibiting Mittag–Leffler type relaxation dynamics at small strains. Only one additional parameter is needed to predict nonlinear rheology, which is introduced through an experimentally measured damping function. Empirical rules such as the Cox–Merz rule and Gleissle mirror relations are frequently used to estimate the nonlinear response of complex fluids from linear rheological data. We use the fractional model framework to assess the performance of such heuristic rules and quantify the systematic offsets, or shift factors, that can be observed between experimental data and the predicted nonlinear response. We also demonstrate how an appropriate choice of fractional constitutive model and damping function results in a nonlinear viscoelastic constitutive model that predicts a flow curve identical to the elastic Herschel-Bulkley model. This new constitutive equation satisfies the Rutgers-Delaware rule, which is appropriate for yielding materials. This K-BKZ framework can be used to generate canonical three-element mechanical models that provide nonlinear viscoelastic generalizations of other empirical inelastic models such as the Cross model. In addition to describing nonlinear viscometric responses, we are also able to provide accurate expressions for the linear viscoelastic behavior of complex materials that exhibit strongly shear-thinning Cross-type or Carreau-type flow curves. The findings in this work provide a coherent and quantitative way of translating between the linear and nonlinear rheology of multiscale materials, using a constitutive modeling approach that involves only a few material parameters

Spatially resolved quantitative rheo-optics of complex fluids in a microfluidic device

In this study, we use microparticle image velocimetry (μ-PIV) and adapt a commercial birefringence microscopy system for making full-field, quantitative measurements of flow-induced birefringence (FIB) for the purpose of microfluidic, optical rheometry of two wormlike micellar solutions. In combination with conventional rheometric techniques, we use our microfluidic rheometer to study the properties of a shear-banding solution of cetylpyridinium chloride (CPyCl) with sodium salicylate (NaSal) and a nominally shear-thinning system of cetyltrimethylammonium bromide (CTAB) with NaSal across many orders of magnitude of deformation rates (10-2 ≤ math ≤ 104s-1). We use μ-PIV to quantify the local kinematics and use the birefringence microscopy system in order to obtain high-resolution measurements of the changes in molecular orientation in the wormlike fluids under strong deformations in a microchannel. The FIB measurements reveal that the CPyCl system exhibits regions of localized, high optical anisotropy indicative of shear bands near the channel walls, whereas the birefringence in the shear-thinning CTAB system varies more smoothly across the width of the channel as the volumetric flow rate is increased. We compare the experimental results to the predictions of a simple constitutive model, and we document the breakdown in the stress-optical rule as the characteristic rate of deformation is increased.National Science Foundation (U.S.) (Graduate Research Fellowship

A novel role for syndecan-3 in angiogenesis.

Syndecan-3 is one of the four members of the syndecan family of heparan sulphate proteoglycans and has been shown to interact with numerous growth factors via its heparan sulphate chains. The extracellular core proteins of syndecan-1,-2 and -4 all possess adhesion regulatory motifs and we hypothesized that syndecan-3 may also possess such characteristics. Here we show that a bacterially expressed GST fusion protein consisting of the entire mature syndecan-3 ectodomain has anti-angiogenic properties and acts via modulating endothelial cell migration. This work identifies syndecan-3 as a possible therapeutic target for anti-angiogenic therapy.This work was funded by Arthritis Research-UK (Grant No. 19207) and funds from the William Harvey Research Foundation both to JRW

Chromosomal instability and lack of cyclin E regulation in hCdc4 mutant human breast cancer cells

INTRODUCTION: Cyclin E, a G(1 )cyclin essential for G(1)–S phase transition, is known to have a profound effect on tumorigenesis. Elevated levels of cyclin E have been associated with breast cancer, and chromosomal instability observed in breast cancer is suggested to be associated with constitutive expression of cyclin E. It was previously demonstrated that SUM149PT human breast cancer cells show very high levels of cyclin E expression by western analysis and that they express a nonfunctional cyclin E ubiquitin ligase due to a mutation in the F-box protein hCdc4. METHODS: We examined cyclin E expression in both MCF10A and SUM149PT cells using western blot analysis and flow cytometry. Immunofluorescence was utilized for the localization of cyclin E in both normal and breast cancer cells. In addition, array comparative genomic hybridization analysis was performed to compare chromosome copy number alterations with levels of cyclin E expression among a panel of breast cancer cell lines. RESULTS: SUM149PT cells overexpress cyclin E on a cell per cell basis for the duration of the cell cycle. High cyclin E levels are maintained throughout the S phase, and SUM149PT cells exhibit an S phase delay or arrest probably due to cyclin E overexpression. In addition, comparative genomic hybridization indicated that SUM149PT cells exhibit many chromosome copy number alterations, which may reflect prior or ongoing genomic instability. However, no direct correlation was observed between cyclin E levels and genomic copy number alteration in a panel of human breast cancer cell lines. CONCLUSIONS: Cyclin E is overexpressed at high levels throughout the cell cycle in SUM149PT cells, which is in stark contrast to cyclin E degradation observed in the mid to late S phase of normal cells. SUM149PT cells are unable to regulate cyclin E and also exhibit many copy number alterations. However, there was a lack of direct correlation between cyclin E overexpression and chromosomal instability across a panel of other breast cancer cell lines examined

Oscillatory squeeze flow for the study of linear viscoelastic behavior

The squeezing of a sample between parallel plates has been used for many years to characterize the rheological behavior of soft, purely viscous materials, and in recent times, small-amplitude oscillatory squeezing has been proposed as a means to determine the linear viscoelastic properties of molten polymers and suspensions. The principal advantage of squeeze flow rheometer over rotational devices is the simplicity of the apparatus. It has no air bearing and is much less expensive and easier to use. Accuracy may be somewhat reduced, but for quality control purposes, it could be quite useful. It might also find application as the central component of a high-throughput rheometer for evaluating experimental materials. The deformation is not simple shear, but equations have been derived to show that the oscillatory compressive (normal) force that is measured can serve as a basis for calculating the storage and loss moduli. These theories as well as instruments that have been developed to generate the required deformation are described, and applications to a variety of materials are described