Volume 15, Issue 1

We investigate the dynamics of the capillary thinning and break-up process for low viscosity elastic fluids such as dilute polymer solutions. Standard measurements of the evolution of the midpoint diameter of the necking fluid filament are augmented by high speed digital video images of the break up dynamics. We show that the successful operation of a capillary thinning device is governed by three important time scales (which characterize the relative importance of inertial, viscous and elastic processes), and also by two important length scales (which specify the initial sample size and the total stretch imposed on the sample). By optimizing the ranges of these geometric parameters, we are able to measure characteristic time scales for tensile stress growth as small as 1 millisecond for a number of model dilute and semi-dilute solutions of polyethylene oxide (PEO) in water and glycerol. If the final aspect ratio of the sample is too small, or the total axial stretch is too great, measurements are limited, respectively, by inertial oscillations of the liquid bridge or by the development of the well-known beads-on-a-string morphology which disrupt the formation of a uniform necking filament. By considering the magnitudes of the natural time scales associated with viscous flow, elastic stress growth and inertial oscillations it is possible to construct an “operability diagram” characterizing successful operation of a capillary breakup extensional rheometer. For Newtonian fluids, viscosities greater than approximately 70 mPas are required; however for dilute solutions of high molecular weight polymer, the minimum viscosity is substantially lower due to the additional elastic stresses arising from molecular extension. For PEO of molecular weight 2 · 10 6 g/mol, it is possible to measure relaxation times of order 1 ms in dilute polymer solutions with zero-shear-rate viscosities on the order of 2 – 10 mPas.

Commercially available, blended methylhydroxyethyl celluloses with similar weight-average molar masses but varying molar mass distributions were characterized by different techniques like steady shear flow and uniaxial elongation in capillary breakup experiments. The determined relaxation times t were then correlated with the absolute molar mass distribution acquired via SEC/MALLS/DRI (combined methods of size-exclusion-chromatography, multi angle laser light scattering and differential refractometer). In order to describe the longest relaxation time of the polymers in uniaxial elongation via integral mean values of the molar mass distribution, defined blends of polystyrene standards with varying molar mass distributions were characterized. The obtained data was scaled via different moments of the molecular weight distribution and could be correlated with the results obtained for the methylhydroxyethyl celluloses.

Viscosity measurements of a suspension of cornstarch in silicone oil, at several concentrations and subject to different electrical field strengths, were conducted. An increase in the apparent viscosity, in correlation with the field strength, which is characteristic of the so-called electrorheological fluids (ERF), was observed. For a given field intensity, the value of the viscosity increases rapidly in the first seconds after the application of the electric field, and then it increases slowly until it finally approaches a saturation value. This behaviour of the apparent viscosity has been related to the microstructure formation due to interactions between dipoles induced by the electric field. Characteristic times, related to structure formation after application of an electric field, are investigated by means of diffuse light transmission and speckle-pattern activity measurements. Two characteristic times were found that should be related to the state of aggregation of the suspended particles: orientation of the non-isotropic particles and later chain formation. These results agree reasonably with that obtained from electrorheological measurements. Microscopic observations of structure formation are also reported.