Extensional rheology of concentrated emulsions as probed by capillary breakup elongational rheometry (CaBER)

Elongational flow behavior of w/o emulsions has been investigated using a capillary breakup elongational rheometer (CaBER) equipped with an advanced image processing system allowing for precise assessment of the full filament shape. The transient neck diameter D(t), time evolution of the neck curvature κ(t), the region of deformation l _def and the filament lifetime t _c are extracted in order to characterize non-uniform filament thinning. Effects of disperse volume fraction ?, droplet size d _sv , and continuous phase viscosity η _c on the flow properties have been investigated. At a critical volume fraction ? _c , strong shear thinning, and an apparent shear yield stress τ _y,s occur and shear flow curves are well described by a Herschel–Bulkley model. In CaBER filaments exhibit sharp necking and t _c as well as κ _max ?=?κ (t?=?t _c ) increase, whereas l _def decreases drastically with increasing ?. For ? <?? _c , D(t) data can be described by a power-law model based on a cylindrical filament approximation using the exponent n and consistency index k from shear experiments. For ??≥?? _c , D(t) data are fitted using a one-dimensional Herschel–Bulkley approach, but k and τ _y,s progressively deviate from shear results as ? increases. We attribute this to the failure of the cylindrical filament assumption. Filament lifetime is proportional to η _c at all ?. Above ? _c, κ _max as well as t _c /η _c scale linearly with τ _y,s . The Laplace pressure at the critical stretch ratio ε _c which is needed to induce capillary thinning can be identified as the elongational yield stress τ _y,e , if the experimental parameters are chosen such that the axial curvature of the filament profile can be neglected. This is a unique and robust method to determine this quantity for soft matter with τ _y ?< 1,000 Pa. For the emulsion series investigated here a ratio τ _y,e /τ _y,s = 2.8 ± 0.4 is found independent of ?. This result is captured by a generalized Herschel–Bulkley model including the third invariant of the strain-rate tensor proposed here for the first time, which implies that τ _y,e and τ _y,s are independent material parameters.     

Birefringence measurements in extensional flow of polyisobutylene around an expanding bubble

Birefringence in liquid polymers offers the possibility of obtaining information about stress in complex flows. In this work, this is done for extensional flows of polyisobutylene in a “breathing bubble” rheometer. In this type of rheometer, a bubble consisting of an incompressible, low-viscosity fluid (usually water) is injected into the sample with a nozzle. Expanding or collapsing the bubble by adding or removing water induces biaxial or uniaxial extension in the surrounding sample. The pressure difference between the bubble and the surroundings can be measured and compared to the predictions of constitutive equations. This measurement only gives one integral value for a complex flow history. In this paper, the birefringence around the bubble is measured in order to learn more about the flow. This is done by comparing pressure and birefringence results to those of standard constitutive equations for a polyisobutylene sample. A good agreement between the pressure and optical measurements and the theory is found with a single value of the stress-optical constant. Received: 25 June 1997 Accepted: 12 November 1997     

Capillary breakup extensional rheometry (CaBER) on semi-dilute and concentrated polyethyleneoxide (PEO) solutions

Semi-dilute ( $c^\ast < c < c_{\rm e}$ ) as well as concentrated, entangled (c?>?c _e) solutions of PEO yield uniformly thinning, cylindrical filaments in capillary breakup extensional rheometry (CaBER) experiments. Up to c?≈ c _e thinning can be characterized by a single elongational relaxation time λ _E. Comparison with the longest shear relaxation time, λ _S reveals that λ _E/λ _S decreases with increasing concentration or molecular weight according to (c[η])^???4/3. This is attributed to the large deformation the solutions experience during filament thinning. A factorable integral model including a single relaxation time and a Soskey or Wagner damping function accounting for the large deformation in CaBER experiments is used to calculate λ _E/λ _S and provides good agreement with experimental results. Irrespective of concentration or molecular weight a beads-on-a-string structure occurs prior to filament breakup at a diameter ratio D/D ₀?≈ 0.01. This instability is supposed to be closely related to a flow-induced phase separation.     

A Simple Model for a Fluid-Filled Open-Cell Foam

A simple microstructure model is used to describe a fluid-filled open-cell foam. In the simplest case it consists of parallel elastic plates with gaps between them, which are filled with a Newtonian fluid. We assume that the load applied to this model material is uniaxial. The constitutive equation is formulated with the pressure of the fluid as an inner variable. The model yields an evolutional equation for the fluid pressure which itself is a field equation, that is a partial differential equation in time and space coordinates. This differential equation is solved for an instantaneously applied constant load and for a harmonically oscillating load. The solution of the differential equation, in combination with the constitutive equation leads to a relation between mean applied load and global strain of the test specimen. Finally, we obtain the creep compliance and the complex modulus of the foam material, respectively. The influence of different geometries of the foam and of different material behaviour of the matrix and fluid on the creep compliance and the complex modulus is discussed.