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.     

Is there a relation between the relaxation time measured in CaBER experiments and the first normal stress coefficient?

We investigate a variety of different semidilute polymer solutions in shear and elongational flow. The shear flow is created in the cone-plate-geometry of a commercial rheometer. We use capillary thinning of a filament that is formed by a polymer solution in the Capillary Breakup Extensional Rheometer (CaBER) as an elongational flow. We compare the relaxation time measured in the CaBER with relaxation times based on the first normal stress difference and the zero shear polymer viscosity that we measure in our rheometer. All of these three measurable quantities depend on different fluid parameters—the viscosity of the solvent, the polymer concentration within the solution, and the molecular weight of the polymers—and on the shear rate (in the shear flow measurements). Nevertheless, we find that the first normal stress coefficient depends quadratically on the CaBER relaxation time. Several scaling laws are presented that could help to explain this empirical relation.     

Determination of axial forces during the capillary breakup of liquid filaments – the tilted CaBER method

The capillary breakup extensional rheometry (CaBER) is a versatile method to characterize the elongational behavior of low-viscosity fluids. Commonly, data evaluation is based on the assumption of zero normal stress in axial direction ( $\upsigma_{\rm zz}=0$ ). In this paper, we present a simple method to determine the axial force using a CaBER device rotated by 90° and analyzing the deflection of the filament due to gravity. Forces in the range of 0.1–1,000?μN could be assessed. Our study includes experimental investigations of Newtonian fructose solutions and silicon oil mixtures (viscosity range, 0.9–60?Pa s) and weakly viscoelastic polyethylene oxide (PEO, $M_{\rm w}=10^{6}$ ?g/mol) solutions covering a concentration range from c?≈?c* (critical overlap concentration) up to c?>?c _e (entanglement concentration). Papageorgiou’s solution for the stress ratio $\upsigma_{\rm zz}/\upsigma_{\rm rr}$ in Newtonian fluids during capillary thinning is experimentally confirmed, but the widely accepted assumption of vanishing axial stress in weakly viscoelastic fluids is not fulfilled for PEO solutions, if c _e is exceeded.     

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.     

Experimental estimation of elongational stresses of dilute polymer solutions and a related examination of some constitutive equations

Elongational stresses of dilute polymer solutions have been estimated by utilizing the flow through small orifices under the condition of no vortex upstream of the orifice plane. The flow was approximated with a linearly converging flow towards an apex of a cone, its validity being partially confirmed by the measured center velocities, and the elongational stresses are determined from the measured thrusts of dilute polymer solutions. On the other hand, elongational stresses were theoretically obtained with the modified Maxwell model and the second order fluid. A comparison was made between the experimental and the theoretical results and the following points were clarified; below an elongational rate of 2 × 10⁴ s⁻¹ the modified Maxwell model gives elongational stresses close to the experimentally determined ones, but above that elongational rate it deviates from the experimental results. The second order fluid is not sufficient to describe the stresses in this kind of elongational flow and an acceleration term such as δ²e^ij/δt² may be necessary in this case.     

On the use of stretched-exponential functions for both linear viscoelastic creep and stress relaxation

The use of the stretched-exponential function to represent both the relaxation function g(t)=(G(t)-G _∞)/(G ₀-G _∞) and the retardation function r(t) = (J _∞+t/η-J(t))/(J _∞-J ₀) of linear viscoelasticity for a given material is investigated. That is, if g(t) is given by exp (?(t/τ)^β), can r(t) be represented as exp (?(t/λ)^µ) for a linear viscoelastic fluid or solid? Here J(t) is the creep compliance, G(t) is the shear modulus, η is the viscosity (η^?1 is finite for a fluid and zero for a solid), G _∞ is the equilibrium modulus G _e for a solid or zero for a fluid, J _∞ is 1/G _e for a solid or the steady-state recoverable compliance for a fluid, G ₀= 1/J ₀ is the instantaneous modulus, and t is the time. It is concluded that g(t) and r(t) cannot both exactly by stretched-exponential functions for a given material. Nevertheless, it is found that both g(t) and r(t) can be approximately represented by stretched-exponential functions for the special case of a fluid with exponents β=µ in the range 0.5 to 0.6, with the correspondence being very close with β=µ=0.5 and λ=2τ. Otherwise, the functions g(t) and r(t) differ, with the deviation being marked for solids. The possible application of a stretched-exponential to represent r(t) for a critical gel is discussed.     

Shear and elongational flow behavior of acrylic thickener solutions. Part II: effect of gel content

We have investigated the effect of crosslink density on shear and elongational flow properties of alkali-swellable acrylic thickener solutions using a mixing series of the two commercial thickeners Sterocoll FD and Sterocoll D as model system. Linear viscoelastic moduli show a smooth transition from weakly elastic to gel-like behavior. Steady shear data are very well described by a single mode Giesekus model at all mixing ratios. Extensional flow behavior has been characterized using the CaBER technique. Corresponding decay of filament diameter is also well fitted by the Giesekus model, except for the highest crosslink densities, when filament deformation is highly non-uniform, but the non-linearity parameter α, which is independent of the mixing ratio, is two orders of magnitude higher in shear compared to elongational flow. Shear relaxation times increase by orders of magnitude, but the characteristic elongational relaxation time decreases weakly, as gel content increases. Accordingly, variation of gel content is a valuable tool to adjust the low shear viscosity in a wide range while keeping extensional flow resistance essentially constant.     

The effect of step-stretch parameters on capillary breakup extensional rheology (CaBER) measurements

Extensional rheometry has only recently been developed into a commercially available tool with the introduction of the capillary breakup extensional rheometer (CaBER). CaBER is currently being used to measure the transient extensional viscosity evolution of mid to low-viscosity viscoelastic fluids. The elegance of capillary breakup extensional experiments lies in the simplicity of the procedure. An initial step-stretch is applied to generate a fluid filament. What follows is a self-driven uniaxial extensional flow in which surface tension is balanced by the extensional stresses resulting from the capillary thinning of the liquid bridge. In this paper, we describe the results from a series of experiments in which the step-stretch parameters of final length, and the extension rate of the stretch were varied and their effects on the measured extensional viscosity and extensional relaxation time were recorded. To focus on the parameter effects, well-characterized surfactant wormlike micelle solutions, polymer solutions, and immiscible polymer blends were used to include a range of characteristic relaxation times and morphologies. Our experimental results demonstrate a strong dependence of extensional rheology on step-stretch conditions for both wormlike micelle solutions and immiscible polymer blends. Both the extensional viscosity and extensional relaxation time of the wormlike micelle solutions were found to decrease with increasing extension rate and strain of the step-stretch. For the case of the immiscible polymer blends, fast step-stretches were found to result in droplet deformation and an overshoot in the extensional viscosity which increased with increasing strain rates. Conversely, the polymer solutions tested were found to be insensitive to step-stretch parameters. In addition, numerical simulations were performed using the appropriate constitutive models to assist in both the interpretation of the CaBER results and the optimization of the experimental protocol. From our results, it is clear that any rheological results obtained using the CaBER technique must be properly considered in the context of the stretch parameters and the effects that preconditioning has on viscoelastic fluids.     

Microsecond relaxation processes in shear and extensional flows of weakly elastic polymer solutions

In this paper, we introduce an experimental protocol to reliably determine extensional relaxation times from capillary thinning experiments of weakly elastic dilute polymer solutions. Relaxation times for polystyrene in diethyl phthalate solutions as low as 80?μ s are reported: the lowest relaxation times in uniaxial extensional flows that have been assessed so far. These data are compared to the linear viscoelastic relaxation times that are obtained from fitting the Zimm spectrum to high frequency oscillatory squeeze flow data measured with a piezo-axial vibrator (PAV). This comparison demonstrates that the extensional relaxation time reduced by the Zimm time, λ _ext/λ _z, is not solely a function of the reduced concentration c/c*, as is commonly stated in the literature: an additional dependence on the molecular weight is observed.     

Some remarks on “Drag coefficients of a slowly moving sphere in Non-Newtonian fluids”

Viscoelastic solutions were ejected vertically downwards into air and various Newtonian fluids. The measured swell increased significantly when ejected into a liquid rather than air. The observed increase is considered a result of both bouyancy and drag forces on the solution. The following dimensions expression relating the ratio of the swell diameter in liquid and air D_L/D_A to the elastic shear compliance of the ejected solution J_e was experimentally observed.(D_L/D_A)⁶-1=30(Δ?/?_s)^{?$\text{1}\text{2}$}([g²η²_N?_s]$\text{1}\text{3}$J_e)^{$\text{3}\text{5}$}, where Δ? is the density difference between the extruded and Newtonian fluid, ?_s is the solution density, g is the gravitational constant, and η_N is the Newtonian fluid viscosity. Thus with this expression a simple extrudate swell technique exists to estimate the elastic shear compliance of a viscoelastic solution.     

The role of solvent viscosity in dilute-solution polymer rheology

Capillary viscometry was performed on dilute non-Newtonian solutions of monodisperse polystyrene in theta solvents. The solvents, blends of low-molecular-weight polystyrene with styrene, had viscosities (η_s) that were varied from 0.22–27 Pa s. Data reduction of the dilute limit, [η]/[η₀] vs. β = [η₀]η_sM$\text{γ}\text{?}$/RT (where $\text{γ}\text{?}$ is shear rate) revealed a parametric dependence on η_s that has not before been reported and is not predicted by most molecular theories of polymer dynamics. It is suggested that an internal viscosity model can explain such a phenomenon.     

An encapsulated dumbbell model for concentrated polymer solutions and melts II. Calculation of material functions and experimental comparisons

The consitutive equation derived in Part I [1] is used to compute steady-state and time-dependent material functions. A procedure is suggested for determining the four independent model parameters (λ_H, b, σ, β) from experimental data.Material functions have been calculated using parameters determined by experimental data for concentrated solutions of nearly monodisperse linear polymers. The theoretical curves for steady shear properties (η and Ψ₁) are in quantitative agreement with the data well into the range of nonlinear behavior. The calculated time-dependent properties (η*, η⁺, Ψ⁺, η^?) are in qualitative agreement with observed behavior. Theoretical curves for elongational viscosity are reasonable, but suitable experimental data are not available for comparison.     

New type of equation for the relation between viscosity and particle content in suspensions

Many disperse systems show a typical non-Newtonian flow at relatively high concentrations of the disperse particle. However, two Newtonian viscosities η_∞ and η₀ can be, respectively, determined at high and low rates of shear. Expect for very low particle content, η_∞/η_s is proportional to exp(mϕ), where η_s is a medium viscosity, m a constant which might reflect the particle-particle interaction and ϕ the volume fraction. In considering this relationship, a new type of equation which describes the relation between the zero shear relative viscosity η_r0( ≡ η₀/η_s) of the disperse system and ϕ is proposed as follows. ln η_r0 = A(p)ϕ + am³ϕ², where A(p), the Einstein-Simha constant, is a function of the axial ratio p of dispersing particles, and a is a constant (⋍ 0.03) which depends slightly on the particle shape.The equation has been compared with the experimental results obtained for several disperse systems. A number of disperse systems of spherical particles are described well by the choice A(p) = 2.5 and a = 0.027, and a system of rod-like particles with p = 50 by the choice A(p) = 215.6 and a = 0.033. m for rod-like particles is larger than that for spherical particles.     

Rheo-optical measurements of the elongational flow of aqueous polymer solutions

An opposed jets rheometer was used to investigate the elongational viscosity as a function of the strain rate for dilute aqueous solutions of polyvinylformamide and polyacrylamide. Critical strain rates at which the enhancement in elongational viscosity occurs were determined for both systems. The influence of the polymer concentration on the elongational viscosity was investigated. The measurements were performed with polymer concentrations less than the critical polymer concentration c_p^* c_p^* . In order to assess the deformation and orientation of the macromolecules, flow-induced birefringence was measured simultaneously.     

An investigation of non-newtonian flow past a sphere

Any experimental work on the flow of a polymer solution or any theoretical analysis on the basis of a visoelastic constitutive equation does not always bring out viscoelastic effects but may be showing a non-Newtonian viscosity effect. Therefore, in order to obtain a clear understanding about viscoelastic effects, it is desirable to have a sufficient knowledge of the non-Newtonian viscosity effect. To facilitate this, finite-difference numerical solutions of non-Newtonian flow were carried out using a non-Newtonian viscous model for the Reynolds numbers of 0.1, 1.0, 20 and 60.Drag force measurements and flow visualization experiments were also performed over a wide range of experimental conditions using polymer solutions. The present work appears to support the following idea: When compared with the Newtonian case on the basis of DV_∞P/η₀, where η₀ is the zero shear viscosity, it is on account of the non-Newtonian viscosity that the friction and pressure drags decrease, that the separating vortices behind the sphere become larger, and that no shift occurs in the streamlines. On the other hand, it is due to viscoelasticity that the normal force drag increases, that the separating vortices behind the sphere become smaller, and that an upstream shift occurs in the streamlines.     

Some exact solutions for rotating flows of a generalized Burgers’ fluid in cylindrical domains

The velocity field and the adequate shear stress corresponding to the flow of a generalized Burgers’ fluid model, between two infinite co-axial cylinders, are determined by means of Laplace and finite Hankel transforms. The motion is due to the inner cylinder that applies a time dependent torsional shear to the fluid. The solutions that have been obtained, presented in series form in terms of usual Bessel functions J₁( ? ), J₂( ? ), Y₁( ? ) and Y₂( ? ), satisfy all imposed initial and boundary conditions. Moreover, the corresponding solutions for Burgers’, Oldroyd-B, Maxwell, second grade, Newtonian fluids and large-time transient solutions for generalized Burgers’ fluid are also obtained as special cases of the present general solutions. The effect of various parameters on large-time and transient solutions of generalized Burgers’ fluid is also discussed. Furthermore, for small values of the material parameters, λ₂ and λ₄ or λ₁, λ₂, λ₃ and λ₄, the general solutions corresponding to generalized Burgers’ fluids are going to those for Oldroyd-B and Newtonian fluids, respectively. Finally, the influence of the pertinent parameters on the fluid motion, as well as a comparison between models, is shown by graphical illustrations.     

Step and steady shear responses of nearly monodisperse highly entangled 1,4-polybutadiene solutions

Nonlinear relaxation dynamics of highly entangled solutions of high molecular weight 1,4-polybutadiene (PB) in a PB oligomer are studied in steady shear and step shear flows. Polymer entanglement densities vary in the range 14hN/N_e(J)⣴, allowing systematic investigation of entanglement effects on nonlinear rheological response. In agreement with previous steady shear studies using well entangled polystyrene solutions, a flow regime is found where both the steady-state shear stress and first normal stress difference remain constant or increase quite slowly with shear rate, leading to a plateau in the steady-state orientation angle. The magnitude of the average orientation angle in the plateau range is in accordance with predictions of a recent theory by Islam and Archer (2001). In step shear, the nonlinear relaxation modulus G(t,%) is approximately factorable into time-dependent G(t) and strain-dependent h(%) functions only at long times, t>5_k, where 5_k,O(F_d0). This finding is consistent with earlier observations for entangled polystyrene solutions; however the complex crossing pattern in G(t,%)h^-1(%) that precede factorability in the latter materials is not observed. For all but the most entangled sample, apparent shear damping functions h (%,t)=(G(t,%))/(G(t)) immediately following imposition of shear are in nearly quantitative accord with the damping function h_DEIA predicted by Doi-Edwards theory.     

Scaling relations for elongational flow of polystyrene melts and concentrated solutions of polystyrene in oligomeric styrene

A consistent model of the rheology of polymer melts and concentrated solutions is presented, based on the idea that the pressures exerted by a polymer chain on the walls of an anisotropic confinement are anisotropic (Doi and Edwards. The Theory of Polymer Dynamics, Oxford University Press, 1986). In a tube model with variable tube diameter, chain stretch and tube diameter reduction are related, and at deformation rates larger than the inverse Rouse time τ _R, the chain is stretched and its confining tube becomes increasingly anisotropic. Tube diameter reduction leads to an interchain pressure in the lateral direction of the tube (Marrucci and Ianniruberto. Macromolecules 37:3934-3942, 2004). Chain stretch is balanced by interchain tube pressure in the lateral direction, which is proportional to the third power of stretch, and by a spring force in the longitudinal direction of the tube, which is linear in stretch. Analyzing elongational viscosity data of Huang et al. (Macromolecules 46:5026-5035, 2013a; ACS Macro Letters 2:741-744, 2013b) shows that dilution of polystyrene by oligomeric styrene does not change the relative interchain tube pressure. Based on this extended interchain pressure concept, scaling relations for linear viscoelasticity and elongational viscosity of polystyrene melts and concentrated solutions of polystyrene in oligomeric styrene are presented based exclusively on the relaxation modulus of a reference polymer melt, the volume fraction of polymer in the solution, and the time-molar-mass shift as well as the time-temperature shift caused by the reduction of the glass transition temperature T _g of the polymer in a solution relative to T _g of the melt.     

Rheology of SiO 2 /(acrylic polymer/epoxy) suspensions. III. Uniaxial elongational viscosity

Uniaxial elongational viscosity of SiO₂/(acrylic polymer/epoxy (AP/EP)) suspensions with various SiO₂ volume fractions (?) in a blend of acrylic polymer and epoxy was investigated at various temperatures (T). The matrix polymer ((AP/EP) blend) contained 70?vol.% of EP. At ?????35?vol.% at T????80°C, where the suspensions were in sol state, strain-hardening behavior was observed. This strain hardening of the suspensions is attributable to the elongational flow properties of (AP/EP) medium. At critical gel state (??=?35?vol.% and T?=?100°C) and in gel state (?????40?vol.%), the elongational viscosity exhibited the strain-softening behavior. These results strongly suggest that the strain softening results from the strain-induced disruption of the network structure of the SiO₂ particles therein.     

Newtonian,power law,and infinite shear flow characteristics of concentrated slurries using percolation theory concepts

There is a strong interest today in concentrated particulate-filled dispersion and slurries in both polymeric and Newtonian fluids. This paper reviews and extends theoretical approaches using percolation theory concepts to characterize the rheological behavior of fluids filled with particulate solids. First, a previously proposed limiting, zero shear viscosity model based on percolation theory concepts is reviewed. This model has been primarily tested with rigid fillers in a Newtonian carrier and polymeric fluids. Second, all Newtonian fluid-based slurries that have a high concentration of filler become pseudoplastic, shear-thinning slurries at some threshold shear rate. A new theory is reviewed and new data are evaluated that correlate the power law constant, n, to cluster formation of the fillers suspended in the fluids in shear flow. Slurry systems reported here cover a size range from 58 nm to 200 μm. Third, this cluster percolation-based rheological analysis is then extended to a newly proposed model for the calculation of the ratio of infinite shear, η_∞, to the zero shear viscosity, η₀. Using literature data, it is demonstrated that measurements of the viscosity ratio, η_∞/η₀, correlate with the power law through the use of an energy dissipation-based model for Bingham rheological fluids.