The rheological characterisation of bread dough using capillary rheometry

An Australian hard wheat flour–water dough has been characterised using parallel plate and capillary rheometers over an extensive range of apparent shear rates (10^− 3–10³ s^− 1) relevant to process conditions. Torsional measurements showed that the shear viscosity of the dough increased with strain to a maximum value and then decreased, suggesting a breakdown of the dough structure. Both torsional and capillary experiments revealed the shear-thinning behaviour of the dough. The wall slip phenomenon in capillary rheometry was investigated and found to be diameter dependent and occurred at a critical shear stress of approximately 5–10 kPa. A two-regime power law behaviour was observed, with the power law index approximately 0.3 in the low shear rate range increasing to 0.67 in the high shear rate range. Pressure fluctuation was observed in the capillary data and increased with shear rate, in particular, at shear rates approaching 10⁴ s^− 1. The results demonstrate that capillary rheometry is a viable means of rheologically testing dough at high shear rates provided pressure fluctuation is carefully monitored and capillary rheometry corrections, including wall slip, are accounted for.     

Measurements and model predictions of transient elongational rheology of polymeric nanocomposites

Transient elongational rheology of two commercial-grade polypropylene (PP) and the organoclay thermoplastic nanocomposites is investigated. A specifically designed fixture consisting of two drums (SER Universal Testing Platform) mounted on a TA Instruments ARES rotational rheometer was used to measure the transient uniaxial extensional viscosity of both polypropylene and nanoclay/PP melts. The Hencky strain rate was varied from 0.001 to 2 s^− 1, and the temperature was fixed at 180°C. The measurements show that the steady-state elongational viscosity was reached at the measured Hencky strains for the polymer and for the nanocomposites. The addition of nanoclay particles to the polymer melt was found to increase the elongation viscosity principally at low strain rates. For example, at a deformation rate of 0.3 s^− 1, the steady-state elongation viscosity for polypropylene was 1.4 × 10⁴ Pa s which was raised to 2.8 × 10⁴ and 4.5 × 10⁴ Pa s after addition of 0.5 and 1.5 vol.% nanoclay, respectively. A mesoscopic rheological model originally developed to predict the motion of ellipsoid particles in viscoelastic media was modified based on the recent developments by Eslami and Grmela (Rheol Acta 47:399–415, 2008) to take into account the polymer chain reptation. We show that the orientation states of the particles and the rheological behavior of the layered particles/thermoplastic hybrids can be quantitatively explained by the proposed model.     

The motion of long bubbles through viscoelastic fluids in capillary tubes

The penetration of long gas bubble through a viscoelastic fluid in a capillary tube has been studied in order to investigate the influence of viscoelastic material properties on the hydrodynamic coating thickness and local flow kinematics. Experiments are conducted for three tailored ideal elastic (Boger) fluids, designed to exhibit similar steady shear properties but substantially different elastic material functions. This allows for the isolation of elastic and extensional material effects on the bubble penetration process. The shear and extensional rheology of the fluid is characterized using rotational and filament stretching rheometers (FSR). The fluids are designed such that the steady-state extensional viscosity measured by the FSR at a Deborah number (De) greater than 1 differs over three orders of magnitude (Trouton ratio = 10³–10⁶). The experiment set up to measure the hydrodynamic coating thickness is designed to provide accurate data over a wide range of capillary numbers (0.01 < Ca < 100). The results indicate that the coating thickness in this process increases with an increase in the extensionally thickening nature of the fluid. Experiments are also conducted using several different capillary tube diameters (0.1 < D < 1 cm), in order to compare responses at similar Ca but different flow De. Suitable scaling methods and nonlinear viscoelastic constitutive equations are explored to characterize the displacement process for polymeric fluids. Bubble tip shapes at different De are recorded using a CCD camera, and measured using an edge detection algorithm. The influence of the mixed flow field on the bubble tip shape is examined. Particle tracking velocimetry experiments are conducted to compare the influence of viscoelastic properties on the velocity field in the vicinity of the bubble tip. Local shear and extension rates are calculated in the vicinity of the bubble tip from the velocity data. The results provide quantitative information on the influence of elastic and extensional properties on the bubble penetration process in gas-assisted injection molding. The bubble shape and velocity field information provides a basis for evaluating the performance of constitutive equations in mixed flow. Received: 19 January 1999 Accepted: 30 June 1999     

Flow-induced crystallization of high-density polyethylene: the effects of shear and uniaxial extension

The effects of shear, uniaxial extension and temperature on the flow-induced crystallization of two different types of high-density polyethylene (a metallocene and a ZN-HDPE) are examined using rheometry. Shear and uniaxial extension experiments were performed at temperatures below and well above the peak melting point of the polyethylenes in order to characterize their flow-induced crystallization behavior at rates relevant to processing (elongational rates up to 30 s^− 1 and shear rates 1 to 1,000 s^− 1 depending on the application). Generally, strain and strain rate found to enhance crystallization in both shear and elongation. In particular, extensional flow was found to be a much stronger stimulus for polymer crystallization compared to shear. At temperatures well above the melting peak point (up to 25°C), polymer crystallized under elongational flow, while there was no sign of crystallization under simple shear. A modified Kolmogorov crystallization model (Kolmogorov, Bull Akad Sci USSR, Class Sci, Math Nat 1:355–359, 1937) proposed by Tanner and Qi (Chem Eng Sci 64:4576–4579, 2009) was used to describe the crystallization kinetics under both shear and elongational flow at different temperatures.     

Rheological characterization and constitutive modeling of bread dough

Bread dough (a flour–water system) has been rheologically characterized using a parallel-plate, an extensional, and a capillary rheometer at room temperature. Based on the linear and nonlinear viscoelastic and viscoplastic data, two constitutive equations have been applied, namely a viscoplastic Herschel–Bulkley model and a viscoelastoplastic K–BKZ model with a yield stress. For cases where time effects are unimportant, the viscoplastic Herschel–Bulkley model can be used. For cases where transient effects are important, it is more appropriate to use the K-BKZ model with the addition of a yield stress. Finally, the wall slip behavior of dough was studied in capillary flow, and an appropriate slip law was formulated. These models characterize the rheological behavior of bread dough and constitute the basic ingredients for flow simulation of dough processing, such as extrusion, calendering, and rolling.     

Rheostructural studies of a discotic mesophase pitch at processing flow conditions

The flow-induced microstructure of a mesophase pitch was studied within custom-made dies for changing wall shear rates from 20 to 1,100 s^− 1, a flow scenario that is typically encountered during fiber spinning. The apparent viscosity values, measured at the nominal wall shear rates ranging from 500 to 2,500 s^− 1 using these dies, remain fairly constant. The microstructure was studied in two orthogonal sections: r–θ (cross section) and r–z (longitudinal mid plane). In these dies, the size of the microstructure gradually decreases toward the wall (to as low as a few micrometers), where shear rate is highest. Furthermore, as observed in the r–θ plane of the capillary, for a significant fraction of the cross section, discotic mesophase has a radial orientation. Thus, the directors of disc-like molecules were aligned in the vorticity (θ) direction. As confirmed from the microstructure in the r–z plane, most of the discotic molecules remain nominally in the flow plane. Orientation of the pitch molecules in the shear flow conditions is consistent with that observed in controlled low-shear rheometric experiments reported earlier. Microstructral investigation suggests that the radial orientation of carbon fibers obtained from a mesophase pitch originates during flow of pitch through the die.     

Wall slip of mayonnaises in viscometers

The shear flow of mayonnaise is generally characterized by an apparent yield stress, shear thinning in steady flow, stress overshoots upon inception of flow and other time-dependent effects. These observations are usually understood to be the result of structural rearrangement within the material. Additionally and separately, the possibility that emulsions may exhibit apparent wall slip on a microscopic scale at a solid-liquid boundary has been reported by some researchers. Thus, observed rheological behavior is likely to be the result of the interplay between these two phenomena. In the present work, it is demonstrated that when measurements are sought to be made on mayonnaise using rotational viscometers visible wall slip occurs, rendering such instruments ineffective for the purpose of making viscosity measurements even at shear rates as low as 10^–3s^–1. The factors that influence the onset and extent of slip are investigated with the help of parallel plate viscometers, and it is concluded that the observed “yielding” of mayonnaise is actually an artifact of the onset of macroscopic slip. Slip effects are also found in capillary flow but are ameliorated with increasing shear rate. To circumvent these problems, it is proposed that extensional viscometry be employed for determining the flow behavior of mayonnaises. Received: 18 August 1997 Accepted: 1 April 1998     

Extensional rheology of a shear-thickening cornstarch and water suspension

A filament-stretching rheometer is used to measure the extensional viscosity of a shear-thickening suspension of cornstarch in water. The experiments are performed at a concentration of 55 wt.%. The shear rheology of these suspensions demonstrates a strong shear-thickening behavior. The extensional rheology of the suspensions demonstrates a Newtonian response at low extension rates. At moderate strain rates, the fluid strain hardens. The speed of the strain hardening and the extensional viscosity achieved increase quickly with increasing extension rate. Above a critical extension rate, the extensional viscosity goes through a maximum and the fluid filaments fail through a brittle fracture at a constant tensile stress. The glassy response of the suspension is likely the result of jamming of particles or clusters of particles at these high extension rates. This same mechanism is responsible for the shear thickening of these suspensions. In capillary breakup extensional rheometry, measurement of these suspensions demonstrates a divergence in the extensional viscosity as the fluid stops draining after a modest strain is accumulated.     

Shear and elongational flow behavior of acrylic thickener solutions

We investigate the effect of hydrophobic aggregation in alkali-swellable acrylic thickener solutions on shear and extensional flow properties at technically relevant polymer concentrations using the commercial thickener Sterocoll FD as model system. Apparent molecular weight of aggregates in water is M _w  ≈ 10⁸ g/mol and decreases by more than an order of magnitude in ethanol. Zero shear viscosity η ₀ is low and shear thinning is weak compared to the high molecular weight of the aggregates. Linear viscoelastic relaxation is described by the Zimm theory up to frequencies of 10⁴ rad/s, demonstrating that no entanglements are present in these solutions. This is further supported by the concentration dependence of η ₀ and is attributed to strong association within the aggregates. Extensional flow behavior is characterized using the capillary break-up extensional rheometry technique including high-speed imaging. Solutions with ϕ ≥ 1% undergo uniform deformation and show pronounced strain hardening up to large Hencky strains. Elongational relaxation times are more than one order of magnitude lower than the longest shear relaxation times, suggesting that aggregates cannot withstand strong flows and do not contribute to the elongational viscosity.

Wall slip and melt fracture of poly(lactides)

The wall slip and melt fracture behaviour of several commercial polylactides (PLAs) as well as their rheological properties under shear and extensional have been investigated. The PLAs have had weight-average molecular weights in the range of 10⁴–10⁵ g/mol and studied in the temperature range of 160–200°C. The solution properties and linear viscoelastic behaviour of melts indicate linear microstructure behaviour. PLAs with molecular weights greater than a certain value were found to slip, with the slip velocity to increase with decrease of molecular weight. The capillary data were found to agree well with linear viscoelastic envelope once correction for slip effects was applied. The onset of melt fracture for the high molecular weight PLAs was found to occur at about 0.2 to 0.3 MPa, depending on the geometrical characteristics of the dies and independent of temperature. Addition of 0.5 wt.% of a polycaprolactone (PCL) into the PLA that exhibits melt fracture was found to be effective in eliminating and delaying the onset of melt fracture to higher shear rates. This is due to significant interfacial slip that occurs in the presence of PCL.     

A comparison of extensional viscosity measurements from various RME rheometers

The transient uniaxial extensional viscosity η _e of linear low density polyethylene (LLDPE) has been measured using the commercial Rheometric Scientific RME and the Münstedt Tensile Rheometer in an effort to compare the performance of available extensional rheometers. The RME indicated a significant strain hardening of the LLDPE, especially at a strain rate of 1 s⁻¹. In contrast, the Münstedt rheometer showed the LLDPE to be only slightly strain hardening. This artificial strain hardening effect in the RME resulted from the strain rate applied to the sample, determined from the sample deformation, being up to 20% less than the set strain rate. These results initiated a round-robin experiment in which the same LLDPE was tested on several RMEs in various locations around the world. All but one of the RMEs indicated a deviation between set and applied strain rates of at least 10%, especially at strain rates above 0.1 s⁻¹. The strain rate deviation was found to depend strongly on the value of the basis length L ₀ , and may result from the upper pair of belts not properly gripping the sample during extension. Thus visual inspection of the sample deformation is necessary to determine the applied strain rate. The most accurate measurements of η _e with respect to the strain rate deviation were obtained when the correct L ₀ value and belt arrangement were used. A list of recommendations for running an RME test is provided. Future work focusing on the fluid mechanics during the test may identify fully the cause of the strain rate deviation, but from a practical point of view the problem can be corrected for in the determination of η _e . Received: 27 September 2000/Accepted: 5 February 2001     

Behaviour of a simple crystallisation model in tube and channel flow

A formulation describing the rheology of crystallising polymers is discussed. For some semi-crystalline polymers where spherulites form as part of the crystallisation process, the use of a suspension-type model is appropriate. Whilst it is possible to so describe simple shearing and elongational rheology during on-going crystallisation with such models, the flow through a capillary tube is much more complex and numerical solution is usually necessary. To give some insight into this complex flow, a ‘step function’ or ‘amorphous-frozen’ model of the viscosity changes due to crystallisation has been devised so that a semi-analytical approach is feasible. We use this simple model and compare the results with recently published experiments in tubes and channels at high (O(10³ s^− 1)) shear rates using poly(butene-1). A direct correlation between simple shear and tube flow crystallisation onset times is found.     

Viscoelastic properties of ultra-high viscosity alginates

Ultra-high viscosity alginates were extracted from the brown seaweeds Lessonia nigrescens (UHV_N, containing 61% mannuronate (M) and 2% guluronate (G)) and Lessonia trabeculata (UHV_T, containing 22% M and 78% G). The viscoelastic behavior of the aqueous solutions of these alginates was determined in shear flow in terms of the shear stress σ ₂₁, the first normal stress difference N ₁, and the shear viscosity η in isotonic NaCl solutions (0.154 mol/L) at T = 298 K in dependence of the shear rate [(g)\dot]\dot{\gamma} for solutions of varying concentrations and molar masses (3–10 × 10⁵ g/mol, homologous series was prepared by ultrasonic degradation). Data obtained in small-amplitude oscillatory shear (SAOS) experiments obey the Cox–Merz rule. For comparison, a commercial alginate with intermediate chemical composition was additionally characterized. Particulate substances which are omnipresent in most alginates influenced the determination of the material functions at low shear rates. We have calculated structure–property relationships for the prediction of the viscosity yield, e.g., η–M _w–c–[(g)\dot]\dot{\gamma} for the Newtonian and non-Newtonian region. For the highest molar masses and concentrations, the elasticity yield in terms of N ₁ could be determined. In addition, the extensional flow behavior of the alginates was measured using capillary breakup extensional rheometry. The results demonstrate that even samples with the same average molar mass but different molar mass distributions can be differentiated in contrast to shear flow or SAOS experiments.     

Rheology and birefringence of Fomblin YR at very high shear rates

The rheological and structural properties of perfluoropolyether (PFPE) lubricant films including viscosity, shear stress, and birefringence were measured at relatively low to extremely high shear rates using a rotational optical rheometer. The viscosity of various films with different thicknesses exhibit Newtonian behavior up to a shear rate 1 × 10⁴ s⁻¹, with a transition to shear-thinning behavior obvious at higher shear rates. Birefringence of these films was also measured for the first time, and these results indicate chain alignment with shear in the shear-thinning regime. The shear rate at which alignment occurs is similar to that of the onset of shear thinning. This correlation between chain alignment and shear thinning provides direct evidence that the ability of PFPEs to lubricate hard drives at high shear rates is a direct consequence of the ability of the applied shear field to align the molecules on a molecular level.     

Transient elongational viscosities of aqueous polyacrylamide solutions measured with an optical rheometer

An anionic polyacrylamide solution was characterized in elongational flow by combining laser-Doppler velocimetry to determine the strain rate in the flow direction and the two-color flow-induced birefringence method to measure the first normal stress difference along the axial centerline of a hyperbolic die. The elongational rate was constant along the axial centerline of the planar hyperbolic die as long as vortices at the die entrance did not occur. The transient elongational viscosity μ ⁺ was determined as a function of the elongational rate. The parameters varied are the Hencky strain rate and the polymer concentration. μ ⁺ showed a pronounced increase over the linear viscoelastic behavior above critical Hencky strains of 1.2 to 1.5; that is, a significant strain hardening could be observed for polyacrylamide solutions. This strain hardening is stronger the higher the elongational rate. A slight enhancement of strain hardening was found by increasing the concentration from 0.5 to 1 g/l. The stress optical coefficient was determined as 1.8 × 10⁻⁷ Pa⁻¹ (0.5 g/l) and 1.2 × 10⁻⁷ Pa⁻¹ (1 g/l).

Dehnviskosität von Kautschukmischungen

It is shown that the extensional viscosity measured by uniaxial stretch may give useful information as to the processability of rubber compounds. A simple apparatus was constructed to measure this rheological property at constant rate of strain. The influence of rubber type, filler, aging, mastication and degree of crosslinking on the reduced stress is represented by diagrams. No steady-state extensional viscosity was obtained for highly filled rubber compounds. It was found that the flow behaviour of rubber compounds can be better characterized with an extensional rheometer than with a high-pressure capillary rheometer.

     

Extensional-flow-induced crystallization of isotactic polypropylene

A filament stretching extensional rheometer with a custom-built oven was used to investigate the effect of uniaxial flow on the crystallization of polypropylene. Prior to stretching, samples were heated to a temperature well above the melt temperature to erase their thermal and mechanical histories and the Janeschitz-Kriegl protocol was applied. The samples were stretched at extension rates in the range of 0.01 s^-1 ￡ [(e)\dot] ￡ 0.75 s^-10.01\,\mbox{s}^{-1}\le \dot{{\varepsilon }}\le 0.75\,{\rm s}^{-1} to a final strain of ε = 3.0. After stretching, the samples were allowed to crystallize isothermally. Differential scanning calorimetry was applied to the crystallized samples to measure the degree of crystallinity. The results showed that a minimum extension rate is required for an increase in percent crystallization to occur and that there is an extension rate for which percent crystallization is maximized. No increase in crystallization was observed for extension rates below a critical extension rate corresponding to a Weissenberg number of approximately Wi = 1. Below this Weissenberg number, the flow is not strong enough to align the contour path of the polymer chains within the melt and as a result there is no change in the final percent crystallization from the quiescent state. Beyond this critical extension rate, the percent crystallization was observed to increase to a maximum, which was 18% greater than the quiescent case, before decaying again at higher extension rates. The increase in crystallinity is likely due to flow-induced orientation and alignment of contour path of the polymer chains in the flow direction. Polarized light microscopy verified an increase in number of spherulites and a decrease in spherulite size with increasing extension rate. In addition, small angle X-ray scattering showed a 7% decrease in inter-lamellar spacing at the transition to flow-induced crystallization. Although an increase in strain resulted in a slight increase in percent crystallization, no significant trends were observed. Crystallization kinetics were examined as a function of extension rate by observing the time required for molten samples to crystallize under uniaxial flow. The crystallization time was defined as the time at which a sudden increase in the transient force measurement was observed. The crystallization time was found to decrease as one over the extension rate, even for extension rates where no increase in percent crystallization was observed. As a result, the onset of extensional-flow-induced crystallization was found to occur at a constant value of strain equal to ε _c  = 5.8.     

Radial filtration during constant-force squeeze flow of soft solids

Various soft solid suspensions were squeezed at constant force between polished and roughened circular glass plates and the time-dependence of the interplate separation was measured. The filterability of suspensions was quantified by their desorptivity S obtained from measurements of capillary suction time. The squeeze flow (SF) of suspensions for which S < 2 μm s^−1/2 was largely consistent with rheological theory, which neglected radial filtration: the relative motion between the liquid and solid phases of the suspension in the radial pressure gradient. Suspensions having S > 2 μm s^−1/2 showed SF behavior that was consistent with the presence of radial filtration.