Shear rheometry and visualization of glass fiber suspensions

The nonlinear rheological behavior of short glass fiber suspensions has been investigated in this work by rotational rheometry and flow visualization. A Newtonian and a Boger fluid (BF) were used as suspending media. The suspensions exhibited shear thinning in the semidilute regime and weaker shear thinning in the transition to the concentrated one. Normal stresses and relative viscosity were higher for the BF suspensions than for the Newtonian ones presumably due to enhanced hydrodynamic interactions resulting from BF elasticity. In addition, relative viscosity of the suspensions increased rapidly with fiber content, suggesting that the rheological behavior in the concentrated regime is dominated by mechanical contacts between fibers. Visualization of individual fibers and their interactions under flow allowed the detection of aggregates, which arise from adhesive contacts. The orientation states of the fibers were quantified by a second order tensor and fast Fourier transforms of the flow field images. Fully oriented states occurred for shear rates around 20 s^− 1. Finally, the energy required to orient the fibers was higher in step forward than in reversal flow experiments due to a change in the spatial distribution of fibers, from isotropic to planar oriented, during the forward experiments.     

Transient shear rheology of carbon nanofiber/polystyrene melt composites

We characterize the transient shear rheology of polystyrene/carbon nanofiber composites. Our experimental measurements of the composites show increasing stress overshoot responses to transient shear as the carbon nanofiber concentration increases. We also find the steady state viscosity reached at long times during application of a constant shear rate increases with increasing carbon nanofiber concentration. Flow reversal experiments show the effects of nanofiber orientation and structural evolution on the composite's rheological response.We present a microstructurally based constitutive model where all but two parameters are determined by rheological characterization of the pure polymer and the shape and concentration of the nanoparticles. The Folgar-Tucker constant, C_I, is treated as a fitting parameter, while several definitions for the shape factors A, B, C and F are evaluated. We make note of the effects each parameter has on the model's predictions. We find that the constitutive model is in agreement with our experimentally measured transient shear rheology of the PS/CNF melt composites for the CNF concentrations and shear rates presented.     

Linear and non-linear viscoelastic properties of ethylene vinyl acetate/nano-crystalline cellulose composites

This paper reports on the melt rheological properties of ethylene vinyl acetate containing between 0 and 10 wt.% of nano-crystalline cellulose (NCC). A complete set of rheological tests including frequency sweeps, shear transients, and uniaxial elongations was performed. Frequency sweeps showed that at low frequencies, a pseudo solid-like behavior was obtained for NCC concentrations higher than 5%. This behavior was related to hydrogen bonding between NCC particles and the creation of particle networks as the result of particle–particle interactions. For transient shear tests, all compositions presented a stress overshoot at high shear rates before reaching a steady state. It was found that the amplitude of this overshoot depends on both NCC content and shear rate. On the other hand, the time to reach the maximum was found to be highly shear rate dependent but concentration dependence was rather weak. For uniaxial extensional flow, higher extensional viscosity was observed with increasing NCC content. On the other hand, strain hardening was found to decrease with increasing NCC content.     

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.     

Rheological behavior of dilute solutions of a side-chain liquid-crystalline polysiloxane in 4,4′-n-octylcyanobiphenyl

The electrorheological (ER) behavior and stress transient response of dilute solutions of a side-chain liquid-crystalline polysiloxane (LCP) in 4,4′-n-octylcyanobiphenyl (8CB) is studied. In the flow-tumbling regime of 8CB, i.e. from T = 34–38 °C, the stress transients of both 8CB and LCP/8CB solutions show oscillatory responses, but with shorter oscillation periodicities for the solution. In the flow-aligning regime of 8CB, i.e. at 39 and 40 °C, a transformation to flow-tumbling is observed in the stress transients of the LCP/8CB solution. In both cases, analysis of the transient responses indicates that the change in Leslie viscosity coefficients on dissolving the LCP are δα₂ < 0 and δα₃ > 0. The amplitude of the ER response, defined as the viscosity difference between the on and off states, Δη = η_on − η_off, is only weakly affected by the dissolution of LCP. These rheological results can be interpreted consistently using a modified version of a hydrodynamic theory by Brochard, provided an additional dissipation mechanism is included, which derives from the presence of an elastic torque between director rotation and LCP orientation. Received: 8 September 1999/Accepted: 13 December 1999     

Rheology and flow-birefringence from viscoelastic polymer-clay solutions

 The shear orientation of viscoelastic clay-polymer solutions was investigated by means of rheology and flow birefringence (Δn). The polymer chains are in dynamic adsorption/desorption equilibrium with the clay particles to form a “network”. The elastic behavior of the network was characterized by constant stress, oscillatory shear, and stress relaxation experiments. Constant stress experiments indicated a yield stress upon which shear flow started and no strain recovery could be observed. Oscillatory shear experiments showed a broad elastic region followed by flow when a critical strain was reached. Stress relaxation experiments showed several relaxation times when the same critical strain was reached. Experiments under steady flow characterized the transient behavior of the network. With increasing steady shear rate a pronounced minimum in birefringence was observed at a critical shear rate. The shear rate dependent viscosity showed near power law behavior and no corresponding critical feature. While birefringence detects orientational effects on a microscopic length scale, rheology averages over macroscopic changes in the sample. The same degree of orientation could be achieved under constant shear rate or constant stress conditions. Received: 25 January 2001 Accepted: 22 May 2001     

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.     

Dispersion state and rheology of hectorite particles in water over a broad range of salt and particle concentrations

The relationship between the rheological properties of deionized aqueous suspensions of hectorite particles and the dispersion states of the particles has been studied with a broad range of salt and particle concentrations. The shear viscosity of the hectorite suspensions decreases drastically after exhaustively deionizing the suspensions with ion-exchange resins. By means of DLS measurements, it is clarified that the average size of the flocs of hectorite particles decreases and reaches the Stokes diameter of the individual particle as the degree of deionization advances. This fact strongly supports the idea that the electrical double layer around the hectorite particles expands significantly in the exhaustively deionized state and the particles are well-dispersed individually and do not form a three-dimensional network structure composed of particles, whereas such a network structure forms in the presence of a large amount of salt. In the case of exhaustively deionized state, the suspension forms a glassy state, at high particle fractions. The results show the importance of the electrical double layer that causes a strong repulsive force among the particles on the particle dispersion state, especially in the exhaustive deionization area below 10^− 4 M, and on the rheological properties; the hectorite suspension can be considered a Newtonian liquid in the deionized state, but it becomes elastic-solid in the presence of salt above a certain concentration confirmed by normal stress measurements.     

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.     

Melt shear rheology of carbon nanofiber/polystyrene composites

The rheological behavior and morphology of carbon nanofiber/polystyrene (CNF/PS) composites in their melt phase have been characterized both through experimental measurements and modeling. Composites prepared in the two different processes of solvent casting and melt blending are contrasted; melt-blended and solvent-cast composites were each prepared with CNF loadings of 2, 5, and 10 wt%. A morphological study revealed that the melt blending process results in composites with shorter CNFs than in the solvent-cast composites, due to damage caused by the higher stresses the CNFs encounter in melt blending, and that both processes retain the diameter of the as-received CNFs. The addition of carbon nanofiber to the polystyrene through either melt blending or solvent casting increases the linear viscoelastic moduli, G′ and G″, and steady-state viscosity, η, in the melt phase monotonically with CNF concentration, more so in solvent cast composites with their longer CNFs. The melt phase of solvent-cast composites with higher CNF concentrations exhibit a plateau of the elastic modulus, G′, at low frequencies, an apparent yield stress, and large first normal stress difference, N ₁, at low strain rates, which can be attributed to contact-based network nanostructure formed by the long CNFs. A nanostructurally-based model for CNF/PS composites in their melt phase is presented which considers the composite system as rigid rods in a viscoelastic fluid matrix. Except for two coupling parameters, all material constants in the model for the composite systems are deduced from morphological and shear flow measurements of its separate nanofiber and polymer melt constituents of the composite. These two coupling parameters are polymer–fiber interaction parameter, σ, and interfiber interaction parameter, C _I. Through comparison with our experimental measurements of the composite systems, we deduce that σ is effectively 1 (corresponding to no polymer–fiber interaction) for all CNF/PS nanocomposites studied. The dependence of CNF orientation on strain rate which we observe in our experiments is captured in the model by considering the interfiber interaction parameter, C _I, as a function of strain rate. Applied to shear flows, the model predicts the melt-phase, steady-state viscosities, and normal stress differences of the CNF/PS composites as functions of shear rate, polymer matrix properties, fiber length, and mass concentration consistent with our experimental measurements.     

Influence of surfactant addition on the rheological properties of aqueous Welan matrices

In the present work the effects produced by the presence of two different surfactants (Abil B 8842 and Triton N 101) on the rheological properties of aqueous welan matrices are studied, both in steady and in oscillatory shear conditions. Welan is an acidic microbial polysaccharide having high thermal, pH, and salt stability. At sufficiently low concentrations it forms aqueous weak gel matrices which can be profitably used to regulate the rheological properties of disperse systems and improve their stability. Different systems are examined, having the same polysaccharide concentration (0.25 wt%) and different surfactant concentrations (up to 40 wt%, far beyond the range of practical interest for emulsion preparation). All the systems exhibit marked shear-thinning properties which can be described quite satisfactorily by the Cross equation. The concentration dependence of the zero-shear-rate viscosity as well as the mechanical spectra confirm that, in the concentration range considered, the aqueous welan systems are typically weakly structured fluids. The influence of both surfactants is examined in detail by comparing the behavior of the different classes of systems. Both surfactants reduce the polymer contribution at low shear, whereas an opposite action is exerted at high concentration and shear. These contrasting effects are ascribed to the different structural features of the polymer matrix under low stresses and high shear conditions, respectively. Received: 6 February 2000 Accepted: 1 November 2000     

Filling the gap between transient and steady shear rheology of aqueous graphene oxide dispersions

Even though the rheological behavior of aqueous graphene oxide (G-O) dispersions has been shown to be strongly time-dependent, only few transient measurements have been reported in the literature. In this work, we attempt to fill the gap between transient and steady shear rheological characterizations of aqueous G-O dispersions in the concentration range of 0.004 < ? <?3.5 wt%, by conducting comprehensive rheological measurements, including oscillatory shear flow, transient shear flow, and steady shear flow. Steady shear measurements have been performed after the evaluation of transient properties of the G-O dispersions, to assure steady-state conditions. We identify the critical concentration ? _c =?0.08 wt% (where G-O sheets start to interact) from oscillatory shear experiments. We find that the rheology of G-O dispersions strongly depends on the G-O concentration ?. Transient measurements of shear viscosity and first normal stress difference suggest that G-O dispersions behave like nematic polymeric liquid crystals at ?/? _c =?25, in agreement with other work reported in the literature. G-O dispersions also display a transition from negative to positive values of the first normal stress difference with increasing shear rates. Experimental findings of aqueous graphene oxide dispersions are compared and discussed with models and experiments reported for nematic polymeric liquid crystals, laponite, and organoclay dispersions.     

Small and large strain rheology of wheat gluten

 The rheological properties of wheat gluten were studied under both small and large deformation and compared with those of the parent flours. The limiting strain of linear viscoelastic behaviour of gluten doughs, 3 × 10⁻², was an order of magnitude larger than that of the flour doughs, 10⁻³. The role of starch in the lower limiting strain of flour doughs was indicated by the exponential decrease in the limiting strain of gluten-starch mixtures with greater quantities of starch. Large strain measurements showed gluten doughs possessed greater shear and elongational viscosities than flour doughs and these differences were greatest at lower shear and elongation rates (0.01 and 0.1 s⁻¹). The larger viscosities of flour and gluten doughs at the low strain rates help to stabilise and prevent the collapse of gas bubbles during bread fermentation and baking. Increasing starch levels in gluten-starch mixtures, at either constant or optimal water levels, lowered the elongational viscosity. Dynamic measurements were, however, more sensitive to the level of water added to the gluten-starch mixtures. The storage modulus decreased with increasing starch levels when constant water levels were used to prepare the mixtures, but when optimal water levels were used the storage modulus increased. Gluten and starch are major contributors to the large and small strain rheological properties of flour doughs; however, gluten-starch mixtures were unable to duplicate exactly the rheological properties of flour doughs, indicating that other flour components such as pentosans, lipids and water soluble proteins also influence dough rheology. Received: 20 March 2001 Accepted: 11 July 2001     

Rheological behavior of concentrated suspensions as affected by the dynamics of the mixing process

The rheological characterizations of concentrated suspensions are generally carried out assuming “well-mixed” suspensions. However, the variation of the concentration distributions of the ingredients of the formulation, i.e., the “goodness of mixing”, the size and shape distributions of the particle clusters and the rheological behavior of the suspension all depend on the thermo-mechanical history that the suspension is exposed to during the mixing process. Here, various experimental tools are used for the characterization of the degree of mixedness (concentration distributions) of various ingredients along with the characterization of rheological material functions, wall slip behavior and the maximum packing fraction of a graphite/elastomer suspension. The degree of mixedness values of the ingredients of the suspensions processed using batch and continuous processes and under differing operating conditions were characterized quantitatively using wide-angle X-ray diffraction and thermo gravimetric analysis and were elucidated under the light of the electrical properties of the suspension as affected by the mixing process. Upon achieving better homogeneity of the graphite particles and the binder and decreases in the size and breadth of the size distributions of particle clusters (as inferred from electrical measurements and maximum packing fraction values), the elasticity (storage modulus) and the shear viscosity (magnitude of the complex viscosity from small-amplitude oscillatory shear and shear viscosity from steady torsional and capillary rheometry) of the suspension decreased significantly and the wall slip velocity values increased. These findings demonstrate the intimate relationships that exist between the rheological behavior of concentrated suspensions and the thermo-mechanical history that they are exposed to during the processing stage and suggest that the preparation conditions for suspensions should be carefully selected and well documented to achieve reproducible characterization of rheological material functions.     

Rheological properties and percolation in suspensions of multiwalled carbon nanotubes in polycarbonate

This paper is concerned with several issues related to the rheological behavior of polycarbonate/multiwalled carbon nanotube nanocomposites. The composites were prepared by diluting a masterbatch of 15 wt.% nanotubes using melt-mixing method, and the dispersion was analyzed by SEM, TEM, and AFM techniques. To understand the percolated structure, the nanocomposites were characterized via a set of rheological, electrical, and thermal conductivity measurements. The rheological measurements revealed that the structure and properties were temperature dependent; the percolation threshold was significantly lower at higher temperature suggesting stronger nanotube interactions. The nanotube networks were also sensitive to the steady shear deformation particularly at high temperature. Following preshearing, the elastic modulus decreased markedly suggesting that the nanotubes became more rigid. These results were analyzed using simple models for suspensions of rod-like particles. Finally, the rheological, electrical, and thermal conductivity percolation thresholds were compared. As expected, the rheological threshold was smaller than the thermal and electrical threshold.     

The effects of salts on the rheological characteristics of a drag-reducing cationic surfactant solution with shear-induced micellar structures

The effect of the counterion salt sodium salicylate (Nasal) on the transient rheological properties of a drag-reducing surfactant system tris (2-hydroxyethyl) tallowalkyl ammonium acetate (TTAA) has been studied with both rheometric and rheo-optical methods. Three types of transient behavior for N₁ and viscosity were identified in 5 mM TTAA solutions depending on the counterion concentration: induction and growth (below equimolar concentration); overshoot and growth (above equimolar concentration); and overshoot then plateau (at high concentrations of Nasal). The transient flow birefringence and orientation angle show trends similar to those of the viscosity and N₁. The second type of transient behavior suggests a two-stage alignment and shear thickening process. The SIS buildup time from the quiescent state, the rebuilding time after a strong preshear, and the relaxation time were also obtained from N₁ measurements, and show a maximum around equimolar conditions. The initial N₁ and viscosity immediately after the flow startup, on the other hand, show a maximum around a ratio of 2.5 to 3 Nasal/TTAA. For solutions with a Nasal concentration in the ratio 1.5 to 3, the steady state values of N₁ and viscosity do not show much variation with Nasal concentration over the shear rate range covered, however. The effect of an addition of sodium chloride (NaCI) to an equimolar Nasal/TTAA solution on the characteristic times and steady state values was also quantified. These rheological results provide us with tools to determine the optimal concentration ratio for practical drag reduction applications.     

Transient shear flow behavior of concentrated long glass fiber suspensions in a sliding plate rheometer

In order to eventually predict the behavior of long fiber suspensions in complex flows commonly found in processing operations, it is necessary to understand their rheology and its connection to the evolution of fiber orientation and configuration in well defined flows. In this paper we report the transient behavior at the startup of shear flow of a polymer melt containing long glass fibers with a length (L) >1 mm, using a sliding plate rheometer (SPR). The operation of the SPR was confirmed by comparing the transient shear viscosity (η⁺) for a polymer melt and a melt containing short glass fibers (L < 1 mm) with measurements obtained from a cone-and-plate device, using a modified sample geometry that was designed to avoid wall effects. For the long fiber systems, measurements could only be obtained in the SPR because these systems would not stay within the gap of the rotational rheometer. Transient stress growth behavior of the long fiber systems was obtained as a function of shear rate and fiber concentration for samples prepared with three different initial orientations. Results showed that, unlike short fiber systems (with a random planar initial orientation) that usually exhibit a single overshoot peak followed by a steady state, η⁺ of the long fiber suspensions often passed through multiple transient regions, depending on the fiber concentration and applied shear rate. Additionally, η⁺ of the long fiber suspensions was found to be highly dependent on the initial orientation of the sheared samples. Finally, the initial and final fiber orientations of the long glass fiber samples were measured and used to initiate an explanation of the viscosity behavior. The results obtained in this research will be useful for future assessment of a quantitative correlation between transient rheology and the evolution of fiber orientation.     

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.     

Rheological properties of long glass fiber filled polypropylene

Long glass fiber-filled polypropylene (PP) composites are produced by pultrusion, and the extrudate is cut at different lengths producing composites containing long fibers of controlled length. The rheological properties of such composites in the molten state have been studied using different rheometers. A capillary rheometer has been constructed and mounted on a molding-injection machine. The shear viscosity of filled PP determined from the capillary rheometer, after corrections for entrance effects, was found to be very close to that of unfilled PP. However, large excess pressure losses at the capillary entrance were observed and these data have been used to obtain an apparent elongational viscosity. The apparent elongational viscosity was shown to be considerably larger than the shear viscosity for PP and filled PP, and it increased markedly with fiber length and fiber content. Rotational rheometers with a parallel-plate geometry were used to investigate the viscoelastic properties of these composites and their behavior was found to be non-linear, exhibiting a yield stress. A model is proposed to describe the shear viscosity from a solid-like behavior at low stresses to fluid-like behavior at high shear stresses taking into account fiber content and orientation. A modified model, proposed for elongational flow, describes relatively well the apparent elongational data.     

The rheology of bread dough made from four commercial flours

 A selection of four commercial flours has been subjected to extensive rheological measurements as part of a comprehensive program of wheat improvement. The results have been used to determine which of the many types of rheological measurements provide significant discrimination between various types of modern baker's flours (including biscuit flours) and to procure data suitable for use in mathematical models describing the dough rheology. The rheological measurements undertaken include oscillatory shear at low amplitude, steady shear at a low shear rate, stress relaxation and extensional viscosity testing. Although oscillatory shear data show minor differences between these flours, the other tests show significant variations and these provide very good discrimination between the different flour types in comparison with conventional dough testing (e.g. by the extensograph). The current dough rheological measurements provide further insight into molecular structure. In the future, mathematical (constitutive) models are expected to provide a means of predicting processing and baking behaviour of bread dough. Received: 27 June 2001 Accepted: 28 August 2001