An empirical constitutive law for concentrated colloidal suspensions in the approach of the glass transition

Concentrated, non-crystallizing colloidal suspensions in their approach of the glass state exhibit distinct dynamics patterns. These patterns suggest a powerlaw rheological constitutive model for near-glass viscoelasticity, as presented here. The rheological parameters used for this model originate in the mode-coupling theory. The proposed constitutive model provides explicit expressions for the steady shear viscosity, the steady normal stress coefficient, the modulus-compliance relation, and the α peak of G″. The relaxation pattern distinctly differs from gelation.     

Normal stress difference in liquid lubricants sheared under high pressure

Although normal stress differences in liquids have conventionally been associated with polymers, aspects of rheological behavior in lubricated concentrated contacts suggest that normal stress difference may be significant in even low molecular weight liquids sheared under high pressure and high shear stress. A torsional flow rheogoniometer was constructed for use at high (300 MPa) pressure. Four typical liquid lubricants were investigated, including one polymer/mineral oil solution. Shear stress and N ₂-N ₂ are reported as functions of shear rate. The effect of pressure variation is reported for two liquids. Results are compared with predictive techniques and a molecular dynamics simulation. Simple low molecular weight lubricant base oils can generate measurable and significant normal stress differences when sheared at high shear stress.     

Leveling and thixotropic characteristics of concentrated zirconia inks for screen-printing

Screen-printing is a cost-effective method for the mass manufacture of zirconia-based solid oxide fuel cells (SOFCs) and oxygen separation membranes. The present work outlines an investigation into the leveling, thixotropic, and screen-printing characteristics of concentrated zirconia inks by a variety of rheological and imaging methods. A combination of viscosity, shear rate jump experiments, creep and recovery analysis, and yield stress measurements were used to assess ink thixotropy. Oscillatory rheometry and scanning electron microscopy/optical microscopy revealed a consistent effect of ethyl cellulose (binder) content upon the thixotropic and leveling characteristics of zirconia inks. While the yield stress (τ ₀), extent of recovery R(%), and rate of recovery (K) increase with increasing binder content, so did the surface roughness and thickness of the screen-printed films. Increasing the binder content not only increases the network strength of the thick films but also leads to increased leveling time. As a result, rheological modifiers are proposed to be necessary to improve the leveling characteristics of zirconia inks without losing the green strength of the thick films.     

The constitutive equation of a dilute suspension of spherical microcapsules

This paper studies the rheological behavior of a dilute suspension of spherical microcapsules, i.e. spherical thin elastic membranes filled with an incompressible liquid. Previous results obtained for the motion of such capsules freely suspended in a simple shear flow are first extended to general linear shear flows. Then the stresslet term in the external flow is computed to order ?², where ?, assumed to be small with respect to unity, is the ratio of viscous to elastic forces acting on the particle. The resulting constitutive equation is of the viscoelastic type and is similar to the one obtained for liquid droplets. It predicts that the microcapsule suspension exhibits a shear dependent viscosity and normal stress effects. The exact dependency of these phenomena on the microscopic parameters of the suspension is explicitly provided by the model.     

Linear and non linear rheology of a wormlike micellar system in presence of sodium tosylate

In this experimental work, we investigate the influence of an organic counterion, sodium tosylate, on the rheological properties of an aqueous solution of CTAB at the concentration of 0.05M. With this system we can clearly see shear thickening for small salt concentrations C _s and only shear thinning behavior at higher C _s characterized by a linear evolution of η=f(γ) in a log-log representation. In these evolutions it is only in a very small domain of concentrations of the salt (near C _s =0.035M) that we can observe a nearly constant plateau of the shear stress against shear rate. The values of σ₀ (characterizing the stress plateau), G ₀ (the plateau modulus) and τ_R (the relaxation time) obtained by dynamical rheological measurements, allow to compare experimental results obtained to predicted values of the theory of Cates corresponding to the occurrence of shear induced banding structures. Received: 22 July 1997 Accepted: 3 February 1998     

An appraisal of rheological models as applied to polymer melt flow

Summary An attempt is made at giving an appraisal of some representative rheological models of both differential and integral type, using the standard rheological measurements of six polymer melts. Experimental data obtained were the steady shear viscosity and the first normal stress difference by means of aWeissenberg rheogoniometer over the range of shear rates: 10^–2 ~ 10 sec^–1, and by means of aHan slit/capillary rheometer over the range of shear rates: 10 ~ 10³ sec^–1. Also measured by means of theWeissenberg rheogoniometer were the dynamic viscosity and dynamic elastic modulus over the range of frequencies: 0.3 × 10^–2 ~ 3 × 10² sec^–1. Rheological models chosen for an appraisal are theSpriggs 4-constant model, theMeister model, and theBogue model.It is found that the capability of the three models considered is about the same in their prediction of the rheological behavior of polymer melts in simple shearing flow. It is pointed out however that, due to the ensuing mathematical complexities, the usefulness of these models is limited to the study of flow problems associated with simple flow situations. Therefore, in analysing the complex flow situations often encountered with various polymer processings, the authors suggest use of the empirical models of the power-law type for both the viscosity and normal stress functions.With 11 figures, 4 schemas and 1 table     

Rheological properties and dispersion stability of magnetorheological (MR) suspensions

In the present article, the rheological responses and dispersion stability of magnetorheological (MR) fluids were investigated experimentally. Suspensions of magnetite and carbonyl iron particles were prepared as model MR fluids. Under an external magnetic field (H ₀) and a steady shear flow, the yield stress depends upon H ₀ ^3/2. The Yield stress depended on the volume fraction of the particle (φ) linearly only at low concentration and increased faster at high fraction. Rheological behavior of MR fluids subjected to a small-strain oscillatory shear flow was investigated as a function of the strain amplitude, frequency, and the external magnetic field. In order to improve the stability of MR fluid, ferromagnetic Co-γ-Fe₂O₃ and CrO₂ particles were added as the stabilizing and thickening agent in the carbonyl iron suspension. Such needle-like particles seem to play a role in the steric repulsion between the relatively large carbonyl iron particles, resulting in improved stability against rapid sedimentation of dense iron particles. Furthermore, the additive-containing MR suspensions exhibited larger yield stress, especially at higher magnetic field strength. Received: 4 April 2000 Accepted: 6 November 2000     

Measurements and scaling of wall shear stress fluctuations

Measurements of velocity and wall shear stress fluctuations were made in an external turbulent boundary layer developed over a towed surface-piercing flat plate. An array of eight flush-mounted wall shear stress sensors was used to compute the space-time correlation function. A methodology for in situ calibration of the sensors for ship hydrodynamic applications is presented. The intensity of the wall shear stress fluctuations, τ _rms/τ _avg was measured as 0.25 and 0.36 for R _θ =3,150 and 2,160 respectively. The probability density is shown to exhibit positive skewness, and lack of flow reversals at the wall. Correlations between velocity and wall shear stress fluctuations are shown to collapse with outer boundary layer length and velocity scales, verifying the existence of large-scale coherent structures which convect and decay along the wall at an angle of inclination varying from 10 to 13° over the range of Reynolds numbers investigated. The wall shear stress convection velocity determined from narrow band correlation measurements is shown to scale with outer variables. The space-time correlation of the wall shear is shown to exhibit a well-defined convective ridge, and to decay 80% over approximately 3δ for R _θ =3,150. Published online: 7 November 2002     

Average and extremal properties of heat transfer and shear stress on a wall surface in Rayleigh–Bénard convection

In this study surface-averaged and extremal properties of heat transfer and shear stress on the upper wall surface of Rayleigh–Bénard convection are numerically examined. The Prandtl number was raised up to 10³, and the Rayleigh number was changed between 10⁴ and 10⁷. As a result, average Nusselt number Nu and shear rate τ/Pr depends on Pr, Ra, and the entire numerical results are distributed between two correlation equations corresponding to small and large Pr. The small and large Pr equations are closely related to steady and unsteady flow regimes, respectively. Nevertheless, a single relation τ/Pr ~ Nu ^3.0 exists to explain the entire results. Similarly the change of local maximal properties Nu _max and τ _max/Pr depends on Pr, Ra, and these values are also distributed between two correlation equations corresponding to small and large Pr cases. Despite such complicated dependence we can obtain a correlation equation as a form of τ _max/Pr ~ Nu _max^2.6, which has not been obtained theoretically.     

Orientation and rheology of rodlike particles with weak Brownian diffusion in a second-order fluid under simple shear flow

An analysis of particle orientation in a dilute suspension of rodlike particles in a second-order fluid was performed to examine the effects of the elasticity of the fluid and of weak Brownian diffusion of the particle on its orientation. Distributions of particle orientation under a simple shear flow with rate of shearg have been obtained as a function of a single nondimensional parameter, ^* =/r _e ² (D/g), which combines the effects of the particle aspect ratior _e , the weak fluid elasticity, and the weak Brownian rotation diffusion coefficientD of the particle. In the limit of larger _e , when the fluid elasticity is strong enough to overcome the rotational diffusion effect on the particle motion, most of the particles will orient close to the vorticity axis. A new shear-thinning mechanism of the shear viscosity of such systems is predicted by the theory.     

Rheology of lyotropic and thermotropic lamellar phases

We investigate the steady-state rheological behaviour of the lamellar phase of a lyotropic system (CpCl, hexanol, brine) and of a thermotropic system (8CB). Power laws characterize the behaviour of the imposed stress as a function of the measured shear rate and similarities are observed for both systems; the same regime γ˙∼σ ^m with m≈1.7 is obtained at low shear stresses corresponding to a texture of oily streaks oriented in the direction of the flow, as shown by microscopic observations. The “onion state” only exists in the case of dilute samples of the lyotropic lamellar phase; the stress then varies as γ˙∼σ ^m with m≈4.8, as already observed by other groups with different systems. Rheological measurements at different temperatures allow determination of different activation energies relating to the still badly understood processes involved in the different rheological regimes. We propose a model which reproduces the experimental power laws and which is based on an analogy with the theory of high-temperature creep in metals and alloys. Received: 19 October 1999/Accepted: 1 November 1999     

Natural Convection in a Cavity Filled with Porous Layers on the Top and Bottom Walls

Natural convection in a partially filled porous square cavity is numerically investigated using SIMPLEC method. The Brinkman-Forchheimer extended model was used to govern the flow in the porous medium region. At the porous-fluid interface, the flow boundary condition imposed is a shear stress jump, which includes both the viscous and inertial effects, together with a continuity of normal stress. The thermal boundary condition is continuity of temperature and heat flux. The results are presented with flow configurations and isotherms, local and average Nusselt number along the cold wall for different Darcy numbers from 10⁻¹ to 10⁻⁶, porosity values from 0.2 to 0.8, Rayleigh numbers from 10³ to 10⁷, and the ratio of porous layer thickness to cavity height from 0 to 0.50. The flow pattern inside the cavity is affected with these parameters and hence the local and global heat transfer. A modified Darcy–Rayleigh number is proposed for the heat convection intensity in porous/fluid filled domains. When its value is less than unit, global heat transfer keeps unchanged. The interfacial stress jump coefficients β ₁ and β ₂ were varied from  −1 to +1, and their effects on the local and average Nusselt numbers, velocity and temperature profiles in the mid-width of the cavity are investigated.     

Generalized flow analysis of non-Newtonian visco-elastic fluid flow through fractal reservoir

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Zur Untersuchung der Anlaufströmung von viskoelastischen Flüssigkeiten

Zusammenfassung Die Eigenschaften von viskoelastischen Flüssigkeiten werden bekanntlich u. a. mit Hilfe von Anlaufvorgängen untersucht. Für die Auswertung dieser Versuche ist es wichtig zu wissen, inwieweit die Trägheit des Stoffes berücksichtigt werden muß. Zur Beantwortung dieser Frage wurde der Anlaufvorgang unter Zugrundelegung einer Oldroyd-Flüssigkeit systematisch studiert. Es wurde gefunden, daß die durch die Trägheit bedingte Ausbreitung von Scherwellen dann vernachlässigt werden kann, wenn die charakteristische Diffusionszeith ² / ₀ klein gegenüber der Relaxationszeit der Flüssigkeit ist.

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Summary The influence of inertia, fluid elasticity and shear thinning properties are studied in detail for the flows of a viscoelastic fluid between two parallel plates, in the case when both plates are initially at rest and one of the plates is suddenly set in motion at a constant velocity. The rheological equation of state used is that given by the four constant Oldroyd model. It is shown that due to inertia, elastic shear waves are propagated in the fluid and that these waves are only important for the flow if the relaxation time and the characteristic diffusion timeh ²/ ₀ are of the same order. Further, it is shown that for a wide range of parameters these shear waves die out before the stress overshoot begins.

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Mit 14 Abbildungen     

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.     

Transient shear flow behavior of polymeric fluids according to the Leonov model

Summary The viscoelastic behavior of polymeric systems based upon the Leonov model has been examined for (i) stress growth and relaxation with intermittent shear flow, (ii) stress relaxation after a step in the shear strain and (iii) elastic recovery after shear flow. A large number of modes have been conveniently incorporated through the determination of the model parameters from conventional rheological data by using an effective least-square procedure. With a sufficient number of modes, the predictions are in very good agreement with corresponding experiments in literature, including the recent data for cases (i) and (ii) obtained by optical methods.The present theory agrees also with the Lodge-Meissner relation ( ₁₁ – ₂₂)/ ₁₂ = ₀ in a step-shear experiment. In general, the Leonov model leads to results which, in these test cases, are comparable to those from Wagner's theory. It is, however, considerably less difficult to apply, thus offering the possibility of analysing flow problems of practical interest.With 16 figures and 1 table     

Rheology and stircasting of (organic) alloys

Partially solidified metal alloys behave thixotropic during stircasting. Some transparent, low melting organic alloys such as NPA behave similarly. We studied the rheological behaviour of NPA during and after stirred nucleation. The shear stress reaches a maximum _max and subsequently decreases. This decrease is explained by the coarsening of dendrites into spherical particles. The maximum shear stress increases with increasing cooling rate and also with decreasing final temperature. The latter increase is more pronounced if the shear rate during solidification is lower. Both effects can be explained in terms of coarsening and particle sizes.     

Characterization of micellar structure dynamics for a drag-reducing surfactant solution under shear: normal stress studies and flow geometry effects

Some surfactant solutions have been observed to exhibit a strong drag reduction behavior in turbulent flow. This effect is generally believed to result from the formation of large cylindrical micelles or micellar structures. To characterize and understand better these fluids, we have studied the transient rheological properties of an efficient drag-reducing aqueous solution: tris (2-hydroxyethyl) tallowalkyl ammonium acetate (TTAA) with added sodium salicylate (NaSal) as counter ion. For a 5/5 mM equimolar TTAA/NaSal solution, there is no measurable first normal stress difference (N ₁) immediately after the inception of shear, but N ₁ begins to increase after a well-defined induction time — presumably as shear-induced structures (SIS) are formed — and it finally reaches a fluctuating plateau region where its average value is two orders of magnitude larger than that of the shear stress. The SIS buildup times obtained by first normal stress measurements were approximately inversely proportional to the shear rate, which is consistent with a kinetic process during which individual micelles are incorporated through shear into large micellar structures. The SIS buildup after a strong preshear and the relaxation processes after flow cessation were also studied and quantified with first normal stress difference measurements. The SIS buildup times and final state were also found to be highly dependent on flow geometry. With an increase in gap between parallel plates, for example, the SIS buildup times decreased, whereas the plateau viscosity increased.     

Tensorial strength analysis of paperboard

Tensorial-type failure criteria with linear and quadratic terms are used to calculate the strength of paperboard under plane stress. Theoretical predictions and experimental data are correlated in all four quadrants of biaxial normal stress with various levels of shear. Several methods are examined for determining the interaction coefficientF ₁₂. Comparisons are made with optimum values obtained from least-squares analyses. The best analytical-experimental agreement at all levels of shear is obtained approximately by using coefficientF ₁₂ equal to zero. The sensitivity ofF ₁₂ to errors in experimental input data is also studied. Reliable correlation with experiment, as well as operational simplicity, make these criteria attractive for predicting the strength of paperboard.     

Rheological determination of peptizing agents in bentonite clays

This paper presents the results of an evaluation of the rheological properties of commercial bentonite suspensions made from peptized and unpeptized clay samples collected over a six year time span. The rheological properties of these suspensions were measured between shear rates of 5.11 to 1022 s^–1 at concentrations of 15, 30, 45, 64.2 and 70 kg/m³. Bingham, power-law and Casson models were then fitted to the shear stress and shear rate values. Parameters derived from these models were then subjected to further analyses. Four rheological methods (termed peptization index tests) were developed to differentiate between peptized and unpeptized bentonite samples.