A unified model for polystyrene–nanorod and polystyrene–nanoplatelet melt composites

We present a unified constitutive model capable of predicting the steady shear rheology of polystyrene (PS)–nanoparticle melt composites, where particles can be rods, platelets, or any geometry in between, as validated against experimental measurements. The composite model incorporates the rheological properties of the polymer matrix, the aspect ratio and characteristic length scale of the nanoparticles, the orientation of the nanoparticles, hydrodynamic particle–particle interactions, the interaction between the nanoparticles and the polymer, and flow conditions of melt processing. We demonstrate that our constitutive model predicts both the steady rheology of PS–carbon nanofiber composites and the steady rheology of PS–nanoclay composites. Along with presenting the model and validating it against experimental measurements, we evaluate three different closure approximations, an important constitutive assumption in a kinetic theory model, for both polymer–nanoparticle systems. Both composite systems are most accurately modeled with a quadratic closure approximation.     

Understanding thixotropic and antithixotropic behavior of viscoelastic micellar solutions and liquid crystalline dispersions. I. The model

A simple model consisting of the Upper Convected Maxwell constitutive equation and a kinetic equation for destruction and construction of structure, first proposed by Fredrickson in 1970, is used here to reproduce the complex rheological behavior of viscoelastic systems that also exhibit thixotropy and rheopexy under shear flow. The model requires five parameters that have physical significance and that can be estimated from rheological measurements. Several steady and unsteady flow situations were analyzed with the model. The model predicts creep behavior, stress relaxation and the presence of thixotropic loops when the sample is subjected to transient stress cycles. Such behavior has been observed with surfactant-based solutions and dispersions. The role of the characteristic time for structure built up, λ, in the extent and shape of the thixotropic loops is demonstrated.     

A thermo-mechanical continuum theory with internal length for cohesionless granular materials

This article continues Part I. Here the non-equilibrium responses of the constitutive variables t (Cauchy stress tensor), q (heat flux vector), h (equilibrated stress vector), Γ (flux term associated with the internal length ℓ), Π (production term associated with ℓ) and f (equilibrated intrinsic body force) as well as the Helmholtz free energy Ψ are postulated by use of a quasi-linear theory for three of four models deduced in Part I. In so doing, together with the equilibrium responses gained in Part I, a complete set of constitutive equations for the constitutive quantities for each model is obtained. The implemented models are applied to investigate typical isothermal steady granular shearing flows with incompressible grains, namely, simple plane shear flow, inclined gravity-driven flow and vertical channel-flow. The emphasis is on the models in which ℓ is considered a material constant (Model I) and an independent dynamic field quantity (Model III). Numerical results show that Model III is more appropriate than Model I since in the former model the effect of the motion of an individual grain can better be taken into account. Such a result is in particular significant for avalanches, since it verifies the existence of a thin layer immediately above the base of an avalanche, in which the grains are colliding strongly with one another, and provides a quantitative means to measure such a thin layer.     

Non-swirling axisymmetric flow of the ω-D fluid

In this paper a constitutive equation for the extra stress tensor τ is considered, which can be used for steady axisymmetric flows when u _ϕ=0 (non-swirling). It is explicit with coefficients which, in case of incompressibility, depend only upon three invariants. As such it should prove useful in numerical calculations, especially so if used in its simplest form, namely the quasi-Newtonian fluid. Here, a purely viscous code can be used. The constitutive equation is self-consistent and receives additional justification from the fact that any constitutive equation is bound to result in the form proposed if the flow is a constant stretch history flow. Received: 30 March 1998 Accepted: 6 August 1998     

Application of Rheological Models in Prediction of Turbulent Slurry Flow

The paper deals with fully developed steady turbulent flow of slurry in a circular straight and smooth pipe. The Kaolin slurry consists of very fine solid particles, so the solid particles concentration, and density, and viscosity are assumed to be constant across the pipe. The mathematical model is based on the time averaged momentum equation. The problem of closure was solved by the Launder and Sharma k-ε turbulence model (Launder and Sharma, Lett Heat Mass Transf 1:131–138, 1974) but with a different turbulence damping function. The turbulence damping function, used in the mathematical model in the present paper, is that proposed by Bartosik (1997). The mathematical model uses the apparent viscosity concept and the apparent viscosity was calculated using two- and three-parameter rheological models, namely Bingham and Herschel–Bulkley. The main aim of the paper is to compare measurements and predictions of the frictional head loss and velocity distribution, taking into account two- and three-parameter rheological models, namely Bingham and Herschel–Bulkley, if the Kaolin slurry possesses low, moderate, and high yield stress. Predictions compared with measurements show an observable advantage of the Herschel–Bulkley rheological model over the Bingham model particularly if the bulk velocity decreases.     

A constitutive model for non-Newtonian materials based on the persistence-of-straining tensor

We present a constitutive equation for non-Newtonian materials which is capable of predicting, independently, steady state rheological material functions both in shear and in extension. The basic assumption is that the extra-stress tensor is a function of both the rate-of-strain tensor, D, and the persistence-of-straining tensor, -\boldsymbol{P}=\boldsymbol{D}\overline{\boldsymbol{W}}-\overline{\boldsymbol {W}}\boldsymbol{D}, introduced in Thompson and de Souza Mendes (Int. J. Eng. Sci. 43(1–2):79–105, 2005). The resulting equation falls within the category of constitutive equations of the form t=t(D,[`(W)])\boldsymbol{\tau}=\boldsymbol{\tau}(\boldsymbol {D},\overline{\boldsymbol{W}}), with the advantage of eliminating the undesirable stress jumps that may occur when [`(W)]\overline {\boldsymbol{W}} becomes locally undetermined. We also show that this formulation is not restricted to motions with constant relative principle stretch history (MWCRPSH), in contrast to what is suggested in the literature. The same basis of tensors that comes from representation theorems also arises from an elastic constitutive equation based on the difference between the Jauman and the Harnoy convected time derivatives, in the limit of small values of the Deborah number.     

Rheological characterization and modeling of end-functionalized polybutadienes

The rheological characterization and modeling of a series of polybutadienes obtained by anionic solution polymerization is presented in this work. The polybutadienes are synthesized using two different initiators: R,R′,R′′-silyloxyalkyllithium (F1) and R,R′,R′′-silylalkyllithium (F3). In addition, a polybutadiene obtained with a conventional alkyllithium initiator (n-butyllithium) is used as a reference. The rheological characterization is carried out under small amplitude oscillatory shear in the stress-controlled mode. Microstructure, molecular weight, and molecular weight distribution are determined by FTIR and GPC. The vinyl content of the polybutadienes synthesized using the functionalized initiators is similar to that obtained with n-butyllithium (8–11%). Materials obtained with F1 show a relatively low polydispersity within a narrow molecular weight range (250,000–300,000 g/mol), while samples obtained with F3 cover a wider range of molecular weights (65,000–670,000 g/mol) and display higher values of polydispersity. In all cases, a parallel reaction using propylene oxide in the termination step is done to place a functional group at the chain ends. The effect of this group on the rheological behavior appears to be negligible. Three rheological models are used and their predictions of the experimental data are compared. The models include the Doi and Edwards reptation model, expressions using a discrete spectrum of relaxation times based in the rubber-like liquid constitutive equation and the fractional Maxwell equation in which a given analytical relaxation-spectrum is used. Relevant relations are obtained between the models' parameters and the molecular properties of these systems, which in turn are related to the presence of functional groups at the polymer chain ends.     

Effect of a hydrotrope on the viscoelastic properties of polymer-like micellar solutions

Low-viscosity micellar aqueous solutions of cetyltrimethylammonium bromide (CTAB) undergo a major change in the presence of the hydrotrope, potassium 1-phenylmethylsulfate (KPhMS), producing a highly viscoelastic entanglement network of polymer-like micelles. The system studied here shows typical shear banding flow behavior, which tends to disappear with increasing the hydrotrope-to-surfactant concentration ratio (C _H / C _S). The linear rheological response was analyzed with the model of Granek–Cates, whereas the nonlinear behavior was reproduced with the Bautista–Manero–Puig (BMP) model. Both models introduce a kinetic equation to account for the breaking and reformation of the micelles, and they predict the linear and nonlinear rheological data very well. This paper was presented at Annual European Rheology Conference (AERC) held in Hersonisos, Crete, Greece, April 27–29, 2006.     

Experimental and conceptual problems in the rheological characterization of wheat flour doughs

Wheat flour dough is an industrially important material and a better understanding of its rheological behavior could have long ranging impact on the agricultural and the food processing industries. However, rheological characterization of dough is proving to be difficult due to a range of testing issues and anomalies in flow behavior. In a cone-and-plate rheometer wheat flour doughs “roll-out” of the gap before steady state viscosities can be established, as discussed by Bloksma and Nieman (1975). However, the mirror image of the transient viscosity-time plot obtained using a cone-and-plate viscometer has been used to obtain an estimate of steady shear viscosity behavior (Gleissle, 1975). To check this transient methodology for doughs, a second method, in addition to cone-and-plate transient flow, for determination of the shear viscosity, was needed. For this, capillary extrusion was chosen. Both a piston-driven and pressure driven capillary rheometer were employed. End corrections were determined to provide information on both the shear viscosity and, following Binding (1988), the extensional viscosity of the doughs. There are few data available on end corrections for doughs, though published data by Kieffer indicate that the corrections are unexpectedly very high. In this present work it was found that the end correction experiments were very difficult and imprecise in part due to the time-dependent nature of the doughs and difficulties in preparing replicate batches required to compare dies of differing L/R values. Further it was unexpectedly found that the samples, though prepared by normal mixing procedures to the “optimum” level, were so heterogeneous that large fluctuations in the pressure at constant output rate (in the piston-driven rheometer) and in output rate at constant pressure (in the pressure-driven instrument) were observed. These fluctuations could be eliminated by overmixing of the doughs, but overmixed doughs are of little practical interest. Although the problems encountered in this work were significant, it was encouraging that even these preliminary studies indicate that rheological measurements are effective in differentiating between spring and winter wheats. Defining a constitutive model for dough rheology still remains a major challenge, as results from one type of testing do not corroborate the findings from a different type of testing. Received: 19 May 1998 Accepted: 27 July 1998     

Rayleigh's transformation for thermally buoyant flows

 Rayleigh's classical transformation t=x/U connecting an unsteady parallel boundary flow to the steady plane Blasius-flow is generalized to t=C·x ^c and applied to the case of natural convection in the vicinity of a vertical flat plate. The parameters C and c of this “chronotopic transformation” (CTT) are determined self-consistently. It is shown that the analytic expressions obtained in this way for temperature and for the main component of the steady velocity field reproduce the “numerically exact” patterns to a good accuracy. Surprisingly, the transversal component of the steady flow (which in the unsteady flow is entirely missing) can also be generated by CTT with a remarkable precision. Moreover, the CTT is also able to extrapolate unsteady buoyant flows to steady ones with a good performance, even if these belong to a different set of boundary conditions (e.g. time-dependent vs. coordinate-dependent wall temperatures). Received on 6 May 1999     

The phenomenological description of the thixotropic behaviour of fresh cement pastes

The present work reports an investigation on the rheological behaviour of fresh cement pastes. Three types of Portland cement were used. The water/cement ratio was varied in the range 0.35 ÷ 0.40. The rheological tests were performed using the coaxial-cylinder viscometer Rotovisko-Haake RV 11. The material to be tested was subjected immediately after mixing to a constant shear rate until a steady value of shear stress (equilibrium value) was attained. All the pastes tested exhibited a flow behaviour of the partially thixotropic type. A rheological model consisting of a sole constitutive equation \(\tau = \tau (\dot \gamma ,t)\) was defined according to the Cheng and Evans approach. The parameters of the constitutive equation were correlated with the cement specific surface and the water/cement ratio.     

Testing of Model Equations for the Mean Dissipation using Kolmogorov Flows

Direct Numerical Simulations (DNS) of Kolmogorov flows are performed at three different Reynolds numbers Re _λ between 110 and 190 by imposing a mean velocity profile in y-direction of the form U(y) = F sin(y) in a periodic box of volume (2π)³. After a few integral times the turbulent flow turns out to be statistically steady. Profiles of mean quantities are then obtained by averaging over planes at constant y. Based on these profiles two different model equations for the mean dissipation ε in the context of two-equation RANS (Reynolds Averaged Navier–Stokes) modelling of turbulence are compared to each other. The high Reynolds number version of the k-ε-model (Jones and Launder, Int J Heat Mass Transfer 15:301–314, 1972), to be called the standard model and a new model by Menter et al. (2006), to be called the Menter–Egorov model, are tested against the DNS results. Both models are solved numerically and it is found that the standard model does not provide a steady solution for the present case, while the Menter–Egorov model does. In addition a fairly good quantitative agreement of the model solution and the DNS data is found for the averaged profiles of the kinetic energy k and the dissipation ε. Furthermore, an analysis based on flow-inherent geometries, called dissipation elements (Wang and Peters, J Fluid Mech 608:113–138, 2008), is used to examine the Menter–Egorov ε model equation. An expression for the evolution of ε is derived by taking appropriate moments of the equation for the evolution of the probability density function (pdf) of the length of dissipation elements. A term-by-term comparison with the model equation allows a prediction of the constants, which with increasing Reynolds number approach the empirical values.     

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     

Investigation of the band texture occurring in hydroxypropylcellulose solutions using rheo-optical, rheological and small angle light scattering techniques

The band texture occurs in lyotropic and thermotropic main-chain polymers after cessation of flow. This paper begins with a review of work concerned with band texture formation following shear and is followed by the presentation of original results obtained during a recent investigation. The evolution of band texture formation in a Klucel EF, 50% hydroxypropylcellulose (HPC) water solution, has been observed using polarized optical microscopy. The relationship determined between the primary shear rate and the rate of evolution of the band texture is complex and three different behaviours have been observed corresponding to three shear rate regions. Both steady flow and dynamic rheological investigations have been conducted on the HPC solution, the results of which have been related to the optical behaviour of the band texture. Data from steady flow investigations suggest that the viscosity of the solution when the band texture is present, decreases following increasing primary shear rates, is shear thinning and increases linearly with the time following its formation. Dynamic investigations suggest a definite link between the band texture evolution and the evolution of both G′ and G′′. In addition, the perfection of the band texture versus the primary shear rate has been quantified by studying the evolution of tan(δ) following the cessation of the primary shear. Dynamic experiments show that the structure of the band texture remains longer than suggested by the optical aspect of the texture. Small angle light scattering patterns have been correlated with the development of the band texture and confirm the continuing presence of the band texture structure following its optical disappearance. Received: 2 March 1999/Accepted: 26 July 1999     

A Molecular-Statistical Basis for the Gent Constitutive Model of Rubber Elasticity

Molecular constitutive models for rubber based on non-Gaussian statistics generally involve the inverse Langevin function. Such models are widely used since they successfully capture the typical strain-hardening at large strains. Limiting chain extensibility constitutive models have also been developed on using phenomenological continuum mechanics approaches. One such model, the Gent model for incompressible isotropic hyperelastic materials, is particularly simple. The strain-energy density in the Gent model depends only on the first invariant I ₁ of the Cauchy–Green strain tensor, is a simple logarithmic function of I ₁ and involves just two material parameters, the shear modulus μ and a parameter J _m which measures a limiting value for I ₁−3 reflecting limiting chain extensibility. In this note, we show that the Gent phenomenological model is a very accurate approximation to a molecular based stretch averaged full-network model involving the inverse Langevin function. It is shown that the Gent model is closely related to that obtained by using a Padè approximant for this function. The constants μ and J _m in the Gent model are given in terms of microscopic properties. Since the Gent model is remarkably simple, and since analytic closed-form solutions to several benchmark boundary-value problems have been obtained recently on using this model, it is thus an attractive alternative to the comparatively complicated molecular models for incompressible rubber involving the inverse Langevin function. This revised version was published online in June 2006 with corrections to the Cover Date.     

Mathematical characteristics of the pom-pom model

 Recently, in order to describe the complex rheological behavior of polymer melts with long side branches like low density polyethylene, new constitutive equations called the pom-pom equations have been derived in the integral/differential form and also in the simplified differential type by McLeish and Larson on the basis of the reptation dynamics with simplified branch structure taken into account. In this study, mathematical stability analysis under short and high frequency wave disturbances has been performed for these constitutive equations. It is proved that the differential model is globally Hadamard stable, as long as the orientation tensor remains positive definite or the smooth strain history in the flow is previously given. However both versions of the model are Hadamard unstable if we neglect the arm withdrawal in the case of maximum backbone stretch. It is also dissipatively unstable, since the steady shear flow curves exhibit non-monotonic dependence on shear rate. Additionally, in the flow regime of creep shear flow where the applied constant shear stress exceeds the maximum achievable value in the steady flow curves, the constitutive equations exhibit severe instability that the solution possesses strong discontinuity at the moment of change of chain dynamics mechanisms. Received: 14 August 2001 Accepted: 18 October 2001     

The Giesekus fluid in ω–D form for steady two-dimensional flows

Using the fact that for simple fluids the most general constitutive equation in constant stretch history flows for the extra stress tensor τ is known in an explicit form, the Giesekus fluid model is cast into this (ω–D) form for two-dimensional flows. The three material functions needed to characterize τ are listed. The explicit results for simple shear and planar elongation reveal that the parameter α should be restricted to values less than 0.5. It is demonstrated that in this explicit form the constitutive equation is free from thermodynamic objections and can thus be used as a starting point for numerical calculations of general, but steady, two-dimensional flows. Received: 9 November 1998 Accepted: 20 May 1999     

A pragmatic approach for deriving constitutive equations endowed with pom–pom attributes

The most important rheological and mathematical features of the pom–pom model are presently used to compare and improve other constitutive models such as the Giesekus and Phan-Thien–Tanner models. A pragmatic methodology is selected that allows derivation of simple constitutive equations, which are suited to possible software implementation. Alterations to the double convected pom–pom, Phan-Thien–Tanner and Giesekus models are proposed and assessed in rheometric flows by comparing model predictions to experimental data.

Rheological analysis of highly concentrated w/o emulsions

A series of highly concentrated lipophilic cosmetic emulsions were analysed, in order to determine their rheological and textural properties, as a function of their microstructure. The originality of this study lies in the methodology used, especially the shear-stress scanning analysis. The results of a very powerful and comprehensive dynamic rheological analysis suggest the existence of two critical volume fraction values: besides the “close-packed” value φ _c , a “slack-packed” value φ₀, close to 0.60 could be demonstrated. It has been shown that the close-packed structure is stable under shear; in constrast, the slack-packed configuration, defined as φ₀<φ<φ _c is unstable under shear. A comparison with theoretical models, especially that of Princen, showed good agreement and allowed the close-packed value φ _c to be defined more precisely as 0.67. The gap between 0.67 and 0.74 is probably indicative of a highly polydisperse distribution, as confirmed by microscopic analysis. Flow experiments confirmed the validity of Princen‘s model. Received: 20 February 1997 Accepted: 20 January 1998     

Pressure Filtration of Australian Bagasse Pulp

A one-dimensional pressure filtration model that can be used to predict the behaviour of bagasse pulp has been developed and verified in this study. The dynamic filtration model uses steady state compressibility parameters determined experimentally by uniaxial loading. The compressibility parameters M and N for depithed bagasse pulp were determined to be in the ranges 3000–8000 kPa and 2.5–3.0 units, respectively. The model also incorporates experimentally determined steady state permeability data from separate experiments to predict the pulp concentration and fibre pressure throughout a pulp mat during dynamic filtration. Under steady state conditions, a variable Kozeny factor required different values for the permeability parameters when compared to a constant Kozeny factor. The specific surface area was 25–30% lower and the swelling factor was 20–25% higher when a variable Kozeny factor was used. Excellent agreement between experimental data and the dynamic filtration model was achieved when a variable Kozeny factor was used.