Influence of high pressure processing on the linear viscoelastic properties of egg yolk dispersions

The effect of high-pressure treatments on the gelation of egg yolk dispersions was studied by using differential scanning calorimetry (DSC) and small amplitude oscillatory shear (SAOS). The influence of pressure of processing and pH were analysed. The DSC results suggest a progressive decrease in thermal denaturation enthalpy as pressure level increases related to protein denaturation. SAOS was used to evaluate the effect of different pressure levels on the linear viscoelastic behaviour of egg yolk dispersions. An increase in the pressure level produces a dramatic change in the linear viscoelastic behaviour undergoing a sol–gel transition. High hydrostatic pressure (HHP) processing was also analysed as a function of pH and solids content. The results obtained confirm that the impact of high pressure on aggregation and network formation can be modulated by pH. HHP processing of egg yolk systems is highly affected by protein concentration particularly when it is compared to heat processing.     

Effects of anionic additives on the rheological behavior of aqueous calcium montmorillonite suspensions

Three different experimental measurements, namely, rheology, particle sizing, and x-ray diffraction (XRD), were used to study the effect of anionic additives on the properties of bentonite suspensions. The three additives were sodium carboxymethylcellulose, xanthan gum, and sodium dodecyl sulfate. Flow curves were obtained from shear stress–shear rate measurements, and the viscoelastic properties were determined from oscillatory and transient measurements. Mineralogical data were evaluated by XRD and the particle size analysis performed by light scattering technique. The presence of the surfactant modifies the face-to-face interactions and yields changes of the mixtures rheological behavior at low deformation rates. Polymers act by coating each clay particle and prevent their agglomeration. Therefore, the additives are responsible for the mechanisms of destructuration and structure reorganization as well as the mixtures viscous and viscoelastic behavior.     

Viscoelastic plastic rheological model for particle filled polymer melts

A viscoelastic plastic model for suspension of small particles in polymer melts has been developed. In this model, the total stress is assumed to be the sum of stress in the polymer matrix and the filler network. A nonlinear viscoelastic model along with a yield criterion were used to represent the stresses in the polymer matrix and the filler network, respectively. The yield function is defined in terms of differential equations with an internal parameter. The internal parameter models the evolution of structure changes during floc rupture and restoration. The theoretical results were obtained for steady and oscillatory shear flow and compared with experimental data for particle filled thermoplastic melt. The experimental data included the steady state shear strress over a wide range of shear rates, the transient stress in a start up shear flow, stress relaxation after cessation of a steady state shear flow, the step shear and the oscillatory shear flow at various amplitudes.     

Effect of flow history on the structure of a non-polar polymer/clay nanocomposite model system

The effect of flow history on the linear and non-linear viscoelastic properties of non-polar polymer nanocomposites (PNCs) has been investigated by means of a suitable model system based on a Newtonian matrix. The structural recovery of this model suspension after cessation of different pre-shear rates was monitored by measuring its linear viscoelastic properties while its structural evolution under shear flow was followed by using stepwise changes in shear rate including flow reversal measurements. To assess the kinetics of the structural evolution at rest and under flow, empirical relations of stretched exponential form were used. It is shown that for different pre-shear rates, different equilibrium structures were reached at rest but with a similar kinetics of recovery. As a result, the low frequency behaviour was typical of solid-like or weak gel material, strongly dependent on the flow history. After any given shear rate under steady state, only one reversible equilibrium structure was reached after a kinetics that was dependent on the pre-shear history. Finally, typical flow reversal responses as observed for PNCs are reported and interpreted in light of the microstructure evolution under flow. This paper was presented at the Annual Meeting of the European Society of Rheology, Hersonisos, Greece April 2006.     

Characterization of polymer dispersions by Fourier transform rheology

Fourier transform rheology is a very sensitive technique to characterize non-linear rheological fluid properties. It has been applied here for the first time to polymer dispersions in water and the results are compared to those from conventional rheology, namely steady and small amplitude oscillatory shear experiments. The investigated systems are mainly based on styrene and n-butylacrylate. A first attempt was made to evaluate how far colloidal parameters like particle volume fraction and ionic strength as well as chemical composition and surface characteristics of the dispersed particles are reflected in FT-rheology spectra. Significantly different non-linearities are observed for highly concentrated dispersions of particles with different T_g. These differences are not detected in linear oscillatory shear and show up in steady shear only at significantly higher shear rates. Particle surface characteristics influence the non-linear response in oscillatory shear significantly and the intensity of the overtones is found to be higher for a dispersion of particles with a “hairy” swollen surface layer as compared to a system of smooth particles, although the solids content was adjusted to match the steady shear viscosity. The intensity of the overtones in FT-rheology strongly decrease upon dilution. At a solid content below 35% no differences are observed in the FT-experiments for the systems investigated here, whereas the differences in steady shear are very pronounced in this concentration range. A significant influence of added salt onto the non-linear response is detected for some systems, which might be correlated to the stability of these systems. The observed phenomena certainly cannot be explained in terms of constitutive equations or microstructural statistical mechanical models at present. Thus, FT-rheology yields information complementary to classical steady or linear oscillatory shear experiments. Received: 11 December 2000 Accepted: 8 April 2001     

The effect of parallel combined steady and oscillatory shear flows on blood and polymer solutions

Human blood at physiological volume concentration exhibits non-Newtonian and thixotropic properties. The blood flow in the microcirculation is pulsatile, initiated from the heart pulse and can be considered as superposition of two partial flows: a) a steady shear, and b) an oscillatory shear. Until now steady and viscoelastic behavior were separately investigated. Here we present the response to the combination of steady and oscillatory shear for human blood, a high molecular weight aqueous polymer solution (polyacrylamide AP 273E) and an aqueous xanthan gum solution. The polyacrylamide and xanthan solutions are fluids that model the rheological properties of human blood. In general, parameters describing blood viscoelasticity became less pronounced as superimposed steady shear increased, especially at low shear region and by elasticity, associated with reduction in RBC aggregation. The response of polymer solutions to superposition shows qualitative similarities with blood by elasticity, but their quantitative response differed from that of blood. By viscosity another behavior was observed. The superposition effect on viscous component was described by a modified Carreau equation and for the elastic component by an exponential equation.Paper in part presented at the Symposium on Rheology and Computational Fluid Mechanics dedicated to the memory of Prof. A. C. Papanastasiou, University of Cyprus, Nicosia, July 4–5, 1996     

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.     

On the Cox-Merz rule for magnetic dispersions

The Cox-Merz rule can be a useful, empirical tool for relating steady and oscillatory shear flow property measurements. Here we test its applicability for magnetic dispersions. Neither the rule nor a previously published modification of it applies for the dispersions, but we demonstrate that the steady shear viscosity and the magnitude of the complex viscosity are nonetheless related. Received: 30 August 2000 Accepted: 21 December 2000     

Linear viscoelastic behavior of copper phthalocyanine dispersions used in printing inks

In this paper we describe the linear viscoelastic properties of copper phthalocyanine (CuPCN) dispersions that are used in the manufacturing of offset lithographic printing inks. Transmission electron microscopy shows that the primary pigment particles are rod-like and have sizes in the range of 10 to 300 nm. Steady shear measurements show that the dispersions are Newtonian at a pigment volume fraction of 0.073 and become increasingly shear thinning as the pigment volume fraction is increased. The strong shear-thinning nature of these dispersions can be attributed to the highly flocculated nature of the dispersions, which is due to interparticle attractions. The structural complexity of the dispersions also results in an unexpected linear viscoelastic response. While at low frequencies (0.1 and 1.0 Hz) the ex tent of the linear region decreases with increasing pigment concentration, at a higher frequency (10 Hz) the extent of the linear region increases with increasing pigment concentration. This increase in the linear region with increasing pigment concentration suggests that at higher frequencies the dispersion is less brittle, and that the rheological behavior is dominated by intra-aggregate associations. In addition, frequency sweeps show that the dispersions behave like a viscoelastic liquid at low pigment concentrations. However, at higher pigment concentrations (yet significantly lower than the maximum packing fraction) the dispersions behave like a cross-linking polymer at its gel point.     

Rheological characterization of bimodal colloidal dispersions

In order to investigate the effect of the particle size distribution on the rheological properties of concentrated colloidal dispersions both steady-state shear and oscillatory measurements have been performed on well-characterized bimodal dispersions of sterically stabilized PMMA particles. Replacing a minor amount of large particles by small ones in a concentrated dispersion, keeping the total effective volume fraction constant, decreases the viscosity quite drastically. On the other hand, replacing a small amount of small particles by big ones hardly effects the viscosity at all. This behavior can be attributed to the deformability of the stabilizing polymer layer. A procedure is proposed to calculate the limiting viscosities in a bimodal colloidal dispersion starting from the characteristics of the monodisperse systems. A good agreement has been obtained between the calculated values and the experimental results. The linear viscoelastic properties of the concentrated dispersions have been investigated by means of oscillatory measurements. The plateau values of the storage modulus for the bimodal dispersions decrease with an increasing fraction of the coarse particles. By substituting the bimodal dispersion by an equivalent monodisperse system the storage modulus can be superimposed on the values for the monodisperse suspensions when plotted as a function of the mean interparticle distance.     

Unsteady-state development of plane couette flow for viscoelastic fluids

Unsteady-state development of plane Couette flow for viscoelastic fluids is analyzed using a constitutive equation that can be obtained from molecular theory, in which the molecules are regarded as finitely extensible dumbbells. Typical features of the flow situation are as follows: (i) For a fluid with moderate elasticity, not only stress overshoot but also velocity overshoot are predicted. (ii) For suitable combinations of elasticity and gap width, and for some time intervals stress propagation and reflection phenomena are predicted. (iii) After a sufficient time has elapsed, the stress state behaves similarly to that corresponding to the start-up of a steady simple shear flow.     

A thermodynamic approach to the rheology of highly interactive filler-polymer mixtures: Part I – Theory

The rheological behavior of highly interactive filler-polymer mixtures is simulated utilizing a double network created by the entangled polymer matrix and the adsorbed polymer. Both networks are represented by a nonlinear viscoelastic constitutive equation. The dependence of rheological properties on filler concentration is taken into account through the bridging density resulting from polymer-filler interactions and a hydrodynamic reinforcement. The relative contribution of both networks is computed through the energy balance consistent with the thermodynamics of the polymer-filler chemical interactions and fluid mechanics. This self-consistent approach allows one to calculate the strain dependence of dynamic properties under oscillatory flow and shear rate dependence of stresses under steady simple shear flow and upon start up and cessation of shear flow. Received: 11 May 2000 Accepted: 8 March 2001     

The squeeze-film flow of a viscoelastic fluid

We report on the use of a numerical method to solve the (inertia-less) squeeze-film flow problem for a viscoelastic fluid. The method is based on a Boundary Element formulation and relies on a time-marching scheme. The viscoelastic fluid is modelled by a constitutive law that allows for a shear stress overshoot mechanism in a suddenly started shear flow. The results show convincingly that the load enhancement sometimes observed experimentally is due to stress overshoot. A simple explanation for the enhancement is suggested; the stress overshoot appears quickly and takes a long time to die away, so that steady-state viscous behaviour is not very relevant.     

Multiple-time scale approach to stress growth in suspensions of rodlike macromolecules

The rheologial properties of a dilute suspension of rigid rodlike macromolecules at the inception of a steady homogeneous flow are examined within the framework of the kinetic theory of polymeric liquids. The cases of simple shear and elongational flows are considered under the assumption of small non-dimensional shear rates, ϵ = κ₀/6D, where D is the rotation diffusion of the particles. The method of multiple-time scales is used to solve the problem and the resulting transport coefficients are shown to reveal new features as compared with the results of the straightforward perturbation technique. In particular, the onset of stress oscillations leading to an undershoot following the overshoot of the shear viscosity and the overshoot of the normal stress difference are detected as ϵ approaches unity.     

椭圆颗粒在剪切流中旋转特性的数值研究

研究颗粒在流体剪切作用下的运动特性是理解和预测颗粒悬浮流流动行为的关键.当流体的惯性不能忽略时,颗粒的运动往往变得非常复杂.本文采用格子Boltzmann方法对中等雷诺数下椭圆颗粒在剪切流中的旋转运动进行了模拟.首先,研究了雷诺数(0Re 170)的影响,结果表明当雷诺数低于临界值时,颗粒以周期性的方式旋转,角速度最小时对应的长轴方向随着雷诺数的增大而逐渐远离水平方向,而且这一倾角与雷诺数呈分段线性关系;当雷诺数大于临界值时,椭圆形颗粒最终保持静止状态,且静止时的转角与雷诺数呈幂函数关系,雷诺数越大,转角越小,椭圆的长轴越远离水平位置.其次,研究了椭圆颗粒的长短轴之比α(1α10)的影响,结果表明颗粒旋转的周期与α呈幂函数关系,α越大,颗粒旋转周期越小.此外,当α超过临界值时,颗粒也在水平位置附近保持静止状态,此时的转角与α也呈幂函数关系,α越大,转角越小.研究还发现,当雷诺数较大时椭圆颗粒在旋转过程中会产生过冲现象.     

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     

Rheology and flow studies of drag-reducing gravel packing fluids

Viscoelastic additives are widely used as drag reducers in the oil and gas industry, and both polymeric additives and micellar surfactants are commonly used in well gravel packing applications. While the behaviour of polymeric additives such as the polysaccharide xanthan gum is well characterized in the literature, much less is known about how the rheology of the viscoelastic surfactants affects drag reduction, despite widespread use. In this study, we performed a number of rheological tests as well as flow loop experiments on solutions of a zwitterionic surfactant to understand the structural characteristics of the fluids in order to make better process predictions. Unlike xanthan, which displays typical viscoelastic liquid characteristics, zwitterionic surfactant-based fluids display elastic gel-like behaviour. The gel-like behaviour suggests long and relatively unbreakable chain lengths of the wormlike micelles in the viscoelastic surfactant solution at room temperature leading to gelation by entanglement. Also, a shear-thickening behaviour of viscoelastic surfactant samples at higher shear rates is observed, possibly as a result of shear-induced structures. Finally, we present a novel representation scheme to depict the flow loop results for drag in the laminar and turbulent regime, and relate this data to the rheological characterization.     

Rheology of compatibilized immiscible viscoelastic polymer blends

Rheological behavior of a PS/PE model viscoelastic immiscible blend compatibilized by two types of interfacial modifiers was investigated. Dynamic, steady shear, and transient experiments were performed to probe the effect of the interfacial modification on the rheological behavior of the blend. While the effect was relatively small in dynamic and steady shear experiments, significant signature of the presence of the copolymer was observed in transient experiments after start up of shear flow. The magnitude of the departure from Doi-Otha theory (worked out for non-compatibilized blends) was evaluated. Received: 6 March 2000 Accepted: 15 June 2000     

Elongational flow behavior of polymeric fluids according to the Leonov model

The viscoelastic behavior of polymeric systems based upon the Leonov model has been examined for (i) the stress growth at constant strain rate, (ii) the stress growth at constant speed and (iii) the elastic recovery in elongational flow. The model parameters have been determined from the available rheological data obtained either in steady shear flow (shear viscosity and first normal-stress difference as a function of shear rate) or oscillatory flow (storage and loss moduli as a function of frequency in the linear region) or from extensional flow at very small strain rates (time-dependent elongation viscosity in the linear viscoelastic limit). In addition, the effect of the parameter characterizing the strain-hardening of the material during elongation has also been studied. The estimation of this parameter has been based upon the structural characteristics of the polymer chain which include the critical molecular weight and molecular weight of an independent segment. Five different polymer melts have been considered with varying number of modes (maximum four modes). Resulting predictions are in fair agreement with corresponding experimental data in the literature.     

Rheological properties of disperse systems at low shear stresses

Three-dimensional network structures can be built up in disperse systems due to long-range colloidal interactions between the dispersed particles. The rheological behaviour of such coagulation structures has been studied by means of creep and recovery experiments at low shear stresses, i.e. by measuring the shear strain as a function of time under constant stress and after removal of stress. Measurements of this type give insight into the elastic and viscous deformations and the retardation times necessary to reach equilibrium or steady-state conditions.Results obtained with dispersions of pigments in polymer solutions and with monodisperse polymer latexes indicate the existence of an equilibrium state at low shear stresses with a predominant elastic deformation and a high viscosity suggesting that the disperse systems investigated do not behave exactly as rigid gels but apparently exhibit a dynamic equilibrium of structural break-down and formation under applied stress. This behaviour is approximately described by a 4-parameter-model with an instantaneous and a steady-state compliance, one retardation time, and a viscosity.At higher shear stresses thixotropic structural break-down occurs resulting in a transition from the rheological behaviour described here to a liquid-like state with a comparatively low viscosity. In this stress range the viscoelastic properties become strongly time-dependent.These measurements give evidence of the presence of two types of deformation: an instantaneous, purely elastic deformation attributable to the unperturbed coagulation structure and the creep-recovery behaviour of an elastic liquid apparently related to the breaking and re-forming of bonds.