Rheological behaviour of nano-composites based on polyamide 6 under shear and elongational flow at high strain rates

In this work, the rheological behaviour of high molecular mass polyamide 6 (PA6)/organo-montmorillonite nano-composites, obtained via melt blending, was investigated under shear and extensional flow. Capillary rheometry was used for the measurement of high shear rate steady state shear viscosity and die entrance pressure losses; further, by the application of a converging flow method (Cogswell model) to these experimental results, elongational viscosity data were indirectly calculated. The extensional behaviour was directly investigated by means of melt spinning experiments, and data of apparent elongational viscosity were determined. The results evidenced that the presence of the organo-clay in filled PA6 melts modifies the rheological behaviour of the material, with respect to the unfilled polymer, in dependence on the type of flow experienced by the fluid. In shear flow, the nano-composites showed a slightly lower viscosity than neat PA6, whereas in elongation, they appeared much more viscous, in dependence on the organo-clay content.     

Linear and non-linear rheological behaviour of cement and silica suspensions. Effect of polymer addition

Oil well cement pastes and model silica suspensions demonstrate similar rheology: in oscillatory shear, beyond a critical stress, a sharp transition is ob- served between gel and liquid behaviour. In creep tests, an apparent yield stress and shear-thinning are followed by the appearance of shear thickening. The minimum viscosity measured in steady shear is close in value to the complex viscosity obtained from oscillatory measurements. The observations can be explained by the formation of liquid trapping aggregates whose compactness may be estimated by fitting the Tsenoglou model, and whose cohesion is reflected in the rigidity of the gel and in the critical strain (or stress) of gel dissolution. Substituting cement or silica particles by polymer redispersible powder causes a decrease of the storage modulus in the gel state and a lower viscosity, while leaving the general features of the flow curve unchanged. Decrease in material rigidity may be due to a weaker inter-particle attraction generated by the polymer presence. The decrease in viscosity is explained by a lessening of water entrapped within the aggregates, which now contain polymer particles which are less hydrophilic than either cement or silica.     

Diffusion effects on the interfacial tension of immiscible polymer blends

Most methods of measuring the interfacial tension between two immiscible polymers are based on the analysis of the shape that a drop of one polymer immersed in the other one exhibits under the action of flow or gravity. In such a situation, the small, yet nonzero mutual solubility between the two polymers acts toward mass transfer between the drop and the surrounding fluid. In this work, diffusion effects on the interfacial tension of the pair polyisobutylene/polydimethylsiloxane have been investigated by drop deformation under shear flow. When the drop was made of polyisobutylene, drop size decreased with time due to diffusion. Drop shrinkage was associated with a significant increase in interfacial tension, until an apparent plateau value was reached. The effect was attributed to a selective migration of molecular weights, which would act to enrich the drop with higher molar mass material. To support such an interpretation, drop viscosity was evaluated by drop shape analysis and it was actually found to increase with time. In some cases, the ratio between drop and continuous phase viscosity became higher than the critical value for drop breakup in shear flow. Upon inverting the phases (i.e., when the drop was made of polydimethylsiloxane), no significant transient effects were observed. In the light of these results, the problem of what are the correct values of interfacial tension and viscosity ratio for a polymer blend of a certain composition will also be discussed. Received: 25 January 1999 Accepted: 24 May 1999     

Solutions of xanthan gum/guar gum mixtures: shear rheology,porous media flow,and solids transport in annular flow

Mixtures of xanthan and guar gum in aqueous solution were studied in two flow situations: simple shear and porous media. In addition, solids transport in vertical annular flow of sand suspensions was explored. The zero shear rate viscosity of the solutions displayed a pronounced synergy: the viscosity of the mixture is higher than that of the polymer solutions in a wide range of relative concentrations of the two polymers, in agreement with previous literature. However, at relatively high shear rates, the viscosity approaches the value of the more viscous xanthan gum solutions at mass fractions of xanthan gum between 0.1 and 0.15, and the degree of synergy substantially decreases. Stress relaxation experiments in simple shear indicate that the polymer mixtures exhibit a well-defined yield stress after relaxation that is absent in solutions of pure polymers. In porous media flow experiments, a synergistic behavior mimicking the shear flow results was obtained for the polymer mixtures at low shear rates. However, at a critical shear rate, the apparent viscosity in porous media flows exceeds the shear viscosity due to the elongational nature of flow in the pores. The solids transport capacity in annular flows is well-represented by trends in shear viscosity and stress relaxation behavior. However, the lack of viscosity synergy at high shear rates limits the applicability of the mixtures as a way to improve solids suspension capacity in annular flows.     

Deformation and breakup of viscoelastic drops in planar extensional flows

A computer-controlled four-roll mill was used to investigate the deformation and break-up of polymeric drops in the well-characterized flow of an immiscible Newtonian fluid. Aqueous polymer solutions ranging in concentration from 160 ppm to 3% by weight were examined. For zero-shear-rate viscosity ratios greater than order 1, the deformation of the drops closely followed that of Newtonian fluids, irrespective of the droplet material. However, drops with viscosity ratios less than order 1 had significantly smaller critical deformations and the critical capillary number was found to be substantially smaller. Two modes of drop break-up were discovered that differed substantially from that observed for Newtonian drops in the inclusion of cusped ends and tip streaming.     

Extensional rheology of concentrated poly(ethylene oxide) solutions

The shear and extensional rheology of three concentrated poly(ethylene oxide) solutions is examined. Shear theology including steady shear viscosity, normal stress difference and linear viscoelastic material functions all collapse onto master curves independent of concentration and temperature. Extensional flow experiments are performed in fiber spinning and opposed nozzles geometries. The concentration dependence of extensional behavior measured using both techniques is presented. The zero-shear viscosity and apparent extensional viscosities measured with both extensional rheometers exhibit a power law dependence with polymer concentration. Strain hardening in the fiber spinning device is found to be of similar magnitude for all test fluids, irrespective of strain rate. The opposed nozzle device measures an apparent extensional viscosity which is one order of magnitude smaller than the value determined with the fiber spinline device. This could be attributed to errors caused by shear, dynamic pressure, and the relatively small strains developed in the opposed nozzle device. This instrument cannot measure local kinematics or stresses, but averages these values over the non-homogenous flow field. These results show that it is not possible to measure the extensional viscosity of non-Newtonian and shear thinning fluids with this device. Fiber spin-line experiments are coupled with a momentum balance and constitutive model to predict stress growth and diameter profiles. A one-mode Giesekus model accurately captures the plateau values of steady and dynamic shear properties, but fails to capture the gradual shear thinning of viscosity. Giesekus model parameters determined from shear rheology are not capable of quantitatively predicting fiber spinline kinematics. However, model parameters fit to a single spinline experiment accurately predict stress growth behavior for different applied spinline tensions.     

Rheological and molecular characterization of linear backbone flexible polymers with the Cole-Cole model relaxation spectrum

The empirical Cole-Cole distribution is an analytical three parameter model of the relaxation spectra that provides accurate fits to experimental dynamic viscosity data for many systems of commercial linear backbone flexible polymers. We demonstrate that for disparate systems of polyethylenes, the three Cole-Cole model parameters have simple power law relationships to moments of the molecular weight distribution enabling direct molecular interpretation of the mechanical relaxation spectrum. A simple relationship between the Cole-Cole distribution and the Cross model for the non-linear flow curve can be deduced utilizing the empirical Cox-Merz rule. Accurately representing the linear viscoelastic material functions with empirical analytical relaxation spectra containing relatively few fitting parameters that can be readily interpreted is a major advance in polymer characterization. The three Cole-Cole parameters effectively replace single point material characterizations such as melt flow index. Development of higher resolution polymer characterization methods is imperative with the advent of metallocene catalyst technology, which enables the molecular weight and backbone architecture to be carefully controlled. Received: 3 March 1998 Accepted: 30 September 1998     

液晶高分子各向异性粘弹性流体本构方程理论

将液晶高分子－各向异性流体的本构方程,建立在Oldroyd随体导数观点基础上。推广上随机Oldroyd B流体模型,提出共转OldroydB流体模型,同时将微观结构的影响通过宏观参数表示出来,使在宏观理论中包含微观结构的贡献,即引入取向物质函数,非线性各向异性黏度函数和各向异性松弛时间及推迟时间等,表征取向运动对黏度和松弛及推迟现象的影响,在此基础上开展了一类新的液晶高分子－Oldroyd型本构方程理论,由该类型本构方程得出的物质函数,液晶高分子流体的第一、第二法向应力差与实验结果一致,解释了液晶高分子溶液的第一、第二法向应力差的特殊流变学行为。     

The modified constrained volume model predictions in shearing flow at nonunity viscosity ratio values

In this paper, the modified constrained volume model, which describes the evolution of anisotropy of immiscible polymer blends, composed of Newtonian components, was examined during shearing motion (steady and oscillatory) at various viscosity ratio values. We found that the linear correction to the rate of deformation tensor causes the droplet to change its volume at viscosity ratio values lower than unity, and to cause premature tumbling at viscosity ratio values larger than unity, in a case where retraction, breakup, and coalescence modules of the model were turned off. The use of Eshelby tensor, together with a closure to relate anisotropy to the Eshelby concentration tensor, mostly solved the problem. The model’s predictions are then shown at various capillary number values and at various viscosity ratio values. Comparison of model predictions to single droplet data at nonunity viscosity ratio value showed good agreement. Finally, model predictions of first normal stress difference during startup of steady shear are compared to experimental rheological results for immiscible polymer blends that are available in literature. Good predictions can be achieved by the introduction of a new switch function that controls the retraction and breakup modules. The model’s predictions at large amplitude oscillatory shear were examined. It was found that linear corrections to the velocity gradient tensor can be used for strains up to 100 %. For larger strain values, the Eshelby concentration tensor must be used.     

From melt flow index to rheogram

A knowledge of the complete flow curve or rheogram of a polymeric melt depicting the variation of the melt viscosity over industrially relevant range of shear rate and temperature is essential in the design of polymer processing equipment, process optimization and trouble-shooting. These data are generated on sophisticated rheometers that are beyond the financial and technical means of most plastics processors. The only flow parameter available to the processor is the melt flow index of the material. In the present work, a method has been proposed to estimate the rheograms of a melt at temperatures relevant to its processing conditions with the use of a master curve, knowing the melt flow index and glass transition temperature of the material. Master curves that coalesce rheograms of different grades at various temperatures have been generated and presented for low density polyethylene, high density polyethylene, polypropylene, polystyrene and styrene-acrylonitrile copolymer.     

Rheology for deposition control of polymer-amended oil sands tailings

Mineral slurries may be dewatered to the point that they manifest non-Newtonian behavior. Many such slurries exhibit both thixotropic and hysteric behavior in their rheology, which has important implications for managing their deposition in tailings impoundments. This paper characterizes the rheology of a mineral slurry with relatively high clay content, which is treated with a high molecular weight anionic polymer to induce flocculation. The rheology exhibits viscosity bifurcation behavior similar to pure clay, including shear history-dependent apparent yield stress values. Rheometry results are presented including stress growth, controlled stress tests, and oscillatory rheometry, all using a vane fixture. The measured rheology is modeled using a previously published viscosity bifurcation model that accounts for hysteresis in the apparent yield stress. The rheology results are used semi-quantitatively to explain deposition rate-dependent behavior seen in flume tests. The geometry of tailings in flume tests with relatively slow deposition is affected by the presence of deposited tailings that have come to rest sufficiently to manifest the yield stress of initially fully structured material, rather than the lower value yield stress that characterizes when the material first comes to a stop. This full recovery of the yield stress seems to be particularly important to managing surface deposition, as zones of tailings that have stopped moving substantially steepen the slope of deposits near the deposition point.     

Numerical simulation studies of the planar entry flow of polymer melts

This paper is concerned with the numerical simulation of planar entry flow using a penalty finite element method and the comparison of predictions with flow visualization and birefringence data for two polymer melts. The Phan-Thien Tanner (PTT) model was fit to the steady state shear and extensional viscosity data and the transient extensional viscosity data of both polystyrene and low-density polyethylene (LDPE) melts to obtain the parameters λ, ξ, and ϵ in this model. Agreement was found between the flow visualization and birefringence data and the predictions of streamlines and stress. With some modification of the constitutive equation, the vortex growth and intensity observed for LDPE could be predicted by the use of the PTT model and the material parameters fit to the rheological properties. Likewise, the flow behavior of polystyrene, in which only small vortices with no growth were observed, was also predicted. Furthermore, it was found that the size and intensity of the vortex could be affected by the parameter ϵ in the PTT model which controls the predictions of the extensional viscosity. Based on these results it seems that accurate simulation of entry flow behavior requires the use of a constitutive equation which is capable of giving realistic preciction's of a fluid's extentional flow properties.     

Time-dependent non-linear dynamics of polymer solutions in microfluidic contraction flow—a numerical study on the role of elongational viscosity

A generalised form of the finitely extensible non-linear elastic (FENE) model for modelling non-linear flow of semi-dilute polymer solutions is proposed. It accounts for conformation-dependent polymer elasticity and predicts shear-thinning shear viscosity, non-linear elongational viscosity and first and second normal stress differences. The rheometric material functions predicted by the model are critically compared with the results of the linear Phan–Thien–Tanner model. The predictabilities of these constitutive models under benchmark flow problems are evaluated by time-dependent simulations, using finite volume method based on a CFD simulation toolbox. The effects of the model parameters, the inertia and the contraction ratio are numerically studied. The modified FENE model qualitatively captures the non-linear flow phenomena of polymer solution in the high elasticity number ( $\mathrm {El}$ ) flow regime observed in experiments. The results show that an accurate growth function of the elongational viscosity is the key to the prediction of the time-dependent highly asymmetric flow patterns.     

Investigation of heat transfer of nanofluids in turbulent flow in a cylindrical channel

Turbulent flow of nanofluids based on the distilled water with aluminum and silicon oxide particles of different sizes in a cylindrical channel is studied. The results of the measurements of the heat transfer coefficient and the pressure difference are presented. The maximum volume concentration of the particles was not greater than two percents. The dependence of the heat transfer coefficient on the nanoparticle concentration and their sizes and material is studied. It is shown that a considerable increase in the nanofluid heat transfer coefficient, compared with the corresponding value for water, may generally be expected. At the same time, the heat transfer coefficient of a nanofluid depends on the nanoparticle size and material; because of this, under certain conditions the nanofluid heat transfer coefficient can turn out to be lower than that of the baseline fluid. Situations, when this can occur, are established. It is for the first time experimentally shown that the nanofluid viscosity coefficient depends not only on the nanoparticle size but also on its material.     

A parameter investigation of shear-induced coalescence in semidilute PIB–PDMS polymer blends: effects of shear rate, shear stress volume fraction, and viscosity

In this work, drop coalescence of polymer blends under shear flow in a parallel flow apparatus was investigated by optical sectioning microscopy. In each experiment, shear rate was set at values low enough to avoid any break-up phenomena. The time evolution of the drop size distribution was determined by motorized sample scanning and iterative acquisition of stacks of images along sample depth. Drop size and location in the acquired images was found by automated image analysis techniques. A systematic experimental campaign to investigate the effects of shear rate (in the range 0.1–0.5 s⁻¹), volume fraction (2.5–10%), and viscosity of the two phases (3–63 Pa s) at different viscosity ratio (0.1–2.3) was carried out. By comparing data from different experiments, it was found that at any strain value, the average drop size decreases monotonically with the shear stress, calculated as the product of shear rate and matrix viscosity. Furthermore, the coalescence rate slowed down with increasing viscosity ratio. Overall, these results provide an extensive set of data, which can be used as a benchmark for modeling shear-induced coalescence in polymer blends.Paper presented at the Annual Meeting of the European Society of Rheology, Grenoble, April 2005.     

An unsymmetric constitutive equation for anisotropic viscoelastic fluid

A continuum constitutive theory of corotational derivative type is developed for the anisotropic viscoelastic fluid–liquid crystalline (LC) polymers. A concept of anisotropic viscoelastic simple fluid is introduced. The stress tensor instead of the velocity gradient tensor D in the classic Leslie–Ericksen theory is described by the first Rivlin–Ericksen tensor A and a spin tensor W measured with respect to a co-rotational coordinate system. A model LCP-H on this theory is proposed and the characteristic unsymmetric behaviour of the shear stress is predicted for LC polymer liquids. Two shear stresses thereby in shear flow of LC polymer liquids lead to internal vortex flow and rotational flow. The conclusion could be of theoretical meaning for the modern liquid crystalline display technology. By using the equation, extrusion–extensional flows of the fluid are studied for fiber spinning of LC polymer melts, the elongational viscosity vs. extension rate with variation of shear rate is given in figures. A considerable increase of elongational viscosity and bifurcation behaviour are observed when the orientational motion of the director vector is considered. The contraction of extrudate of LC polymer melts is caused by the high elongational viscosity. For anisotropic viscoelastic fluids, an important advance has been made in the investigation on the constitutive equation on the basis of which a series of new anisotropic non-Newtonian fluid problems can be addressed. The project supported by the National Natural Science Foundation of China (10372100, 19832050) (Key project). The English text was polished by Yunming Chen.     

The role of elongational viscosity in the mechanism of drag reduction by polymer additives

The role of elongational viscosity in the mechanism of drag reduction by polymer additives is investigated qualitatively by means of direct numerical simulations of a turbulent pipe flow. For the polymer solution, a generalised Newtonian constitutive model is utilised in which the viscosity depends on the second and third invariant of the rate-of-strain tensor via an elongation parameter. This elongation parameter is capable of identifying elongational type of regions within the flow. The simulations show that complementary to stretching of the polymers, also compression must be incorporated to have drag reduction, contrary to many suggestions done in the literature on the mechanism which assume that stretching of the polymers is most important.     

Extensional behavior influence on viscoelastic turbulent channel flow

In this work we use in the simulation of a viscoelastic turbulent channel flow a modification of the finitely extensible of non-linear elastic dumbbells with the Peterlin approximation (FENE-P) constitutive model for dilute polymer solutions, applicable to high extensional deformations. The new feature introduced by this modification is that the free energy of the polymer (since it is assumed to be entirely entropically driven) remains always bounded (FENE-PB). The characteristics of the model under steady shear flow, pure elongational flow and transient extensional behavior are presented. It is found that the FENE-PB model is more shear thinning than FENE-P. Most importantly, it also shows a higher extensional viscosity than the FENE-P model. Although the steady-state Trouton ratio asymptotically reaches at high extensional rates the same limit as the FENE-P model, the transition from the Newtonian value is sharper and faster. We use the FENE-PB model in direct numerical simulations (DNS) of viscoelastic turbulent channel flow using spectral approximations. The results for various statistics of the flow and the polymer conformation, when compared against those obtained with the original FENE-P model and the same rheological parameters, show an enhanced polymer-induced drag reduction effect and enhanced deformation of the polymer molecules. This indicates that it is not only the asymptotic but also details from the extensional rheological behavior that matter in quantitatively specifying turbulent viscoelastic flow behavior.     

Exponential shear flow of branched polyethylenes in rotational parallel-plate geometry

Exponential shear flow, as a strong flow with the potential to generate a high degree of molecular stretching, has attracted considerable interest in recent years. So far, exponential shear flow has been realized by either sliding-plate or cone-and-plate (CP) geometry. Both geometries guarantee homogeneous shear flow. Here, we present experimental data on exponential shear flow of several long-chain branched polyethylene melts with different degrees of strain hardening obtained by using parallel-plate (PP) geometry in a rotational rheometer. This type of geometry, which is standard in linear-viscoelastic characterization of polymer materials, produces inhomogeneous shear flow. A comparison of exponential shear flow data obtained by PP and CP geometry is made. Additionally, the experimental data are compared to predictions of the rubber-like liquid (RLL) and the molecular stress function (MSF) theories. For this purpose, the relaxation spectra of the polymer melts considered were obtained by standard linear-viscoelastic characterization. In addition, two irrotational parameters and one rotational parameter are required by the MSF theory. While the irrotational parameters were obtained from fitting to elongational viscosity data, the value of the rotational parameter was used as given in the literature. It can be concluded that viable experimental data in exponential shear flow can be obtained by PP geometry. For finite linear-viscoelasticity (RLL theory), predictions of reduced shear stress for CP and PP geometry coincide, but nonlinear material behavior (as modeled by the MSF theory) leads to small differences between both geometries. Furthermore, it is shown that the MSF predictions are in excellent agreement with the experimental data in exponential shear flow and that this type of flow leads to much less chain stretching than elongational flow.Dedicated to the memory of Prof. Arthur S. Lodge (1922–2005).     

A model long-discontinuous-fiber filled thermoplastic melt in extensional flow

The shear cell model works for dilute fiber filled systems in extensional flow. This research investigates the suitability of the idea for highly aligned fibers in a concentrated suspension. A model fiber-filled polymer system made from nylon fibers in low-density polyethylene provided a means of controlling the material parameters. Two systems, with fiber aspect ratios of 20 and 100, containing 50% 0.5 mm fibers by volume are investigated. The thickness of the polymer layer, i.e. with fibers this size, allows bulk viscosity data to be compared with the data from the filled fluid. A weaving process created the discontinuous fiber/polyethylene preforms with high alignment of the fibers and with control of the fiber to fiber overlap. Testing the polyethylene in simple shear and extending the nylon/polyethylene provided the data needed to check the micro mechanics. A cone and plate rheometer and a capillary instrument produced the viscosity/strain rate data that characterized the specific polyethylene used in the composite. A furnace inset placed in an Instron hydraulic test machine allowed extension of the filled system at strain rates from 0.002 to 0.4 s⁻¹. The shear experiments show that the low-density polyethylene is a simple shear-thinning melt that provides a good model fluid. The extension of the filled systems shows an increase of the apparent extensional viscosity from that of neat polyethylene. Apparent viscosity rises two to three orders of magnitude for the systems investigated. The micromechanics allowed the conversion of the extensional data from the two filled systems to the shear viscosity of the polymer surrounding the fibers. The calculated polyethylene viscosity compares well with the data from the standard rheometers. The shear cell approach may be applied to highly aligned, high fiber-volume-fraction suspensions when the viscosity of the polymer is known at the scale of the film surrounding each fiber.