Ideal elastic fluids of different viscosity and elasticity levels

Four constant viscosity, highly elastic fluids of different viscosity and elasticity levels are presented. The viscosity ranges from 4 × 10^?3 to 5.0 Pa s and the Maxwell relaxation time varies from 0.09 to 4.5 s. The steady and dynamic shear properties are determined. These fluids comply with the requirements of the simple fluid theory except for theG′ andN ₁/2 data where a slight deviation is observed. The results suggest the possibility of preparing a wide range of constant viscosity elastic fluids with specific values of viscosity and relaxation time by manipulating polymer molecular parameters as well as polymer concentration, solvent viscosity and salt addition. The effects of each of these parameters on the rheological behaviour are examined.     

Scaling relations for elongational flow of polystyrene melts and concentrated solutions of polystyrene in oligomeric styrene

A consistent model of the rheology of polymer melts and concentrated solutions is presented, based on the idea that the pressures exerted by a polymer chain on the walls of an anisotropic confinement are anisotropic (Doi and Edwards. The Theory of Polymer Dynamics, Oxford University Press, 1986). In a tube model with variable tube diameter, chain stretch and tube diameter reduction are related, and at deformation rates larger than the inverse Rouse time τ _R, the chain is stretched and its confining tube becomes increasingly anisotropic. Tube diameter reduction leads to an interchain pressure in the lateral direction of the tube (Marrucci and Ianniruberto. Macromolecules 37:3934-3942, 2004). Chain stretch is balanced by interchain tube pressure in the lateral direction, which is proportional to the third power of stretch, and by a spring force in the longitudinal direction of the tube, which is linear in stretch. Analyzing elongational viscosity data of Huang et al. (Macromolecules 46:5026-5035, 2013a; ACS Macro Letters 2:741-744, 2013b) shows that dilution of polystyrene by oligomeric styrene does not change the relative interchain tube pressure. Based on this extended interchain pressure concept, scaling relations for linear viscoelasticity and elongational viscosity of polystyrene melts and concentrated solutions of polystyrene in oligomeric styrene are presented based exclusively on the relaxation modulus of a reference polymer melt, the volume fraction of polymer in the solution, and the time-molar-mass shift as well as the time-temperature shift caused by the reduction of the glass transition temperature T _g of the polymer in a solution relative to T _g of the melt.     

Compliance of actin filament networks measured by particle-tracking microrheology and diffusing wave spectroscopy

We monitor the time-dependent shear compliance of a solution of semi-flexible polymers, using diffusing wave spectroscopy (DWS) and video-enhanced single-particle-tracking (SPT) microrheology. These two techniques use the small thermally excited motion of probing microspheres to interrogate the local properties of polymer solutions. The solutions consist of networks of actin filaments which are long semi-flexible polymers. We establish a relationship between the mean square displacement (MSD) of microspheres imbedded in the solution and the time-dependent creep compliance of the solution, <Δr ²(t)>=(k _B T/πa)J(t). Here, J(t) is the creep compliance, <Δr ²(t)> is the mean-square displacement, and a is the radius of the microsphere chosen to be larger than the mesh size of the polymer network. DWS allows us to measure mean square displacements with microsecond temporal resolution and Ångström spatial resolution. At short times, the mean square displacement of a 0.96μm diameter sphere in a concentrated actin solution displays sub-diffusion. <Δr ²(t)>∝t ^{, with a characteristic exponent =0.78±0.05, which reflects the finite rigidity of actin. At long times, the MSD reaches a plateau, with a magnitude that decreases with concentration. The creep compliance is shown to be a weak function of polymer concentration and scales as J _p ∝c –1.2±0.3. This exponent is correctly described by a recent model describing the viscoelasticity of semi-flexible polymer solutions. The DWS and video-enhanced SPT measurements of the compliance plateau agree quantitatively with compliance measured independently using classical mechanical rheometry for a viscous oil and for a solution of flexible polymers. This paper extends the use of DWS and single-particle-tracking to probe the local mechanical properties of polymer networks, shows for the first time the proportionality between mean square displacement and local creep compliance, and therefore presents a new, direct way to extract the viscoelastic properties of polymer systems and complex fluids.}     

Laminar Mixed Convection Adjacent to Vertical Continuously Stretching Sheets With Variable Viscosity and Variable Thermal Diffusivity

The paper presents a study of the laminar mixed convection adjacent to vertical continuously stretching sheets, taking into account the effects of variable viscosity and variable thermal diffusivity. The similarity solutions are reported for isothermal sheet moving with a velocity of the form u_w=Bx^0.5 and a continuous linearly stretching sheet with a linear surface temperature distribution. The equations of conservation of mass, momentum and energy, which govern the flow and heat transfer, are solved numerically by using the shooting method. The numerical results obtained for the flow and heat transfer characteristics reveal many interesting behaviors. The numerical results show that, variable viscosity, variable thermal diffusivity, the velocity exponent parameter, the temperature exponent parameter and the buoyancy force parameter have significant influences on the velocity and temperature profiles, shear stress and Nusselt number in two cases air and water.     

Fractal analysis of a circulating flow field with two different velocity laws

The turbulent shear flow around a rotating cylinder in a quiescent flow is a simple case of a rotating turbulent flow field, where centrifugal force works. Two different power-law mean-velocity distributions exist in this flow field. One is U∝1/r and the other is U∝1/r², where r is a distance from the surface of a cylinder. The behavior of chaos and fractal properties for this complex flow field are investigated. The former concerns the dynamic property in fluid flow and the latter is useful to characterize complex flow patterns or the distribution of turbulence quantities. From the instantaneous velocity signal, we defined the iso-velocity set, and its fractal property was investigated both in the U∝1/r and U∝1/r² region. The instantaneous Reynolds stress is found to be a key factor in this fractal property as conceived for the flat plate boundary layer. The intermittency chaos was applied to investigate the turbulent and non-turbulent distribution in the outer region. A simple one-dimensional model could be useful to identify turbulent and non-turbulent distributions even in this complex flow.     

Hydrodynamic diffusivity of spherical particles in polymer solution

In this research experiments were performed to examine the hydrodynamic diffusion of spherical particles in a highly filled suspension. The suspension consisted of nearly monodisperse polymethylmethacrylate spheres in a density matched polymer solution. The polymer solution was prepared by dissolving 0–700 ppm of polyacrylamide in a mixture of ethyleneglycol and glycerine. The polymer solution did not show appreciable shear thinning. The particle loading was varied from 30 to 55%. The hydrodynamic diffusivity was estimated by measuring the time-dependent viscosity when the suspension was subjected to a circular Couette flow with an air bubble trapped under the rotor of the Couette apparatus. The results show that the dimensionless diffusivity (D/γ˙a ²) of particles in polymer solution is not proportional to shear rate (γ˙), as in the case of a Newtonian fluid, but that it decreases with increasing shear rate. The diffusivity also decreases with increasing polymer concentration. It is suggested that the elongational thickening behaviour and the increased lubrication force due to the first normal stress difference may be responsible for the reduction of diffusivity in the polymer solution. Received: 18 January 2000 Accepted: 6 April 2000     

Integral and differential constitutive equations for entangled polymers with simple versions of CCR and force balance on entanglements

The theory of Doi and Edwards for entangled polymers has been recently modified for the case of fast flows to account for convective contributions to molecular dynamics. The flow-induced relative motion between neighboring chains removes constraints and speeds up relaxation. Convective constraint release (CCR) may thus explain why the shear stress is seen to approach a plateau at high shear rates instead of decreasing as predicted by the basic theory. In slow flows, as well as in step strain, another discrepancy between theory and observations can be found in the normal stress ratio in shear Ψ=−N₂/N₁. The theoretical value for Ψ at low deformations is 1/7 whereas measured values for well-entangled systems are systematically larger. We have recently considered the possibility that this discrepancy arises because force balance requirements at the entanglement nodes are ignored in the classical theory. Accordingly, we have proposed a change in the orientational tensor Q. Here, we sum up on these recent findings by proposing single-relaxation-time constitutive equations of the integral or rate type incorporating those concepts in a simple way. Such equations should be suitable for numerical simulation of complex flows. Received: 1 January 2000 Accepted: 8 August 2000     

The weak shear kinetic phase diagram for nematic polymers

We study the shear problem for nematic polymers as modeled by the molecular kinetic theory of Doi (1981), focusing on the anomalous slow flow regime. We provide the kinetic phase diagram of monodomain (MD) attractors and phase transitions vs normalized nematic concentration (N) and weak normalized shear rate (Peclet number, Pe). We then overlay all rheological features typically reported in experiments: alignment properties, normal stress differences and shear stress. These features play a critical role in the synthesis between theory and experiment for nematic polymers (Larson 1999; Doi and Edwards 1986). MD type is routinely used for rheological shear characterization: cf., flow-aligning 5CB (Mather et al. 1996a), tumbling PBT (Srinivasarao and Berry 1991), and 8CB (Mather et al. 1996b), evidence for a wagging regime (Mewis et al. 1997), out-of-plane kayaking modes (Larson and Ottinger 1991), and evidence for chaotic major director dynamics (Bandyopadhyay et al. 2000). MD transitions correlate with sign changes in normal stresses (Larson and Ottinger 1991; Magda et al. 1991; Kiss and Porter 1978, 1980). Furthermore, structure formation in shear devices appears to be correlated with monodomain precursor dynamics (Tan and Berry 2003; Forest et al. 2002a). In this paper we combine seminal kinetic theory results (Kuzuu and Doi 1983, 1984; Larson 1990; Larson and Ottinger 1991; Faraoni et al. 1999; Grosso et al. 2001), symmetry observations (Forest et al. 2002b), and mesoscopic results on the fate of orientational degeneracy in weak shear (Forest and Wang 2003; Forest et al. 2003a), together with our resolved numerical simulations, to provide the kinetic flow-phase diagram of Doi theory in the weak shear regime, 0<Pe<1, for infinitely thin rods. We report the "birth" of key rheological features at the onset of flow: sign changes and local maxima and minima in normal stress differences (N₁ and N₂) associated with MD transitions. These results serve as the basis for continuation of the kinetic phase diagram to Pe>1 ; as the definitive benchmark for any mesoscopic or continuum model; and experimental data can be compared in order to determine accuracy and limitations of the Doi theory in weak shear.     

Rheological modeling of the diffusion process and the interphase of symmetrical bilayers based on PVDF and PMMA with varying molecular weights

The diffusion process in the molten state at a polymer/polymer interface of symmetrical and model bilayers has been investigated using a small-amplitude oscillatory shear measurement. The polymers employed in this study were poly (vinylidene fluoride) (PVDF) and poly (methyl methacrylate) (PMMA) of varying molecular weights and polydispersities. The measurements were conducted in the linear viscoelastic regime (small deformations) so as to decouple the effect of flow from the diffusion. The focus of this paper has been to investigate the effects of healing time, angular frequency (ω), temperature, and molecular weight on the inter-diffusion and the triggered interphase between the neighboring layers. The kinetics of diffusion, based on the evolution of the apparent diffusion coefficient (D _a) versus the healing time, was experimentally obtained. The transition from the non-Fickian to the normal Fickian region for the inter-diffusion at the interface was clearly observed, qualitatively consistent with the reptation model, but it occurred at a critical time greater than the reptation time (τ _rep). In non-Fickian region, effects of frequency and temperature were studied with regard to the ratio of the apparent diffusion coefficient to the self-diffusion coefficient (D _a/D _s). The D _s determined in the Fickian region was found to be consistent with Graessley’s model as well as with the literatures. And the dependence of the D_s on the frequency agreed well with the Doi–Edwards theory, in particular, scaling as $D_{\rm s} \sim \omega^{1/2}$ at ω?>?1/τ _e and $D_{\rm s} \sim \omega^{0}$ at ω?<?1/τ _rep. Our experimental results also confirmed that the dependence of the D _s on the temperature for PMMA and PVDF can be well described by the Arrhenius law. Moreover, blends of PMMAs have been proposed in order to be able to change the $\overline M_\emph{w} $ . The rheological investigations of these corresponding bilayers rendered it possible to monitor the effect of $\overline M_\emph{w} $ on the diffusion process. The obtained results gave $D_{\rm s} \sim \overline M_\emph{w}^{-1}$ , thus corroborating some earlier studies and some experimental results recently reported by Time-Resolved Neutron Reflectivity Measurements. Lastly, the thickness of the interphase and its corresponding viscoelastic properties could be theoretically determined as a function of the healing?time.     

On the relative magnitudes of viscous,elastic and texture stresses in liquid crystalline PBG solutions

The relative contributions of the viscous, elastic, and texture stresses in flows of modestly concentrated liquid crystalline solutions of poly(-benzyl glutamate) or PBG, at low shear rates are assessed by comparing published experimental rheological and light-scattering data to theoretical predictions. The data considered include ratios of Leslie-Ericksen viscosities, the shear viscosity jump at the transition from the isotropic to the liquid-crystalline state, the dependence of the shear viscosity on concentration, and the fraction of slowly relaxing stress after cessation of shearing flow. We quantify the relative contributions of viscous and elastic stresses by estimating from these data a value for the parameter ß^* _{V str} D ^* _r /kT, where _str , is the solvent-polymer friction coefficient and D _r ^* is the rotary diffusivity in the isotropic phase at the concentration where the isotropic phase becomes unstable to liquid crystalline order. The experimental evidence suggests a value \^* _v 0.03, five times lower than the value, 0.15, for dilute solutions. The relative contributions of elastic and texture stresses can be quantified by a parameter in the mesoscopic theory for polydomain nematics; a value of 0.03 gives reasonable agreement with transient shearing experiments, and predicts that the shear viscosity will show an upturn at high polymer concentrations, in agreement with experiments.Dedicated to Prof. Dr. J. Meissner on the occasion of his retirement from the chair of Polymer Physics at the Eidgenössische Technische Hochschule (ETH) Zürich, Switzerland     

Viscoelastic properties of a silicone resin during crosslinking

Viscoelastic properties of a silicone resin crosslinked at various extents were characterised by means of rheology. The influence of temperature on the viscoelastic properties of the material as-delivered and in a state pre-crosslinked approximately to the gel point has been investigated by dynamic-mechanical measurements. While the glass transition temperature is increased by the crosslinking, no changes of the free volume fraction at T _g and its thermal expansion coefficient were observed. Taking the different glass transition temperatures into account, it could be shown that the corresponding WLF-parameters are the same. The molar mass and, hence, the viscosity of the material can be increased by a heat treatment. The dependence of the zero shear-rate viscosity on the weight average molar mass indicates that the existence of entanglements of the polymer molecules is not very probable.     

Determination of the weight-average molecular weight of polyamide-6 on the basis of melt viscosity

A theory of a two-point rheometrical method of determination of the weight-average molecular weightM _w of polyamide-6 is presented. The method is based on the measurement of the instantaneous values of zero-shear-rate viscosity of the degrading polymer melt, and a formula is derived which enables the calculation of the initial value ofM _w (i.e. at zero-residence-time in molten state) of the investigated sample. The experimental verification of the method proves its applicability. The considerations carried out may be regarded as a first step towards developing a theory of an in-line rheometer for a continuous determination ofM _w .     

Carbon nanotube glycol nanofluids: Photo-thermal properties,thermal conductivities and rheological behavior

The efficiency and effectiveness of solar energy capture and storage are to a large extent functions of the heat transfer and storage capacity of the medium used. This paper investigates the potential of using carbon nanotube (CNT)-glycol nanosuspension as such a medium, prepared by freeze drying-ultrasonic dispersing after oxidation treatment with HNO₃. The influences of the mass fraction of CNTs glycol nanofluids and temperatures on photo-thermal properties, thermal conductivities and rheological behavior were investigated. The results show that CNTs with oxidation treatment exhibited good dispersing performance. Strong optical absorption of the CNTs glycol nanofluids was detected in the range of 200–2500 nm. At room temperature, 18% enhancement was found in the photo-thermal conversion efficiency of the 0.5% mass fraction CNTs glycol nanofluids in comparison to the basic fluids, without significant increase in viscosity. At 55 °C, CNTs glycol nanofluids with 4.0% mass fraction exhibited much lower viscosity and 25.4% higher thermal conductivity in comparison to that of pure glycol at room temperature.     

Role of inclusion stiffness and interfacial strength on dynamic matrix crack growth: An experimental study

Experimental simulations of dynamic crack growth past inclusions of two different elastic moduli, stiff (glass) and compliant (polyurethane) relative to the matrix (epoxy), are carried out in a 2D setting. Full-field surface deformations are mapped in the crack–inclusion vicinity optically. The crack growth behavior as a function of inclusion–matrix interfacial strength and the inclusion location relative to the crack is studied under stress-wave loading conditions. An ultra high-speed rotating mirror-type digital camera is used to record random speckle patterns in the crack–inclusion vicinity to quantify in-plane displacement fields. The crack-tip deformation histories from the time of impact until complete fracture are mapped and fracture parameters are extracted. The crack front is arrested by the symmetrically located compliant inclusion for about half the duration needed for complete fracture event. The dynamically propagating crack is attracted and trapped by the weakly bonded inclusion interface for both stiff and compliant symmetrically located inclusion cases, whereas it is deflected away by the strongly bonded stiff inclusion and attracted by strongly bonded compliant inclusion when located eccentrically. The crack is arrested by a strongly bonded compliant inclusion for a significant fraction of the total dynamic event and is longer than the one for the weakly bonded counterpart. The compliant inclusion cases show higher fracture toughness than the stiff inclusion cases. Measured crack-tip mode-mixities correlate well with the observed crack attraction and repulsion mechanisms. Macroscopic examination of fracture surfaces reveals much higher surface roughness and ruggedness after crack–inclusion interaction for compliant inclusion than the stiff one. Implications of these observations on the dynamic fracture behavior of micron size A-glass and polyamide (PA6) particle filled epoxy is demonstrated. Filled-epoxy with 3% V_f of PA6 filler is shown to produce the same dynamic fracture toughness enhancement as the one due to 10% V_f glass.     

Adaptive boundary control of the unforced generalized Korteweg–de Vries–Burgers equation

This paper deals with the adaptive control problem of the unforced generalized Korteweg?Cde Vries?CBurgers (GKdVB) equation when the spatial domain is [0,1]. Three adaptive control laws are designed for the GKdVB equation when either the kinematic viscosity ?? or the dynamic viscosity ?? is unknown, or when both viscosities ?? and ?? are unknowns. Using the Lyapunov theory, the L ²-global exponential stability of the solutions of this equation is shown for each of the proposed control laws. Also, numerical simulations based on the Finite Element method (FEM) are given to illustrate the analytical results.     

Experimental study on the capillary thinning of entangled polymer solutions

The transient elongation behavior of entangled polymer and wormlike micelles (WLM) solutions has been investigated using capillary breakup extensional rheometry (CaBER). The transient force ratio X = 0.713 reveals the existence of an intermediate Newtonian thinning region for polystyrene and WLM solutions prior to the viscoelastic thinning. The exponential decay of X(t) in the first period of thinning defines an elongational relaxation time λ _x which is equal to elongational relaxation time λ _e obtained from exponential diameter decay D(t) indicating that the initial stress decay is controlled by the same molecular relaxation process as the strain hardening observed in the terminal regime of filament thinning. Deviations in true and apparent elongational viscosity are discussed in terms of X(t). A minimum Trouton ratio is observed which decreases exponentially with increasing polymer concentration leveling off at Tr_min = 3 for the solutions exhibiting intermediate Newtonian thinning and Tr_min ≈ 10 otherwise. The relaxation time ratio λ _e/ λ _s, where λ _s is the terminal shear relaxation time, decreases exponentially with increasing polymer concentration and the data for all investigated solutions collapse onto a master curve irrespective of polymer molecular weight or solvent viscosity when plotted versus the reduced concentration c[ η], with [ η] being the intrinsic viscosity. This confirms the strong effect of the nonlinear deformation in CaBER experiments on entangled polymer solutions as suggested earlier. On the other hand, λ _e ≈λ _s is found for all WLM solutions clearly indicating that these nonlinear deformations do not affect the capillary thinning process of these living polymer systems.     

The rheology of polymeric liquid crystals

The molecular theory of Doi has been used as a framework to characterize the rheological behavior of polymeric liquid crystals at the low deformation rates for which it was derived, and an appropriate extension for high deformation rates is presented. The essential physics behind the Doi formulation has, however, been retained in its entirety. The resulting four-parameter equation enables prediction of the shearing behavior at low and high deformation rates, of the stress in extensional flows, of the isotropic-anisotropic phase transition and of the molecular orientation. Extensional data over nearly three decades of elongation rate (10^–2–10¹) and shearing data over six decades of shear rate (10^–2–10⁴) have been correlated using this analysis. Experimental data are presented for both homogeneous and inhomogeneous shearing stress fields. For the latter, a 20-fold range of capillary tube diameters has been employed and no effects of system geometry or the inhomogeneity of the flow-field are observed. Such an independence of the rheological properties from these effects does not occur for low molecular weight liquid crystals and this is, perhaps, the first time this has been reported for polymeric lyotropic liquid crystals; the physical basis for this major difference is discussed briefly. A Semi-empirical constant in eq. (18), N/m² - c rod concentration, rods/m³ - c ^* critical rod concentration at which the isotropic phase becomes unstable, rods/m³ - C interaction potential in the Doi theory defined in eq. (3) - d rod diameter, m - D semi-empirical constant in eq. (19), s^–1 - D _r lumped rotational diffusivity defined in eq. (4), s^–1 - rotational diffusivity of rods in a concentrated (liquid crystalline) system, s^–1 - D _ro rotational diffusivity of a dilute solution of rods, s^–1 - f distribution function defining rod orientation - F tensorial term in the Doi theory defined in eq. (7) (or eq. (19)), s^–1 - G tensorial term in the Doi theory defined in eq. (8) - K _B Boltzmann constant, 1.38 × 10^–23 J/K-molecule - L rod length, m - S scalar order parameter - S tensor order parameter defined in eq. (5) - t time, s - T absolute temperature, K - u unit vector describing the orientation of an individual rod - rate of change ofu due to macroscopic flow, s^–1 - v fluid velocity vector, m/s - v velocity gradient tensor defined in eq. (9), s^–1 - V mean field (aligning) potential defined in eq. (2) - x coordinate direction, m - Kronecker delta (= 0 if = 1 if = ) - _r ratio of viscosity of suspension to that of the solvent at the same shear stress - _s solvent viscosity, Pa · s - ^* viscosity at the critical concentrationc ^*, Pa · s - v ₁, v₂ numerical factors in eqs. (3) and (4), respectively - deviatoric stress tensor, N/m² - volume fraction of rods - ⁰ constant in eq. (16) - ^* volume fraction of rods at the critical concentrationc ^* - average over the distribution functionf(u, t) (= d ²u f(u, t)) - gradient operator - d ²u integral over the surface of the sphere (|u| = 1)     

Rheology of SiO 2 /(acrylic polymer/epoxy) suspensions. III. Uniaxial elongational viscosity

Uniaxial elongational viscosity of SiO₂/(acrylic polymer/epoxy (AP/EP)) suspensions with various SiO₂ volume fractions (?) in a blend of acrylic polymer and epoxy was investigated at various temperatures (T). The matrix polymer ((AP/EP) blend) contained 70?vol.% of EP. At ?????35?vol.% at T????80°C, where the suspensions were in sol state, strain-hardening behavior was observed. This strain hardening of the suspensions is attributable to the elongational flow properties of (AP/EP) medium. At critical gel state (??=?35?vol.% and T?=?100°C) and in gel state (?????40?vol.%), the elongational viscosity exhibited the strain-softening behavior. These results strongly suggest that the strain softening results from the strain-induced disruption of the network structure of the SiO₂ particles therein.