An evaluation of the Larson-Doi model for liquid crystalline polymers using recoil

The mesoscopic models for the rheological properties of liquid crystalline polymers proposed by Larson and Doi in 1991 and Kawaguchi and Denn in 1999 are based on phenomenological expressions that describe the evolution of the defect density and the contribution of the “texture” to the stress. In the present work, we attempt to assess some of these assumptions by monitoring how the energy stored in the texture of liquid crystalline materials evolves during shear flows. For that purpose, strain recovery is measured as a function of the applied strain for flow reversal and intermittent flow. Solutions of poly-benzylglutamate in m-cresol, hydroxypropylcellulose in water and a nematic surfactant solution are used as model systems. Although the behaviour is described qualitatively by the model, discrepancies between the predictions and the experiments are observed, especially when the shear history includes rest periods. Received: 14 July 1999 /Accepted: 30 August 1999     

Transient rheological behavior of tumbling side-chain liquid crystal polymers and determination of their λ parameters

The transient rheological behavior of several thermotropic nematic side-chain liquid crystal polysiloxanes is investigated. A homopolymer with a low-temperature smectic phase and two random copolymers, one consisting of smectogenic and non-smectogenic mesogens, the other one containing two spacers of different lengths, are studied. All systems are of tumbling type and exhibit oscillations in transient shear stress and first normal stress difference. Only the copolymer with mixed spacers shows a temperature-dependent transition from tumbling to flow-aligning within the nematic phase. The rheological response is slightly different for each polymer. The reactive parameter λ was calculated from the period of the oscillations and compared with rheo-NMR results. For all polymers, λ increases with increasing temperature. The sign of λ, obtained from NMR experiments, is positive for the copolymer with mixed spacers and negative for the other two systems, indicating a prolate shape of the first system and oblate shapes of the other two. Received: 30 April 1999 /Accepted: 2 August 1999     

Theory of interfacial dynamics of nematic polymers

 The interfacial momentum and torque balance equations for deforming interfaces between nematic polymers and isotropic viscous fluids are derived and analyzed with respect to shape selection and interfacial nematic ordering. It is found that the interfacial momentum balance equation for nematic interfaces involves bending forces that act normal to the interface, and that interfacial pressure jumps may exist even for planar surfaces. In addition tangential forces on nematic interfaces arise in the presence of surface gradients of the tensor order parameter. The torque balance equation shows that couple stress jumps are balanced by the surface molecular field. The interfacial balance equations are shown to be coupled such that nematic ordering depends on shape and vice versa. The governing dimensionless numbers for deforming nematic polymer interfaces are identified and the limiting regimes are discussed in reference to related experimental data. It is found that the ratio of Frank elasticity to surface anchoring controls whether the surface tensor order parameter deviates from its preferred equilibrium value. Whether the shape is affected, depends on the relative magnitudes of the isotropic surface tension, Frank bulk elasticity, and anchoring energy, and capillary number. Received: 16 April 1999/Accepted: 19 August 1999     

Non-symmetric viscoelasticity of anisotropic polymer liquids

The liquid crystalline (LC) polymers are considered as anisotropic viscoelastic liquids with nonsymmetric stresses. A simple constitutive equation for nematic polymers describing the coupled relaxation of symmetric and antisymmetric parts of the stress tensor is formulated. For illustration of non-symmetric anisotropic viscoelasticity, the simplest viscometric flows of polymeric nematics in the magnetic field are considered. The frequency and shear rate dependencies of extended set of Miesowicz viscosities are predicted. Received: 23 March 1999/Accepted: 13 December 1999     

Electrorheology of nematic liquid crystals in uniform shear flow

A hydrodynamic model for the electrorheological effect in a polymeric nematic confined in a rectangular cell is studied. The competition between a constant electric and a uniform shear flow is explicitly considered. For the final stationary state where the induced reorientation of the director has already occurred, we show that the averaged viscosity is enhanced. For this same state several rheological properties such as the first normal stress difference and the force between the cell plates are also analytically calculated as a function of position, the applied field, and Reynolds' number. These results are compared with those obtained previously for a pressure driven flow. The scope and limitations of the model and methods employed are discussed. Received: 23 November 1999/Accepted: 13 June 2000     

Dynamics of shear aligning of nematic liquid crystal monodomains

The equations of linear and angular momentum for nematic liquid crystals have been described with Ericksen's transversely isotropic fluid [TIF] model and solved for start-up of shear flow at constant rate and varying initial alignment conditions. An analytical solution for the rotation provides predictions of the nematic director which closely agree with experimental results of Boudreau et al. (1999), supporting the validity of Ericksen's TIF model. The solution is limited to flows where the effects of director gradients are negligible. Received: 13 September 1999/Accepted: 24 January 2000     

Dependence of the dynamic moduli of heterogeneous nematic polymers on planar anchoring relative to flow direction

We analyze the dynamic moduli of nematic polymers in a parallel plate oscillatory shear experiment from a Doi?CMarrucci?CGreco orientation tensor formulation, paying special attention to the inherent connection between rheological properties and wall anchoring conditions. We assume standard experimental procedures in which the plates have been rubbed to achieve strong nematic anchoring parallel to the rubbing direction. We derive the heterogeneous, harmonic response of the nematic liquid in the weak oscillatory shear regime of linear viscoelasticity. The response function is parameterized by the orientational anchoring condition and, in particular, by the angle of rotation between the rubbing direction and the flow direction. From this analysis, we read off the frequency-dependent storage and loss moduli. The dominant effect is in the storage modulus where for high frequencies rubbing aligned with the vorticity axis can cause G ^?? to be two to three orders of magnitude larger than rubbing in the flow direction. This anchoring dependency shows the significance of the order parameter fluctuations of tensor-based models: the Leslie?CEricksen theory predicts zero storage modulus for vorticity-aligned anchoring. For low frequencies, this effect is reversed with flow-aligned anchoring maximizing G ^?? in a manner similar to the Leslie?CEricksen theory although we predict a nonzero modulus for vorticity-aligned anchoring.     

Influence of drag-reducing polymers on turbulence: effects of Reynolds number, concentration and mixing

 Measurements of turbulence properties of solutions of polymers have been made over a large range of drag-reduction, in a fully-developed channel flow. At flows close to maximum drag-reduction the Reynolds stresses were approximately zero over the whole cross section of the channel. Added mean polymer stresses were observed in the viscous wall region for small drag-reduction and over the whole cross-section for large drag-reduction. Even though the Reynolds stresses are zero, the velocity profile is not parabolic because of the presence of these mean stresses. We interpret the results by arguing that the interaction of turbulence with the polymers introduces mean and fluctuating polymer stresses which can create turbulence. The observation that the turbulence modification depends on the manner by which the polymers are introduced into the flow supports the notion that the polymers need to form aggregates in order to be effective. Received: 29 September 1998 / Accepted: 10 February 1999     

A model of traps for yield in amorphous glassy polymers

Summary  Constitutive equations are derived for the viscoelastic and viscoplastic behavior of amorphous glassy polymers at isothermal loading with small strains. The model is based on the trapping concept: a disordered medium is treated as an ensemble of plastic flow units (with the characteristic size of micrometers), which, in turn, consist of a number of cooperative rearranging regions (with the characteristic length of nanometers). The viscoelastic response is described by rearrangement of relaxing regions, whereas the viscoplastic behavior is modeled as irreversible deformation of plastic units. Adjustable parameters are found by fitting observations for aromatic polyesters, nylon-66, polycarbonate block copolymers and an epoxy glass. Fair agreement is demonstrated between experimental data and results of numerical simulation. Received 17 November 1999; accepted for publication 23 March 2000     

The effect of a zwitterionic and cationic surfactant in turbulent flows

A zwitterionic and a cationic surfactant were compared concerning their effectiveness in drag reduction. Both reach even lower friction factors than can be determined by the known maximum drag reduction asymptote in polymers. It is shown that both the maximum effectiveness and the range of surfactant activity depend not only on the temperature and concentration of the solution, but also on the length of the direct entering section and on the quality of water. The influence of the particular locality of the flow rate regulation is also notified. Received: 1 December 1999/Accepted: 30 April 2000     

Macroscopic theory of orientation transitions in the extensional flow of side-chain nematic polymers

A macroscopic continuum mechanical model for incompressible side-chain nematic polymers, under isothermal conditions is given. The model is a synthesis of a transient network model and the standard nematorheological model. Simplifications in the model yield constitutive equations that are identical to well known Theological models for polymer melts and for low molar mass nematics. A detailed analysis of four possible composite orientation modes of polymer backbone and mesogenic side groups in uniaxial extensional flow is given. It is shown that the thermal sensitivity of the viscoelastic parameters leads to thermally-induced orientation transitions. The extension rate sensitivity of the competition between elastic and flow orienting effects leads to flow-induced orientation transition. The role of smectic A fluctuations in thermally-induced transitions during uniaxial extensional nematic flow is elucidated. The model is able to predict and explain the experimentally observed orientation modes and thermally-induced orientation transitions of a side-chain nematic polymer subjected to uniaxial extensional flow.     

Flow in micellar cubic crystals

 We investigate and compare the mechanical properties of two micellar cubic crystals. Both are obtained from aqueous triblock-copolymer solutions of similar block structure, (PEO)₇₆(PPO)₂₉(PEO)₇₆ and (PEO)₁₂₇(PPO)₄₈(PEO)₁₂₇, designated Pluronic F68 and F108 respectively. Extensive small angle X-ray scattering experiments under shear and common rheometry provide the following results: (i) the solid phases of the two polymeric solutions are constituted of micelles that are ordered in a bcc (F68) and fcc (F108) structure. The overall appearance of both unsheared samples is polycrystalline; (ii) SAXS showed that both systems undergo a structural reorientation under shear, with the dense planes arranged parallel to the velocity - vorticity plane, thus facilitating flow; (iii) F68 showed a clear transition in the flow curve, associated with a textural change, but the F108 system exhibited a continuous evolution; (iv) the bcc crystal appears to have no measurable yield stress and flows even for low applied stresses. This was in contrast to the fcc sample which showed a clear yield stress, separating creep and flow regimes. Received: 30 November 1999/Accepted: 30 November 1999     

Quantitative NMR velocity imaging of a main-chain liquid crystalline polymer flowing through an abrupt contraction

 The flow of isotropic and liquid crystalline (LC) hydroxypropylcellulose (HPC) aqueous solutions into an abrupt axisymmetric contraction has been quantitatively measured by pulsed-field-gradient NMR techniques. Steady-state axial velocity profiles, acquired upstream of the contraction, reveal a large contraction entry length for the LC solution. This entry flow field exists over an order of magnitude change in flow rate and is attributed to elasticity that is associated with polydomain liquid crystallinity. Pronounced, off-centerline velocity maxima (in an axisymmetric flow field) were present upstream of the contraction, in the entry flow region. Apparently, a more viscous and elastic core of fluid was present along the centerline; this fluid resisted elongational strain more than the fluid closer to the walls. Quantitative velocity profiles were extracted from displacement distributions and corrected for elongational dispersion. The isotropic solution velocity profiles matched those obtained from viscoelastic simulations using an approximate Doi-Edwards model, parameterized with independent rheological data. Received: 29 April 1999/Accepted: 30 August 1999     

Computational rheooptics of liquid crystal polymers

A computational rheooptical model based on the integration of liquid crystal polymer flow equations and two well-known polarized light transmission methods is formulated and applied to the ubiquitous periodic banded textures observed in sheared lyotropic nematic polymers. The selected optical methods are the matrix-type Berreman method and the finite-difference time-domain (FDTD) direct numerical simulation method. The optical response of a single unit cell of the periodic banded texture of sheared lyotropic nematic polymers to polarized light propagation under cross-polars is analyzed and correlated to the shear-induced orientation field previously reported in Han and Rey [W.H. Han, A.D. Rey, Theory and simulation of optical banded textures of nematics polymer during shear flow, Macromolecules 28 (1995) 8401–8405]. The role of orientation gradients on the optical response is elucidated and shown to be source of lack of accuracy of the Berreman matrix method. The findings provide robust guidelines on the applicability and accuracy of matrix and direct numerical simulation optical methods. Computational rheooptics of liquid crystal polymers based on the FDTD method is an additional tool to understand flow-induced texture formation when used in the direct forward mode, and in quantitative assessments of rheological material properties when used in backward mode.     

Wavelet multi-scale analysis of the circular cylinder wake under synthetic jets control

The wavelet method is used to study the multi-scale vortical structures of the flow around a circular cylinder without and with synthetic jet control at Re = 950. The velocity field is decomposed into 9 wavelet components, including one approximation component and 8 detail components. The first component shows the flow characteristics at low frequency. The dominant components represent large-scale vortical structures in the flow and they show similar distributions for the same wake pattern. Other detail components reflect the characteristics of relatively small-scale structures. The individual vortex dynamics underlying the complex flow can be extracted and thus reconstructed by the approximation and dominant components. Thus, we show an effective approach to reveal the flow physics from the complex flow.     

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.     

Measurement of velocity and velocity derivatives based on pattern tracking in 3D LIF images

Pattern tracking in consecutive 3D LIF images based on least squares matching (LSM) of grey levels has been developed recently for velocity and velocity gradient measurements. The shortcomings of this method are clearly shown. The present article presents an improvement on this method by introducing a local multi-patch (LMP) technique through the LSM approach. The method is validated using the flow field of a turbulent channel flow obtained by direct numerical simulation (DNS) and a synthetic image with grey-level patterns. The results show that LMP matching allows the determination of the velocity and the velocity gradient fields with high accuracy including the second derivatives. Measurements of a round non-buoyant jet are presented which demonstrate the good performance of the method when applied under laboratory conditions. This method can also be applied on two-dimensional images provided that the flow is strictly two-dimensional. Received: 7 July 1999/Accepted: 13 November 1999     

Ordering effects in shear flows of discotic polymers

The tensorial mechanical model of Farhoudi and Rey (1993) for uniaxial, rodlike, spatially homogeneous and monodomain nematics is modified to describe the microstructural response of discotic nematic network polymers in rectilinear simple shear flow. The particular topological features of the discotic phase are taken into account by a proper modification of the phenomenological parameters. Asymptotic and numerical solutions of the microstructural balance equations indicate the appearance of tumbling, oscillating, and stationary flow regimes as the strength of shear increases, as is the case for rod-like nematic polymers (Marrucci, 1991). The tumbling-oscillating transition is characterized by a diverging tumbling function , while the oscillating-stationary transition is characterized by a single steady value smaller than —1. The stable steady states of the stationary regime are shown to belong to the family of unstable isotropic solutions that exist at small shear rates, and are characterized by a director angle close to, but less than +90° to the flow direction.     

Brownian dynamics simulation of rodlike polymers under shear flow

The highly nonlinear behaviors of rodlike polymers in nematic phase under shear flow are studied with Brownian dynamics simulation. The LebwohlLasher nematogen model is taken as the prototype of the simulation and the mean-field approximation is avoided. By considering the nearest-neighbor intermolecular interaction, the spatial orientational correlation is introduced and therefore the spatial inhomogeneity such as the multiple-domain effect can automatically be incorporated. The transient order parameters, birefringence axes, shear stresses and first normal stress differences are calculated. The important finding of this work is that the director wagging and damped oscillation share the same molecular origin as director tumbling. The only difference is that the system is split into micro-domains which tumble with different phase angles in the wagging and damped oscillation regimes. The tumbling of the director of the whole system is suppressed due to the spatial inhomogeneity of director fields and then the damped oscillation of macroscopic stresses becomes predominant. The negative first normal stress difference exists at moderate shear rates, where both elasticity and viscosity play important role. Our simulation results including some dimensionless scaling parameters find good agreement with experimental observations in literature.