SAXS observation of RCM1 under cyclical shear

A cylinder forming poly(styrene-b-butadiene-b-styrene) triblock copolymer melt is cyclically processed through a capillary at a high shear rate in the Cambridge Multipass Rheometer (MPR). In situ X-ray diffraction experiments enable observation of the effect of the shear on the block copolymer (BCP) nanophase orientation, both during and after processing. Temporal resolution of the X-ray exposures is increased, whilst retaining intensity, by exploiting the cyclical nature of the shear and the material's response to it; short exposures from many cycles, individually having few counts, are added together to produce well resolved X-ray patterns. Orientation of the cylinders reduces during processing, then increases during pauses between processing. The loss of orientation is attributed to the high shear rate deforming the melt faster than the structure can respond, whilst it is believed that melt relaxation, linked to the compressibility of the material, produces much lower shear rates after mechanical processing has ceased, which induces strong orientation of the nanostructure.

Structure, rheology and shear alignment of Pluronic block copolymer mixtures

The structure and flow behaviour of binary mixtures of Pluronic block copolymers P85 and P123 is investigated by small-angle scattering, rheometry and mobility tests. Micelle dimensions are probed by dynamic light scattering. The micelle hydrodynamic radius for the 50/50 mixture is larger than that for either P85 or P123 alone, Clue to the formation of mixed micelles with a higher association number. The phase diagram for 50/50 mixtures contains regions Of Cubic and hexagonal phases similar to those for the parent homopolymers, however the region of stability of the cubic phase is enhanced at low temperature and concentrations above 40 wt%. This is ascribed to favourable packing of the mixed micelles containing core blocks with two different chain lengths, but similar corona chain lengths. The shear flow alignment of face-centred cubic and hexagonal phases is probed by in situ small-angle X-ray or neutron scattering with simultaneous rheology. The hexagonal phase can be aligned using steady shear in a Couette geometry, however the high modulus Cubic phase cannot be aligned well in this way. This requires the application of oscillatory shear or compression. (C) 2008 Elsevier Inc. All rights reserved.

Velocity profiles and frictional pressure drop for shear thinning materials in lid-driven cavities with fully developed axial flow

A finite element numerical study has been carried out on the isothermal flow of power law fluids in lid-driven cavities with axial throughflow. The effects of the tangential flow Reynolds number (Re-U), axial flow Reynolds number (Re-W), cavity aspect ratio and shear thinning property of the fluids on tangential and axial velocity distributions and the frictional pressure drop are studied. Where comparison is possible, very good agreement is found between current numerical results and published asymptotic and numerical results. For shear thinning materials in long thin cavities in the tangential flow dominated flow regime, the numerical results show that the frictional pressure drop lies between two extreme conditions, namely the results for duct flow and analytical results from lubrication theory. For shear thinning materials in a lid-driven cavity, the interaction between the tangential flow and axial flow is very complex because the flow is dependent on the flow Reynolds numbers and the ratio of the average axial velocity and the lid velocity. For both Newtonian and shear thinning fluids, the axial velocity peak is shifted and the frictional pressure drop is increased with increasing tangential flow Reynolds number. The results are highly relevant to industrial devices such as screw extruders and scraped surface heat exchangers. (c) 2006 Elsevier Ltd. All rights reserved.

Dynamics of shear-induced orientation transitions in block copolymers

This review discusses liquid crystal phase formation by biopolymers in solution. Lyotropic mesophases have been observed for several classes of biopolymer including DNA, peptides, polymer/peptide conjugates, glycopolymers and proteoglycans. Nematic or chiral nematic (cholesteric) phases are the most commonly observed mesophases, in which the rod-like fibrils have only orientational order. Hexagonal columnar phases are observed for several systems (DNA, PBLG, polymer/peptide hybrids) at higher concentration. Lamellar (smectic) phases are reported less often, although there are examples such as the layer arrangement of amylopectin side chains in starch. Possible explanations for the observed structures are discussed. The biological role of liquid crystal phases for several of these systems is outlined. Commonly, they may serve as a template to align fibrils for defined structural roles when the biopolymer is extruded and dried, for instance in the production of silk by spiders or silkworms, or of chitin in arthropod shells. In other cases, liquid crystal phase formation may occur in vivo simply as a consequence of high concentration, for instance the high packing density of DNA within cell nuclei.

Dynamic shear modulus of isotropic elastomers

We have investigated the dynamic mechanical behavior of two cross-linked polymer networks with very different topologies: one made of backbones randomly linked along their length; the other with fixed-length strands uniformly cross-linked at their ends. The samples were analyzed using oscillatory shear, at very small strains corresponding to the linear regime. This was carried out at a range of frequencies, and at temperatures ranging from the glass plateau, through the glass transition, and well into the rubbery region. Through the glass transition, the data obeyed the time-temperature superposition principle, and could be analyzed using WLF treatment. At higher temperatures, in the rubbery region, the storage modulus was found to deviate from this, taking a value that is independent of frequency. This value increased linearly with temperature, as expected for the entropic rubber elasticity, but with a substantial negative offset inconsistent with straightforward enthalpic effects. Conversely, the loss modulus continued to follow time-temperature superposition, decreasing with increasing temperature, and showing a power-law dependence on frequency.

A highly oriented cubic phase formed by lipids under shear

We demonstrate the formation of a macroscopically oriented inverse bicontinuous cubic (QII) lipid phase from a sponge (L3) phase by controlled hydration during shear flow. The L3 phase was the monoolein/ butanediol/water system; the addition of water reduces the butanediol concentration, inducing the formation of a diamond (QIID) cubic phase, which is oriented by the shear flow. The phenomenon was reproduced in both capillary and Couette geometries, indicating that this represents a robust general route for the production of highly aligned bulkQII samples, with applications in nanomaterial templating and protein research.

Orientational behaviour of thermotropic and lyotropic liquid crystal polymer systems under shear flow

A comparison is made of the development of global orientation during shearing of lyotropic solutions of hydroxypropylcellulose with that observed for the thermotropic phase of hydroxypropylcellulose. At shear rates the behaviour of the two systems is similar, both during steady-state shear, and in terms of relaxation following cessation of shear flow. At low shear rates, the levels of orientation observed for the thermotropic system are substantially greater than observed for the lyotropic solutions. The relationship of these differences to variations in molecular parameters, viscous stress and to director tumbling is discussed.

A novel X-ray rheometer for in situ studies of polymer melts and solutions during shear flow

A novel X-ray rheometer based on a parallel plate geometry is described. This system allows time-resolved X-ray scattering intensity data to be obtained from polymeric samples subjected to shear flow. The range of quantitative structural parameters, such as molecular orientation and inter chain correlations, which can be obtained from the data is highlighted. Examples of the utility of X-ray scattering in examining optically opaque samples and the extraction of 〈P2〉 and 〈P4〉 orientation parameters are given using anisotropic hydroxypropylcellulose solutions as the sample.

WAXS studies of global molecular orientation induced in nematic liquid crystals by simple shear flow

Global molecular orientation function coefficients for the nematic liquid crystal 4-cyano 4'-nn -pentylbiphenyl (5CB) in shear flow are presented, being extracted from 2-dimensional Wide-Angle X-ray Scattering data. A linear increase in orientation parameter P2 is observed with a logarithmic increase in shear rate. It is proposed that this arises from an increased number of LC directors aligning to the shear axis. Upon cessation of shear flow, the anisotropy is seen to relax away completely, over a time scale which is inversely proportional to the previously applied shear rate.

Viscous coupling of shear-free turbulence across nearly flat fluid interfaces

The interactions between shear-free turbulence in two regions (denoted as + and − on either side of a nearly flat horizontal interface are shown here to be controlled by several mechanisms, which depend on the magnitudes of the ratios of the densities, ρ+/ρ−, and kinematic viscosities of the fluids, μ+/μ−, and the root mean square (r.m.s.) velocities of the turbulence, u0+/u0−, above and below the interface. This study focuses on gas–liquid interfaces so that ρ+/ρ− ≪ 1 and also on where turbulence is generated either above or below the interface so that u0+/u0− is either very large or very small. It is assumed that vertical buoyancy forces across the interface are much larger than internal forces so that the interface is nearly flat, and coupling between turbulence on either side of the interface is determined by viscous stresses. A formal linearized rapid-distortion analysis with viscous effects is developed by extending the previous study by Hunt & Graham (J. Fluid Mech., vol. 84, 1978, pp. 209–235) of shear-free turbulence near rigid plane boundaries. The physical processes accounted for in our model include both the blocking effect of the interface on normal components of the turbulence and the viscous coupling of the horizontal field across thin interfacial viscous boundary layers. The horizontal divergence in the perturbation velocity field in the viscous layer drives weak inviscid irrotational velocity fluctuations outside the viscous boundary layers in a mechanism analogous to Ekman pumping. The analysis shows the following. (i) The blocking effects are similar to those near rigid boundaries on each side of the interface, but through the action of the thin viscous layers above and below the interface, the horizontal and vertical velocity components differ from those near a rigid surface and are correlated or anti-correlated respectively. (ii) Because of the growth of the viscous layers on either side of the interface, the ratio uI/u0, where uI is the r.m.s. of the interfacial velocity fluctuations and u0 the r.m.s. of the homogeneous turbulence far from the interface, does not vary with time. If the turbulence is driven in the lower layer with ρ+/ρ− ≪ 1 and u0+/u0− ≪ 1, then uI/u0− ~ 1 when Re (=u0−L−/ν−) ≫ 1 and R = (ρ−/ρ+)(v−/v+)1/2 ≫ 1. If the turbulence is driven in the upper layer with ρ+/ρ− ≪ 1 and u0+/u0− ≫ 1, then uI/u0+ ~ 1/(1 + R). (iii) Nonlinear effects become significant over periods greater than Lagrangian time scales. When turbulence is generated in the lower layer, and the Reynolds number is high enough, motions in the upper viscous layer are turbulent. The horizontal vorticity tends to decrease, and the vertical vorticity of the eddies dominates their asymptotic structure. When turbulence is generated in the upper layer, and the Reynolds number is less than about 106–107, the fluctuations in the viscous layer do not become turbulent. Nonlinear processes at the interface increase the ratio uI/u0+ for sheared or shear-free turbulence in the gas above its linear value of uI/u0+ ~ 1/(1 + R) to (ρ+/ρ−)1/2 ~ 1/30 for air–water interfaces. This estimate agrees with the direct numerical simulation results from Lombardi, De Angelis & Bannerjee (Phys. Fluids, vol. 8, no. 6, 1996, pp. 1643–1665). Because the linear viscous–inertial coupling mechanism is still significant, the eddy motions on either side of the interface have a similar horizontal structure, although their vertical structure differs.

The effect of wind shear and curvature on the gravity wave drag produced by a ridge

The analytical model proposed by Teixeira, Miranda, and Valente is modified to calculate the gravity wave drag exerted by a stratified flow over a 2D mountain ridge. The drag is found to be more strongly affected by the vertical variation of the background velocity than for an axisymmetric mountain. In the hydrostatic approximation, the corrections to the drag due to this effect do not depend on the detailed shape of the ridge as long as this is exactly 2D. Besides the drag, all the perturbed quantities of the flow at the surface, including the pressure, may be calculated analytically.

An analytical model of mountain wave drag for wind profiles with shear and curvature

An analytical model is developed to predict the surface drag exerted by internal gravity waves on an isolated axisymmetric mountain over which there is a stratified flow with a velocity profile that varies relatively slowly with height. The model is linear with respect to the perturbations induced by the mountain, and solves the Taylor–Goldstein equation with variable coefficients using a Wentzel–Kramers–Brillouin (WKB) approximation, formally valid for high Richardson numbers, Ri. The WKB solution is extended to a higher order than in previous studies, enabling a rigorous treatment of the effects of shear and curvature of the wind profile on the surface drag. In the hydrostatic approximation, closed formulas for the drag are derived for generic wind profiles, where the relative magnitude of the corrections to the leading-order drag (valid for a constant wind profile) does not depend on the detailed shape of the orography. The drag is found to vary proportionally to Ri21, decreasing as Ri decreases for a wind that varies linearly with height, and increasing as Ri decreases for a wind that rotates with height maintaining its magnitude. In these two cases the surface drag is predicted to be aligned with the surface wind. When one of the wind components varies linearly with height and the other is constant, the surface drag is misaligned with the surface wind, especially for relatively small Ri. All these results are shown to be in fairly good agreement with numerical simulations of mesoscale nonhydrostatic models, for high and even moderate values of Ri.

Dissipation of shear-free turbulence near boundaries

The rapid-distortion model of Hunt & Graham (1978) for the initial distortion of turbulence by a flat boundary is extended to account fully for viscous processes. Two types of boundary are considered: a solid wall and a free surface. The model is shown to be formally valid provided two conditions are satisfied. The first condition is that time is short compared with the decorrelation time of the energy-containing eddies, so that nonlinear processes can be neglected. The second condition is that the viscous layer near the boundary, where tangential motions adjust to the boundary condition, is thin compared with the scales of the smallest eddies. The viscous layer can then be treated using thin-boundary-layer methods. Given these conditions, the distorted turbulence near the boundary is related to the undistorted turbulence, and thence profiles of turbulence dissipation rate near the two types of boundary are calculated and shown to agree extremely well with profiles obtained by Perot & Moin (1993) by direct numerical simulation. The dissipation rates are higher near a solid wall than in the bulk of the flow because the no-slip boundary condition leads to large velocity gradients across the viscous layer. In contrast, the weaker constraint of no stress at a free surface leads to the dissipation rate close to a free surface actually being smaller than in the bulk of the flow. This explains why tangential velocity fluctuations parallel to a free surface are so large. In addition we show that it is the adjustment of the large energy-containing eddies across the viscous layer that controls the dissipation rate, which explains why rapid-distortion theory can give quantitatively accurate values for the dissipation rate. We also find that the dissipation rate obtained from the model evaluated at the time when the model is expected to fail actually yields useful estimates of the dissipation obtained from the direct numerical simulation at times when the nonlinear processes are significant. We conclude that the main role of nonlinear processes is to arrest growth by linear processes of the viscous layer after about one large-eddy turnover time.

Shear banding in molecular dynamics of polymer melts

In order to establish constitutive equations for a viscoelastic fluid uniform shear flow is usually required. However, in the last 10 years S. Q. Wang and co-workers have demonstrated that some entangled polymers do not flow with the uniform shear rate as usually assumed, but instead choose to separate into fast and slow flowing regions. This phenomenon, known as shear banding, causes flow instabilities and in principle invalidates all rheological measurements when it occurs. In this Letter we report the first observation of shear banding in molecular dynamics simulations of entangled polymer melts. We show that our observations are in a very good agreement with the phenomenology developed by Fielding and Olmsted. Our findings provide a simple way of validating the empirical macroscopic phenomenology of shear banding. © 2012 American Physical Society