Viscosity, anisotropic

Several studies of photochemical transformations of solutes have sought to exploit the unusually high viscosities, anisotropic cybotactic regions, and helical macrostructures that cholesteric phases provide. Only in selected cases have the... 

Originally, the basic idea was realized without an FC switch by a continuous or one-tum rotation of the sample perpendicular to the external magnetic field direction, in order to induce a flow but such a mechanical rotation is, similar to a mechanical FC switch, much too slow to establish reproducible states of motions in common, low-viscosity anisotropic liquids such measurements were therefore restricted to high-viscosity liquid crystalline polymers. Fast electronic FC eliminates these restrictions, but to date the new tedmique has only been used with proton spin signals owing to instrumental limitations. ... 

A particularly interesting test of the above rule of thumb would be blends containing the HIQ polymer described in Section 5.4.2 in which the unusual positive thermal coefficient of viscosity was attributed to the coexistence of isotropic and anisotropic domains of the coploymer, as determined by the distribution of copolymer ratios and therefore local chain stiffness. As temperature increased, the fraction of the high viscosity isotropic phase increases at the expense of the low-viscosity anisotropic phase. This polymer by itself as the LCP component would open a degree of freedom in varying the viscosity ratio. Furthermore, blending this HIQ LCP with more conventional LCPs with which it is misdble would expand the window of control of the LCP component. 

In packed beds of particles possessing small pores, dilute aqueous solutions of hydroly2ed polyacrylamide will sometimes exhibit dilatant behavior iastead of the usual shear thinning behavior seen ia simple shear or Couette flow. In elongational flow, such as flow through porous sandstone, flow resistance can iacrease with flow rate due to iacreases ia elongational viscosity and normal stress differences. The iacrease ia normal stress differences with shear rate is typical of isotropic polymer solutions. Normal stress differences of anisotropic polymers, such as xanthan ia water, are shear rate iadependent (25,26). 

Molecules of nematic Hquid crystals also are aligned in flow fields which results in a viscosity that is lower than that of the isotropic Hquid the rod-shaped molecules easily stream past one another when oriented. Flow may be impeded if an electric or magnetic field is appHed to counter the flow orientation the viscosity then becomes an anisotropic property. 

The polyamides are soluble in high strength sulfuric acid or in mixtures of hexamethylphosphoramide, /V, /V- dim ethyl acetam i de and LiCl. In the latter, compHcated relationships exist between solvent composition and the temperature at which the Hquid crystal phase forms. The polyamide solutions show an abmpt decrease in viscosity which is characteristic of mesophase formation when a critical volume fraction of polymer ( ) is exceeded. The viscosity may decrease, however, in the Hquid crystal phase if the molecular ordering allows the rod-shaped entities to gHde past one another more easily despite the higher concentration. The Hquid crystal phase is optically anisotropic and the texture is nematic. The nematic texture can be transformed to a chiral nematic texture by adding chiral species as a dopant or incorporating a chiral unit in the main chain as a copolymer (30). 

Because of the rotation of the N—N bond, X-500 is considerably more flexible than the polyamides discussed above. A higher polymer volume fraction is required for an anisotropic phase to appear. In solution, the X-500 polymer is not anisotropic at rest but becomes so when sheared. The characteristic viscosity anomaly which occurs at the onset of Hquid crystal formation appears only at higher shear rates for X-500. The critical volume fraction ( ) shifts to lower polymer concentrations under conditions of greater shear (32). The mechanical orientation that is necessary for Hquid crystal formation must occur during the spinning process which enhances the alignment of the macromolecules. 

More advanced models, for example the algebraic stress model (ASM) and the Reynolds stress model (RSM), are not based on the eddy-viscosity concept and can thus account for anisotropic turbulence thereby giving still better predictions of flows. In addition to the transport equations, however, the algebraic equations for the Reynolds stress tensor also have to be solved. These models are therefore computationally far more complex than simple closure models (Kuipers and van Swaaij, 1997). 

Quite specific effects in the flow of dispersions of long fibers are connected with particles orientation in the flow. Indeed, the state of fibers during the flow changes greatly as compared the initial state, so that the material in a steady-state flow is an anisotropic medium. Therefore the viscosity of such a suspension may become independent of a fiber s length [30], The most strong effects caused by a deformation of anisotropic particles should be expected in transient flows, in particular if the particles themselves are flexible and deformed in the flow. 

This is obvious for the simplest case of nondeformable anisotropic particles. Even if such particles do not change the form, i.e. they are rigid, a new in principle effect in comparison to spherical particles, is their turn upon the flow of dispersion. For suspensions of anisodiametrical particles we can introduce a new characteristic time parameter Dr-1, equal to an inverse value of the coefficient of rotational diffusion and, correspondingly, a dimensionless parameter C = yDr 1. The value of Dr is expressed via the ratio of semiaxes of ellipsoid to the viscosity of a dispersion medium. 

Continuous transition of state is possible only between isotropic states it may thus occur between amorphous glass (i.e., supercooled liquid of great viscosity) and liquid ( sealing-wax type of fusion ), or between liquid and vapour, but probably never between anisotropic forms, or between these and isotropic states. This conclusion, derived from purely thermodynamic considerations, is also supported by molecular theory. 

A typical liquid-crystal molecule, such as p-azoxyanisole, is long and rodlike (14). Their rodlike shape enables the molecules to stack together like dry, uncooked spaghetti they lie parallel to one another but are free to slide past one another along their long axes. Liquid crystals are anisotropic because of this ordering. Anisotropic materials have properties that depend on the direction of measurement. The viscosity of liquid crystals is least in the direction parallel to the long... 

Benzene is an isotropic solvent its viscosity is the same in every direction. However, a liquid crystal solvent is an anisotropic solvent its viscosity is smaller in the direction parallel to the long axis of the molecule than the perpendicular direction. Methylhenzene is a small, spherical molecule, so its interactions with either solvent are similar in all directions. 

The coordinates (x, y, z) define the (velocity, gradient, vorticity) axes, respectively. For non-Newtonian viscoelastic liquids, such flow results not only in shear stress, but in anisotropic normal stresses, describable by the first and second normal stress differences (oxx-Oyy) and (o - ozz). The shear-rate dependent viscosity and normal stress coefficients are then [1]... 

Figure 4.9 illustrates time-gated imaging of rotational correlation time. Briefly, excitation by linearly polarized radiation will excite fluorophores with dipole components parallel to the excitation polarization axis and so the fluorescence emission will be anisotropically polarized immediately after excitation, with more emission polarized parallel than perpendicular to the polarization axis (r0). Subsequently, however, collisions with solvent molecules will tend to randomize the fluorophore orientations and the emission anistropy will decrease with time (r(t)). The characteristic timescale over which the fluorescence anisotropy decreases can be described (in the simplest case of a spherical molecule) by an exponential decay with a time constant, 6, which is the rotational correlation time and is approximately proportional to the local solvent viscosity and to the size of the fluorophore. Provided that... 

Another rotational diffusion model known as the anisotropic viscosity model156,157 is very similar to the above model, and its main feature is to diagonalize the rotational diffusion tensor in the L frame defined by the director. A similar (but not the same) expression as Eq. (71) is J R(r)co)... 

If one follows the solution viscosity in concentrated sulfuric acid with increasing polymer concentration, then one observes first a rise, afterwards, however, an abrupt decrease (about 5 to 15%, depending on the type of polymers and the experimental conditions). This transition is identical with the transformation of an optical isotropic to an optical anisotropic liquid crystalline solution with nematic behavior. Such solutions in the state of rest are weakly clouded and become opalescent when they are stirred they show birefringence, i.e., they depolarize linear polarized light. The two phases, formed at the critical concentration, can be separated by centrifugation to an isotropic and an anisotropic phase. A high amount of anisotropic phase is desirable for the fiber properties. This can be obtained by variation of the molecular weight, the solvent, the temperature, and the polymer concentration. 

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