Shear rate crystallization

Flow processes iaside the spinneret are governed by shear viscosity and shear rate. PET is a non-Newtonian elastic fluid. Spinning filament tension and molecular orientation depend on polymer temperature and viscosity, spinneret capillary diameter and length, spin speed, rate of filament cooling, inertia, and air drag (69,70). These variables combine to attenuate the fiber and orient and sometimes crystallize the molecular chains (71). 

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. 

The dynamics of reactor flow is also important for its effect on the crystal agglomeration, since the intensity of turbulent shear dominates the orthoki-netic mechanism for both processes of aggregation and disruption. The mean shear rate is estimated as (see Harnby etai, 1992)... 

Figure 8.17 EJfect of estimated shear rate on the size of crystal agglomerates Jones etal., 1992a)...

As a consequence of the high shear rate to which the rubber is subjected at the nip of the mill crystallization occurs at temperatures of up to 80 °C in compounds based on SE-BR and U-BR, and this phenomenon is responsible for the improvement in the processing behaviour. 

For a nematic polymer in a transition region from LC to isotropic state, maximal viscosity is observed at low shear rates j. For a smectic polymer in the same temperature range only a break in the curve is observed on a lgq — 1/T plot. This difference is apparently determined by the same reasons that control the difference in rheological behaviour of low-molecular nematics and smectics 126). A polymeric character of liquid crystals is revealed in higher values of the activation energy (Ef) of viscous flow in a mesophase, e.g., Ef for a smectic polymer is 103 kJ/mole, for a nematic polymer3 80-140kJ/mole. 

Smectic A liquid crystals are known to be rather sensitive to dilatations of the layers. As shown in [34, 35], a relative dilatation of less than 10-4 parallel to the layer normal suffices to cause an undulation instability of the smectic layers. Above this very small, but finite, critical dilatation the liquid crystal develops undulations of the layers to reduce the strain locally. Later on Oswald and Ben-Abraham considered dilated smectic A under shear [36], When a shear flow is applied (with a parallel orientation of the layers), the onset for undulations is unchanged only if the wave vector of the undulations points in the vorticity direction (a similar situation was later considered in [37]). Whenever this wave vector has a component in the flow direction, the onset of the undulation instability is increased by a portion proportional to the applied shear rate. 

As discussed in section 7.1.6.4, semidilute solutions of rodlike polymers can be expected to follow the stress-optical rule as long as the concentration is sufficiently below the onset of the isotropic to nematic transition. Certainly, once such a system becomes nematic and anisotropic, the stress-optical rule cannot be expected to apply. This problem was studied in detail using an instrument capable of combined stress and birefringence measurements by Mead and Larson [109] on solutions of poly(y benzyl L-glutamate) in m-cresol. A pretransitional increase in the stress-optical coefficient was observed as the concentration approached the transition to a nematic state, in agreement of calculations based on the Doi model of polymer liquid crystals [63]. In addition to a dependence on concentration, the stress-optical coefficient was also seen to be dependent on shear rate, and on time for transient shear flows. 

R. G. Larson and D. W. Mead, Time and shear-rate scaling laws for liquid crystal polymers, J. Rheol., 33,1251 (1989). 

Many processes involve criteria other than solids suspension, for example, crystallization, precipitation, and many types of leaching and chemical reactions. In crystallization, the shear rate around the impeller and other mixing variables can affect the rate of nucleation, and can affect the ultimate particle size. In some cases, the shear rate can be such that it can break down forces within the solid particle and can affect the ultimate particle size and shape. There are some very fragile precipitate crystals that are very much affected by the mixer variables. 

Another peculiar property of LCPs is shown in Fig. 15.47, where the transient behaviour of the shear stress after start up of steady shear flow is shown for Vectra A900 at 290 °C at two shear rates. We will come back to this behaviour in Chap. 16 for lyotropic systems where this behaviour is quite common and in contradistinction to the transient behaviour of conventional polymers, as presented in Fig. 15.9. This damped oscillatory behaviour is also found for simple rheological models as the Jeffreys model (Te Nijenhuis 2005) and according to Burghardt and Fuller, it is explicable by the classic Leslie-Ericksen theory for the flow of liquid crystals, which tumble, rather than align, in shear flow. Moreover, it is extra complicated due to the interaction between the tumbling of the molecules and the evolving defect density (polynomial structure) of the LCP, which become finer, at start up, or coarser, after cessation of flow. 

The steady state is reached after several oscillations and the time of the minima and maxima may be scaled by qt, where q is the constant shear rate. As already said in Chap. 15, this behaviour is according to Burghardt and Fuller explicable by the classic Leslie-Ericksen theory for the flow of liquid crystals, which tumble, rather than align, in shear flow. Again it is far beyond the scope of this book to go into detail of this theory. 

The next system studied was novel in that the lower phase was a homogeneous lamellar liquid crystal containing a synthetic sulfonate surfactant in equilibrium with an excess oil phase. No previous observations of liquid crystalline flow through porous media have been reported. The initial viscosity of the liquid crystalIjiie phase was a relatively low 10 cp at a shear rate of 4.5 s -. The interfacial tension between liquid crystal and oleic phase was 0.018 dyne/cm (14). 

Polymers with longer side-chains (Ciq and Cjs) exhibit non-Newtonian viscosity at room temperature, and the viscosity decreases with increasing shear rate. Because the side-chain T s for and C s polymers are above room temperature, network formation via intermolecular crystallization of the paraffinic side-chains is believed to be responsible for the unusually high... 

Polymorphism is the ability of a molecule to take more than one crystalline form depending on its arrangement within the crystal lattice. In lipids, differences in hydrocarbon chain packing and variations in the angle of tilt of the hydrocarbon chain packing differentiate polymorphic forms. The crystallization behavior of TAG, including crystallization rate, crystal size, morphology, and total crystallinity, are affected by polymorphism. The molecular structure of the TAG and several external factors like temperature, pressure, rate of crystalhzation, impurities, and shear rate influence polymorphism (5). 

Garbolino et al. (65) studied the effects of shear rate on crystallization of a confectionery coating fat (hydrogenated and fractionated mixture of soybean and cottonseed oils) using ultrasonic sensors. They hypothesized that primary nucleation is less likely to be affected by shear and suggested that crystal nuclei probably form from heterogeneous nucleation sites (dust particles or other suspended insoluble materials and imperfections in the container walls). They also suggested that... 

As for the effects of the shear stress, it was shown by a Synchrotron radiation X-ray diffraction study that transformations from metastable to more stable forms, especially to Form V, were accelerated by high shear stress (110). Figure 25 shows the time variation of relative intensities of X-ray diffraction peaks of CB crystals formed after cooling from 50°C to 18°C at a rate of 3°C/min. In the case of no shear. Form III appeared at first after the temperature reached at 18°C, and then Form IV crystallized at the expense of Form III. On the other hand, applying the shear stress at 1440 s caused accelerated transformation from Form III to Form V, without the occurrence of Form IV. The same result was observed with lower shear rates (19), and the persistence time of Form III was reduced as the shear rate was increased. Mazaanti et al also observed that the orientation of CB crystals are aligned with the shear flow (110). These results indicated that temperature and shear treatments are the tools for tailoring the desired polymorphic structures of fats. 

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