Viscosity orientational

When processing thermoplastic materials, material properties not only dictate drying and processing conditions, viscosity, orientation, and shrinkage, but also the processing techniques and equipment that can be used. The next section reviews material properties with an emphasis on processing temperatures, particle properties, melt viscosity and elasticity, and orientation, relaxation, crystallization, and shrinkage. 

The list of properties that can (and have been) used to gauge water models is quite long. In addition to those just mentioned, there are many thermodynamic properties such as heat capacity, surface tension, free energy, and temperature (or pressure) where the maximum density of water occurs for a specified pressure (or temperature) and various structures for ice. There are also dynamic properties such as viscosity, orientational decay times, and vibrational density of states that can be determined using simulations. 

The viscosity of a suspension of ellipsoids depends on the orientation of the particle with respect to the flow streamlines. The ellipsoidal particle causes more disruption of the flow when it is perpendicular to the streamlines than when it is aligned with them the viscosity in the former case is greater than in the latter. For small particles the randomizing effect of Brownian motion is assumed to override any tendency to assume a preferred orientation in the flow. 

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). 

EOY speeds are the most recent development in PET spinning (78). Properties are similar to HOY and appear to be limited by the differential cooling rate from filament surface to filament core. This leads to radial distribution of viscosity, stress, and, consequentiy, molecular orientation (75). Eiber tensde strength is limited. Nevertheless, speeds up to 7000 m /min are commercial and forecasts are for speeds up to 9000 m /min by the year 2000 (79). Speeds to 9000 m/min have been studied (68,80,81). 

C. Characteristically, these nematic melts show the persistence of orientational order under the influence of elongational flow fields which result in low melt viscosities under typical fiber formation conditions even at high molecular weights. 

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. 

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. 

Other Factors Affecting the Viscosity of Dispersions. Factors other than concentration affect the viscosity of dispersions. A dispersion of nonspherical particles tends to be more viscous than predicted if the Brownian motion is great enough to maintain a random orientation of the particles. However, at low temperatures or high solvent viscosities, the Brownian motion is small and the particle alignment in flow (streamlining) results in unexpectedly lower viscosities. This is a form of shear thinning. 

Phenolics. PVP readily complexes phenolics of all types to some degree, the actual extent depending on stmctural features such as number and orientation of hydroxyls and electron density of the associated aromatic system. A model has been proposed (102). Complexation with phenoHcs can result in reduced PVP viscosity and even polymer-complex precipitation (103). 

The physical picture in concentrated electrolytes is more apdy described by the theory of ionic association (18,19). It was pointed out that as the solutions become more concentrated, the opportunity to form ion pairs held by electrostatic attraction increases (18). This tendency increases for ions with smaller ionic radius and in the lower dielectric constant solvents used for lithium batteries. A significant amount of ion-pairing and triple-ion formation exists in the high concentration electrolytes used in batteries. The ions are solvated, causing solvent molecules to be highly oriented and polarized. In concentrated solutions the ions are close together and the attraction between them increases ion-pairing of the electrolyte. Solvation can tie up a considerable amount of solvent and increase the viscosity of concentrated solutions. 

It is difficult for dye solutions in water to penetrate synthetic fibers such as polyester, cellulose triacetate, polyamides, and polyacryUcs which are somewhat hydrophobic. The rate of water imbibition differs with each fiber as shown in Table 1 as compared to viscose (see Fibers, regenerated CELLULOSics), which imbibes water at the rate of 100% (1). The low imbibition rate is attributed to the high T obtained when the polymeric fibers are drawn. During this drawing operation the polymer chains become highly oriented and tightly packed, forming a stmcture practically free of voids. 

The liquid crystal polymers consist of rod-like molecules which, during shear, tend to orient in the direction of shear. Because of the molecular order the molecules flow past each other with comparative ease and the melts have a low viscosity. When the melt is cooled the molecules retain their orientation, giving self-reinforcing materials that are extremely strong in the direction of orientation. 

The dielectric constant of unsymmetrical molecules containing dipoles (polar molecules) will be dependent on the internal viscosity of the dielectric. If very hard frozen ethyl alcohol is used as the dielectric the dielectric constant is approximately 3 at the melting point, when the molecules are free to orient themselves, the dielectric constant is about 55. Further heating reduces the ratio by increasing the energy of molecular motions which tend to disorient the molecules but at room temperature the dielectric constant is still as high as 35. 

At extremely high shear rates, however, the degree of orientation reaches a maximum so that a further decrease in effective viscosity cannot occur—the polymer in this range again becomes Newtonian. 

In Chapter 3 it was pointed out that certain rod-like polymers showed many of the attributes of liquid crystals in the melt. In particular, these molecules were oriented in shear to such an extent that interchain entanglement was small and the melts had a low viscosity. On cooling of the melt these rod-like molecules remained oriented, effectively self-reinforcing the polymer in the direction of flow. The essential differences in the properties of liquid crystal polymers... 

Since the system is processed as thermoplastics are processed, its reprocessability was studied under repeated cycles of extrusion in the MPT. Results of reprocessability studies are shown in Table 5. It is evident that after the first cycle viscosity increased slightly, which may be due to the orientation effect. In the subsequent cycles viscosity remained almost constant. Therefore, it is concluded that the zinc stearate plasticized zinc salt of m-EPDM is melt processable just as thermoplastics. 

Miscibility or compatibility provided by the compatibilizer or TLCP itself can affect the dimensional stability of in situ composites. The feature of ultra-high modulus and low viscosity melt of a nematic liquid crystalline polymer is suitable to induce greater dimensional stability in the composites. For drawn amorphous polymers, if the formed articles are exposed to sufficiently high temperatures, the extended chains are retracted by the entropic driving force of the stretched backbone, similar to the contraction of the stretched rubber network [61,62]. The presence of filler in the extruded articles significantly reduces the total extent of recoil. This can be attributed to the orientation of the fibers in the direction of drawing, which may act as a constraint for a certain amount of polymeric material surrounding them. 

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