The Polymer Solution

We shall refer to electrolytes which do not affect the charge of the polymer as indifferent electrolytes. In the situation illustrated by reaction (8.B), the HCl and NaOH are clearly not indifferent. We shall also assume that the indifferent electrolytes are 100% ionized in the polymer solution. 

We consider this system in an osmotic pressure experiment based on a membrane which is permeable to all components except the polymeric ion P that is, solvent molecules, M" , and X can pass through the membrane freely to establish the osmotic equilibrium, and only the polymer is restrained. It does not matter whether pure solvent or a salt solution is introduced across the membrane from the polymer solution or whether the latter initially contains salt or not. At equilibrium both sides of the osmometer contain solvent, M , and X in such proportions as to satisfy the constaints imposed by electroneutrality and equilibrium conditions. 

Solution Filtration. The polymer solution, free of unacetylated ceUulose, rigid particle contaminants, and dirt, must pass through spinnerets with holes of 30—80 ]lni diameter. Multistage filtration, usuaUy through plate-and-frame filter presses with fabric and paper filter media, removes the extraneous matter before extmsion. Undesirable gelatinous particles, such as the hemiceUulose acetates from ceUulose impurities, tend to be sheared into smaller particles rather than removed. The solution is also aUowed to degas in hoi ding tanks after each state of filtration. 

In the case of solvent spinning, ie, secondary acetate, polyacrylonitrile, and poly(vinyl chloride), the FWA is added to the polymer solution. An exception is gel-whitening of polyacrylonitrile, where the wet tow is treated after spinning in a washbath containing FWA. 

Concentration and Molecular Weight Effects. The viscosity of aqueous solutions of poly(ethylene oxide) depends on the concentration of the polymer solute, the molecular weight, the solution temperature, concentration of dissolved inorganic salts, and the shear rate. Viscosity increases with concentration and this dependence becomes more pronounced with increasing molecular weight. This combined effect is shown in Figure 3, in which solution viscosity is presented as a function of concentration for various molecular weight polymers. 

Dilute Polymer Solutions. The measurement of dilute solution viscosities of polymers is widely used for polymer characterization. Very low concentrations reduce intermolecular interactions and allow measurement of polymer—solvent interactions. These measurements ate usually made in capillary viscometers, some of which have provisions for direct dilution of the polymer solution. The key viscosity parameter for polymer characterization is the limiting viscosity number or intrinsic viscosity, [Tj]. It is calculated by extrapolation of the viscosity number (reduced viscosity) or the logarithmic viscosity number (inherent viscosity) to zero concentration. 

The viscosity ratio or relative viscosity, Tj p is the ratio of the viscosity of the polymer solution to the viscosity of the pure solvent. In capillary viscometer measurements, the relative viscosity (dimensionless) is the ratio of the flow time for the solution t to the flow time for the solvent /q (Table 2). The specific (sp) viscosity (dimensionless) is also defined in Table 2, as is the viscosity number or reduced (red) viscosity, which has the units of cubic meters per kilogram (m /kg) or deciUters per gram (dL/g). The logarithmic viscosity number or inherent (inh) viscosity likewise has the units m /kg or dL/g. For Tj g and Tj p, the concentration of polymer, is expressed in convenient units, traditionally g/100 cm but kg/m in SI units. The viscosity number and logarithmic viscosity number vary with concentration, but each can be extrapolated (Fig. 9) to zero concentration to give the limiting viscosity number (intrinsic viscosity) (Table 2). 

Macroscopically, the solvent and precipitant are no longer discontinuous at the polymer surface, but diffuse through it. The polymer film is a continuum with a surface rich in precipitant and poor in solvent. Microscopically, as the precipitant concentration increases, the polymer solution separates into two interspersed Hquid phases one rich in polymer and the other poor. The polymer concentration must be high enough to allow a continuous polymer-rich phase but not so high as to preclude a continuous polymer-poor phase. 

Chisso-Asahi uses a spouted bed process for the production of their coated materials (12). A 12,000 t/yr faciHty is located in Japan. The semicontinuous process consists of two batch fluid-bed coaters. A dilute polymer solution is prepared by dissolving 5% polymer and release controlling agent into a chlorinated hydrocarbon solvent such as trichloroethylene. The solution is metered into the spouted bed where it is appHed to the fertilizer core. Hot air, used to fluidize the granules, evaporates the solvent which is recovered and reintroduced into the process. Mineral talc, when used, is either slurried into the polymer solution or introduced into the fluidizing air. 

The crowning development in MW determination was the invention of gel permeation chromatography, the antecedents of which began in 1952 and which was finally perfected by Moore (1964). A column is filled with pieces of cross-linked macroporous resin and a polymer solution (gel) is made to flow through the column. The polymer solute permeates the column more slowly when the molecules are small, and the distribution of molecules after a time is linked not only to the average MW but also, for the first time with these techniques, to the vital parameter of MW distribution. 

A switching valve (low pressure) may be used to divert the eluent from the detector to the fraction collector as soon as the polymer is detected. Another switching valve can be used to select the polymer solution or the solvent for introduction into the pump. 

The nonuniform displacement can occur in the injection of the polymer solution and in the injection of the solvent. The former will be manifested in early fractions. The latter will be seen in the broadening of the distribution in late fractions and in the prolonged time necessary to wash the column. 

We employed a comparative Z-scan procedure, wherein we perform a reduced-aperture Z-scan on CS2 immediately followed by reduced and open-aperture Z-scans on the polymer solution at a particular wavelength. The peak on-axis intensity, /0, is then calculated from the CS2 peak to valley transmission change using previously measured values for its non-linear axis of refraction. Based on the work of Sheik-Bahae et al the equation for /0is given by 37]... 

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