Viscosity reduction Subject

Ultrasonic waves also bring about a reduction in the viscosity of nitrocellulose. The effect is more marked the higher the initial viscosity, and thus the longer the nitrocellulose chains (Sollner [93] Schmidt and Rommel [94]). For instance, nitrocellulose with a molecular weight of 123,000, estimated by means of Staudinger s viscosity equation, subjected in solution form to the action of ultrasonic waves suffered a degradation to a molecular weight of 70,000-80,000. 

The presence of gel molecules may be interpreted as a part of the size distribution. The effect of gel is to introduce a very long relaxation time. It exhibits viscosity enhancement at the low shear rate and viscosity reduction at the high shear rate. This occurs with both macrogel and microgel. The details of this mechanism are subjects for future study. 

As shown experimentally by Piest [75], cotton which was subjected to various operations, e.g. bleaching, treatment with alkalis or acids, strong heating prior to nitration furnishes nitrocellulose solutions of low viscosity. At the same time an increase in the solubility of the nitrocotton was also observed. This is evidence that the cellulose molecules are shortened and their content of terminal group is increased. A certain proportion of hydrocellulose and oxycellulose may result. The total effect is to bring about an increase in the reductive properties of the cellulose, i.e. an increase of the copper number. 

At this point it seems of interest to include a graph obtained on a quite different polymer, viz. cellulose tricarbanilate. Results from a series of ten sharp fractions of this polymer will be discussed in Chapter 5 in connection with the limits of validity of the present theory. In Fig. 3.5 a double logarithmic plot of FR vs. is given for a molecular weight of 720000. This figure refers to a 0.1 wt. per cent solution in benzophenone. It appears that the temperature reduction is perfect. Moreover, the JeR-value for fiN smaller than one is very close to the JeR value obtained from Figure 3.1 for anionic polystyrenes in bromo-benzene. As in the case of Fig. 3.1, pN is calculated from zero shear viscosity. The correspondence of Figs. 3.1 and 3.5 shows that also the molecules of cellulose tricarbanilate behave like flexible linear chain molecules. For more details on this subject reference is made to Chapter 5. 

The operation of polymerization reactors is subject to different sorts of instabilities, which may be caused by thermal, viscous, hydrodynamic and kinetic effects, among other reasons. For instance, the increase of the system viscosity (or polymer build-up on heat transfer surfaces) leads to significant reduction of heat transfer coefficients and... 

For K > 2 the drops deform into stable filaments, which only upon reduction of k disintegrate by the capillarity forces into mini-droplets. The deformation and breakup processes require time - in shear flows the reduced time to break is tb > 100- When values of the capillarity number and the reduced time are within the region of drop breakup, the mechanism of breakup depends on the viscosity ratio, A, - in shear flow, when X > 3.8, the drops may deform, but they cannot break. Dispersing in extensional flow field is not subjected to this limitation. Furthermore, for this deformation mode Kcr (being proportional to drop diameter) is significantly smaller than that in shear (Grace 1982). 

Several models that include the effect of pressure on viscosity are outlined herein. For applications at high pressures, one may also require estimates of the viscosity of liquid hydrocarbons and their mixtures with dissolved gases (such as with CO2, Nj, H2S, etc.) because, due to the high solubility of such gases in hydrocarbon mixtures at elevated pressures, there is a very large reduction in the mixture viscosity. Indeed, such behavior is part of the basis for enhanced oil recovery by miscible gas injection. Even though the effect of dissolved gases is beyond the scope of this chapter, some comments about this are included due to the importance of this subject. 

In the case of a ternary acrylonitrile-based copolymer, subjected to spinning from a solution, a more pronounced reduction of its intrinsic viscosity is observed, indeed, when working with more diluted solutions (having, nevertheless, a minimum concentration of 10%), Figure 3.280. 

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