Viscosity reacting polymer

Polymer rheology can respond nonllnearly to shear rates, as shown in Fig. 3.4. As discussed above, a Newtonian material has a linear relationship between shear stress and shear rate, and the slope of the response Is the shear viscosity. Many polymers at very low shear rates approach a Newtonian response. As the shear rate is increased most commercial polymers have a decrease in the rate of stress increase. That is, the extension of the shear stress function tends to have a lower local slope as the shear rate is increased. This Is an example of a pseudoplastic material, also known as a shear-thinning material. Pseudoplastic materials show a decrease in shear viscosity as the shear rate increases. Dilatant materials Increase in shear viscosity as the shear rate increases. Finally, a Bingham plastic requires an initial shear stress, to, before it will flow, and then it reacts to shear rate in the same manner as a Newtonian polymer. It thus appears as an elastic material until it begins to flow and then responds like a viscous fluid. All of these viscous responses may be observed when dealing with commercial and experimental polymers. 

Rheology of Curing Thermosets. A curing thermoset polymer has a conversion or cure dependent viscosity that increases as the molecular weight of the reacting polymer increases. For vinyl ester whose curing history is shown in Fig. 2.38 [29], the viscosity behaves as shown in Fig. 2.39 [29],... 

Hence, a complete model for viscosity of a reacting polymer must contain the effects of strain rate, 7, temperature, T, and degree of cure, c, such as... 

Polymer Carboxylic Acid Mole % Oxirane Reacted Polymer Viscosity, Polymer cstk Catalyst Miscibility... 

The viscosity of polymers is very high in the condensed state, and only small molecules can freely move and react in the reaction medium. The variety of reagents (or substrates) that can be used under these conditions is thus limited, and most of the reactions involving polymers require the presence of a solvent. The lack of solubility of some of the polymers restricts the possibilities of modifying them. 

The cellulose molecule contains three hydroxyl groups which can react and leave the chain backbone intact. These alcohol groups can be esterified with acetic anhydride to form cellulose acetate. This polymer is spun into the fiber acetate rayon. Similarly, the alcohol groups in cellulose react with CS2 in the presence of strong base to produce cellulose xanthates. When extruded into fibers, this material is called viscose rayon, and when extruded into sheets, cellophane. In both the acetate and xanthate formation, some chain degradation also occurs, so the resulting polymer chains are shorter than those in the starting cellulose. 

To produce a spandex fiber by reaction spinning, a 1000—3500 molecular weight polyester or polyether glycol reacts with a diisocyanate at a molar ratio of about 1 2. The viscosity of this isocyanate-terrninated prepolymer may be adjusted by adding small amounts of an inert solvent, and then extmded into a coagulating bath that contains a diamine so that filament and polymer formation occur simultaneously. Reactions are completed as the filaments are cured and solvent evaporated on a belt dryer. After appHcation of a finish, the fibers are wound on tubes or bobbins and rewound if necessary to reduce interfiber cohesion. 

Polyamides, like other macromolecules, degrade as a result of mechanical stress either in the melt phase, in solution, or in the soHd state (124). Degradation in the fluid state is usually detected via a change in viscosity or molecular weight distribution (125). However, in the soHd state it is possible to observe the free radicals formed as a result of polymer chains breaking under the appHed stress. If the polymer is protected from oxygen, then alkyl radicals can be observed (126). However, if the sample is exposed to air then the radicals react with oxygen in a manner similar to thermo- and photooxidation. These reactions lead to the formation of microcracks, embrittlement, and fracture, which can eventually result in failure of the fiber, film, or plastic article. 

As the polymer molecules form and dissociate from the catalyst, they remain ia solution. The viscosity of the solution increases with increasing polymer concentration. The practical upper limit of solution viscosity is dictated by considerations of heat transfer, mass transfer, and fluid flow. At a mbber soflds concentration of 8—10%, a further increase in the solution viscosity becomes impractical, and the polymerisation is stopped hy killing the catalyst. This is usually done by vigorously stirring the solution with water. If this is not done quickly, the unkilled catalyst continues to react, leading to uncontrolled side reactions, resulting in an increase in Mooney viscosity called Mooney Jumping. 

The polymer plays several roles in this composition. First, it reduces shrinkage. Second, it increases the viscosity of the adhesive to the point where it can be easily applied. It also speeds the rate of cure. As will be discussed in the section on initiators, the boron compound reacts with atmospheric oxygen to form free radicals. 

The explanation for autoacceleration is as follows. As polymerisation proceeds there is an increase in the viscosity of the reaction mixture which reduces the mobility of the reacting species. Growing polymer molecules are more affected by this than either the molecules of monomer or the fragments arising from decomposition of the initiator. Hence termination reactions slow down and eventually stop, while initiation and propagation reactions still continue. Such a decrease in the rate of the termination steps thus leads to the observed increase in the overall rate of polymerisation. 

When two polymers interact or react with each other, they are likely to provide a compatible, even a miscible, blend. Epoxidized natural rubber (ENR) interacts with chloro-sulfonated polyethylene (Hypalon) and polyvinyl chloride (PVC) forming partially miscible and miscible blends, respectively, due to the reaction between chlorosulfonic acid group and chlorine with epoxy group of ENR. Chiu et al. have studied the blends of chlorinated polyethylene (CR) with ENR at blend ratios of 75 25, 50 50, and 25 75, as well as pure rubbers using sulfur (Sg), 2-mercapto-benzothiazole, and 2-benzothiazole disulfide as vulcanizing agents [32]. They have studied Mooney viscosity, scorch... 

Irish moss extract, or carrageenin, is a negatively charged polymer which reacts with positively charged protein molecules, imparting rapid increase in mix viscosity. There are many types used for ice cream, depending on the final use. It is generally used in conjunction with CMC or locust bean to prevent mix separation. Levels between 0.02 and 0.10% are recommended. 

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