Viscous polymers

It has been proven in [107] that the exudation kinetics of the inhibiting liquid from film samples produced of a mixture of PE - - mineral oil - - contact Cl (Vital, GRM) by pressing under the polymer viscous flow temperature is... 

Stress Relaxation Swelling of polymer, viscous yield of network, reptation [53]... 

A recent design of the maximum bubble pressure instrument for measurement of dynamic surface tension allows resolution in the millisecond time frame [119, 120]. This was accomplished by increasing the system volume relative to that of the bubble and by using electric and acoustic sensors to track the bubble formation frequency. Miller and co-workers also assessed the hydrodynamic effects arising at short bubble formation times with experiments on very viscous liquids [121]. They proposed a correction procedure to improve reliability at short times. This technique is applicable to the study of surfactant and polymer adsorption from solution [101, 120]. 

Polymers have found widespread applications because of their mechanical behaviour. They combine the mechanical properties of elastic solids and viscous fluids. Therefore, they are regarded as viscoelastic materials. Viscoelastic... 

A polymer chain can be approximated by a set of balls connected by springs. The springs account for the elastic behaviour of the chain and the beads are subject to viscous forces. In the Rouse model [35], the elastic force due to a spring connecting two beads is f= bAr, where Ar is the extension of the spring and the spring constant is ii = rtRis the root-mean-square distance of two successive beads. The viscous force that acts on a bead is... 

Demand for temperature controlled troughs came from the material scientists who worked witli large molecules and polymers tliat establish viscous films. Such troughs allow a deeper understanding of tire distinct phases and tire transitions in LB films and give more complete pressure-area isotlienns (see d) below). 

The majority of polymer flow processes are characterized as low Reynolds number Stokes (i.e. creeping) flow regimes. Therefore in the formulation of finite element models for polymeric flow systems the inertia terms in the equation of motion are usually neglected. In addition, highly viscous polymer flow systems are, in general, dominated by stress and pressure variations and in comparison the body forces acting upon them are small and can be safely ignored. 

Place 10 g. of hquid methyl methacrylate in a test-tube, add 10-20 mg. of benzoyl peroxide (Section IV, 196), stopper the test-tube loosely and heat in a boiling water bath. After 20-25 minutes, the hquid suddenly becomes very viscous and soon sets to a hard, colourless mass of the polymer. 

Irregularities such as branch points, comonomer units, and cross-links lead to amorphous polymers. They do not have true melting points but instead have glass transition temperatures at which the rigid and glasslike material becomes a viscous liquid as the temperature is raised. 

In this chapter we examine the flow behavior of bulk polymers in the liquid state. Such substances are characterized by very high viscosities, a property which is directly traceable to the chain structure of the molecules. All substances are viscous, even low molecular weight gases. The enhancement of this property due to the molecular structure of polymers is one of the most striking features of these materials. 

Our approach in this chapter is to alternate between experimental results and theoretical models to acquire familiarity with both the phenomena and the theories proposed to explain them. We shall consider a model for viscous flow due to Eyring which is based on the migration of vacancies or holes in the liquid. A theory developed by Debye will give a first view of the molecular weight dependence of viscosity an equation derived by Bueche will extend that view. Finally, a model for the snakelike wiggling of a polymer chain through an array of other molecules, due to deGennes, Doi, and Edwards, will be taken up. 

One of the striking omissions from our discussion has been an explicit consideration of polymer molecular weight on the viscous behavior of the sample. This omission will be corrected in the next section. 

In this chapter we examine the elastic behavior of polymers. We shall see that this behavior is quite different from the elasticity displayed by metals and substances composed of small molecules. This is a direct consequence of the chain structure of the polymer molecules. In many polymers elasticity does not occur alone, but coupled with viscous phenomena. The combination of these effects is called viscoelasticity. We shall examine this behavior as well. 

Next let us consider the differences in molecular architecture between polymers which exclusively display viscous flow and those which display a purely elastic response. To attribute the entire effect to molecular structure we assume the polymers are compared at the same temperature. Crosslinking between different chains is the structural feature responsible for elastic response in polymer samples. If the crosslinking is totally effective, we can regard the entire sample as one giant molecule, since the entire volume is permeated by a continuous network of chains. This result was anticipated in the discussion of the Bueche theory for chain entanglements in the last chapter, when we observed that viscosity would be infinite with entanglements if there were no slippage between chains. 

Through the dashpot a viscous contribution was present in both the Maxwell and Voigt models and is essential to the entire picture of viscoelasticity. These have been the viscosities of mechanical units which produce equivalent behavior to that shown by polymers. While they help us understand and describe observed behavior, they do not give us the actual viscosity of the material itself. 

This concludes our discussion of the viscosity of polymer solutions per se, although various aspects of the viscous resistance to particle motion continue to appear in the remainder of the chapter. We began this chapter by discussing the intrinsic viscosity and the friction factor for rigid spheres. Now that we have developed the intrinsic viscosity well beyond that first introduction, we shall do the same (more or less) for the friction factor. We turn to this in the next section, considering the relationship between the friction factor and diffusion. 

Gyclodextrins. As indicated previously, the native cyclodextrins, which are thermally stable, have been used extensively in Hquid chromatographic chiral separations, but their utihty in gc appHcations was hampered because their highly crystallinity and insolubiUty in most organic solvents made them difficult to formulate into a gc stationary phase. However, some functionali2ed cyclodextrins form viscous oils suitable for gc stationary-phase coatings and have been used either neat or diluted in a polysiloxane polymer as chiral stationary phases for gc (119). Some of the derivati2ed cyclodextrins which have been adapted to gc phases are 3-0-acetyl-2,6-di-0-pentyl, 3-0-butyryl-2,6-di-0-pentyl,... 

Hot Plate, Infrared, and Hot Gas Welding. These processes involve external means to heat thermoplastic polymers to a viscous state in... 

Polyamines can also be made by reaction of ethylene dichloride with amines (18). Products of this type are sometimes formed as by-products in the manufacture of amines. A third type of polyamine is polyethyleneimine [9002-98-6] which can be made by several routes the most frequently used method is the polymeriza tion of azitidine [151 -56 ] (18,26). The process can be adjusted to vary the amount of branching (see Imines, cyclic). Polyamines are considerably lower in molecular weight compared to acrylamide polymers, and therefore their solution viscosities are much lower. They are sold commercially as viscous solutions containing 1—20% polymer, and also any by-product salts from the polymerization reaction. The charge on polyamines depends on the pH of the medium. They can be quaternized to make their charge independent of pH (18). 

The monomer can also be copolymerized with acrylamide. Because of the high chain-transfer rate of aUyflc radicals, the molecular weights tend to be lower than for acryflc polymers. These polymers are sold either as a viscous solution or a dry powder made by suspension polymeriza tion (see Allyl monomers AND POLYPffiRS). 

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