Chain mobility

This intricate mode of crystallization requires more time to accomplish than, say, the entry of small ions into growing salt crystals. This, coupled with low chain mobility due to viscous effects, makes the rate of crystallization slow and accounts in part for the fact that with rapid cooling-called quenching-the temperature drops below T without crystallization. 

The greater the undercooling, the more rapidly the polymer crystallizes. This is due to the increased probability of nucleation the more supercooled the liquid becomes. Although the data in Fig. 4.8 are not extensive enough to show it, this trend does not continue without limit. As the crystallization temperature is lowered still further, the rate passes through a maximum and then drops off as Tg is approached. This eventual decrease in rate is due to decreasing chain mobility which offsets the nucleation effect. 

Sluggish chain mobility and low free volume result in low diffusion constants, and when combined with low solubiUty of gases lead to very low permeabihty. The diffiisivity of several gases in butyl mbber and natural mbber are shown in Table 3 (82) (see Barrier polymers). 

In the case of an amorphous polymer the glass transition temperature will define whether or not a material is glass-like or rubbery at a given temperature. If, however, the polymer will crystallise, rubbery behaviour may be limited since the orderly arrangement of molecules in the crystalline structure by necessity limits the chain mobility. In these circumstances the transition temperature is of less consequence in assessing the physical properties of the polymer. 

The effect of the substituents on chain mobility and chain packing has been related to the gas transport properties [209]. Role of symmetry of methyl group placement on bisphenol rings in PES shows the permeability coefficients in the following order ... 

With increasing CP ionization, increasing chain mobility and the disordering of the local structure, the saturation of CP with protein in all cases becomes... 

The formation of ECC is not only an extension of a portion of the macromolecule but also a mutual orientational ordering of these portions belonging to different molecules (intermolecular crystallization), as a result of which the structure of ECC is similar to that of a nematic liquid crystal. After the melt is supercooled below the melting temperature, the processes of mutual orientation related to the displacement of molecules virtually cannot occur because the viscosity of the system drastically increases and the chain mobility decreases. Hence, the state of one-dimensional orientational order should be already attained in the melt. During crystallization this ordering ensures the aggregation of extended portions to crystals of the ECC type fixed by intermolecular interactons on cooling. 

Deuteron NMR — A new Tool for Studying Chain Mobility and Orientation in Polymers... 

The number of the constraints to chain mobility shown in Fig. 16 decreases with increasing temperature, reflecting the increase of the free volume. From a comparison of the spectra in Fig. 15 with line shapes calculated for flexible chains on a diamond lattice 23 (one can infer that the average length of the flexible unit increases from 3-5 bonds at room temperyture to about 10-15 bonds at 380 K. Our model thus can quantitatively explain the gradual increase of the number of conformations accessible to the chain motion. The earlier XH wide line data 72 are also in accord with our findings. 

Molecular Motion in amorphous atactic polystyrene (PS) is more complicated and a number of relaxation processes, a through 5 have been detected by various techniques as reviewed recently by Sillescu74). Of course, motions above and below the glass transition temperature Tg have to be treated separately, as well as chain and side group mobility, respectively. Motion well above Tg as well as phenyl motion in the glassy state, involving rapid 180° jumps around their axes to the backbone has been discussed in detail in Ref.17). Here we will concentrate on chain mobility in the vicinity of the glass transition. 

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