Motion in polymers

Figure 12.4. Hierarchy of length scales of structure and time scales of motion in polymers. Tg denotes the glass transition temperature. After Uhlherr and Theodorou (1998) (courtesy Elsevier...

Now, let s look at a polymeric system. To begin with, the motion in polymer chains is hindered. The massive size of the polymer itself and the intermolecular forces within the chains create an inflexible system, especially when compared to the aqueous systems with which we are most familiar. Secondly, the entropy of mixing is not actually as great as that seen in typical solution formation. Polymers are inherently highly entropic, so the benefit of mixing them together is modest. Therefore, any two polymers that form a miscible blend depend primarily... 

J. J. Gilman, Plastic Relaxation via Twist Disclination Motion in Polymers, Jour. Appl. Phys., 44, 2233 (1973). 

There has been extensive effort in recent years to use coordinated experimental and simulation studies of polymer melts to better understand the connection between polymer motion and conformational dynamics. Although no experimental method directly measures conformational dynamics, several experimental probes of molecular motion are spatially local or are sensitive to local motions in polymers. Coordinated simulation and experimental studies of local motion in polymers have been conducted for dielectric relaxation,152-158 dynamic neutron scattering,157,159-164 and NMR spin-lattice relaxation.17,152,165-168 A particularly important outcome of these studies is the improved understanding of the relationship between the probed motions of the polymer chains and the underlying conformational dynamics that leads to observed motions. In the following discussion, we will focus on the... 

The lower cycle represents the chemical changes occurring during polymerization and relates them to the free volume of the system. In general, free volume of a polymer system is the total volume minus the volume occupied by the atoms and molecules. The occupied volume might be a calculated van der Waals excluded volume [139] or the fluctuation volume swept by the center of gravity of the molecules as a result of thermal motion [140,141]. Despite the obscurity in an exact definition for the occupied volume, many of the molecular motions in polymer systems, such as diffusion and volume relaxation, can be related to the free volume in the polymer, and therefore many free volume based models are used in predicting polymerization behavior [117,126,138]. 

The cooperative segmental motion in polymer molecules can be considered as a crankshaft motion of six atoms in the polymer chain. According to H. Eyring, the viscosity of a polymer melt decreases exponentially in accordance with the enthalpy of activation AHa instead of the energy of activation Ea as stated in the Arrhenius equation. 

Nuclear resonance studies of motion in polymers. Makromol. Chem. 34, 67-88 (1959). 

We have been interested in the nature of cooperative motions in polymers for some time and have used carbon-13 nuclear magnetic resonance for examining main-chain motions in solids (22-27). Carbon-13 nmr with cross-polarization and magic-angle... 

In Section IB we showed that carbon-13 rotating-frame relaxation measurements can be used to measure cooperative main-chain motions in polymers (28). We report here the effect of CO2 on the main-chain motions of PVC. 

Vol. 1, "Molecular Motion in Polymers by ESR" Harwood Academic Publ. GmbH Chur, Switzerland, 1979. 

Polymer Backbone Motion. Alternate descriptions of molecular motion utilize an effectively non-exponential autocorrelation function to describe polymer dynamics. One formalism is the use of a log-/2 distribution of correlation times in place of a single correlation time(14). Such a description may simulate the various time scales for overall and internal motions in polymers. 

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