Cooling entanglement

In Chapter 3 it was pointed out that certain rod-like polymers showed many of the attributes of liquid crystals in the melt. In particular, these molecules were oriented in shear to such an extent that interchain entanglement was small and the melts had a low viscosity. On cooling of the melt these rod-like molecules remained oriented, effectively self-reinforcing the polymer in the direction of flow. The essential differences in the properties of liquid crystal polymers... 

The solidity of gel electrolytes results from chain entanglements. At high temperatures they flow like liquids, but on cooling they show a small increase in the shear modulus at temperatures well above T. This is the liquid-to-rubber transition. The values of shear modulus and viscosity for rubbery solids are considerably lower than those for glass forming liquids at an equivalent structural relaxation time. The local or microscopic viscosity relaxation time of the rubbery material, which is reflected in the 7], obeys a VTF equation with a pre-exponential factor equivalent to that for small-molecule liquids. Above the liquid-to-rubber transition, the VTF equation is also obeyed but the pre-exponential term for viscosity is much larger than is typical for small-molecule liquids and is dependent on the polymer molecular weight. 

Analogous results have been found for stress relaxation. In fibers, orientation increases the stress relaxation modulus compared to the unoriented polymer (69,247,248,250). Orientation also appears in some cases to decrease the rate, as well as the absolute value, at which the stress relaxes, especially at long times. However, in other cases, the stress relaxes more rapidly in the direction parallel to the chain orientation despite the increase in modulus (247.248,250). It appears that orientation can in some cases increase the ease with which one chain can slip by another. This could result from elimination of some chain entanglements or from more than normal free volume due to the quench-cooling of oriented polymers. 

Low temperature crystallography is a discipline deeply entangled with the techniques of X-ray diffraction on cooled samples and very often cryo-crystallog-raphy and low temperature dijfraction are used as synonymous. This reflects a more general problem of crystallography, a science often considered just at the level of a technique, a confusion that hopefully this book will contribute to remove. 

This interplay between system-bath entanglement and system-probe entanglement and its effect on system cooling is still under active investigation by our group. 

Fouling produces dirty and inefficient cooling systems, impeding the flow of cooling water. It involves the physical adherence to surfaces and mutual entanglement of insoluble salts, corrosion products, oils, fats, and other process contaminants, air-blown debris, and the like. Where... 

Fig. 25 Viscoelastic behavior of a semi-dilute solution of DNA. Elastic modulus (G, filled symbols) and viscous modulus (G", open symbols) are plotted, together with their ratio G"IG = tan 5 (solid curve), for a 93 mg/mL DNA solution subjected to a heating-cooling cycle. The entanglement of DNA helices and, at high temperature, of single strands causes the almost monotonous increase of the dynamic moduli. Reproduced with permission from [110]...

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