Glass motion

ELDOR has been employed to study a number of systems such as inorganic compounds, organic compounds, biologically important compounds and glasses. The potential of ELDOR for studying slow molecular motions has been recognized by Freed and coworkers [29, 30]. 

In those cases where stirring for short periods is necessary, this may usually be accomphshed by gentle rotation of the vessel thus imparting a swirhng motion to its contents. If the vessel cannot conveniently be moved, a hand-operated stirrer constructed entirely of glass (compare Fig. II, 10, 4 and Fig. II, 10, 2) will be found satisfactory provided the glass loop is not too large. 

Rare-earth compounds containing lanthanum are extensively used in carbon lighting applications, especially by the motion picture industry for studio lighting and projection. This application consumes about 25 percent of the rare-earth compounds produced. La203 improves the alkali resistance of glass, and is used in making special optical glasses. Small amounts of lanthanum, as an additive, can be used to produce nodular cast iron. 

The kinetic nature of the glass transition should be clear from the last chapter, where we first identified this transition by a change in the mechanical properties of a sample in very rapid deformations. In that chapter we concluded that molecular motion could simply not keep up with these high-frequency deformations. The complementarity between time and temperature enters the picture in this way. At lower temperatures the motion of molecules becomes more sluggish and equivalent effects on mechanical properties are produced by cooling as by frequency variations. We shall return to an examination of this time-temperature equivalency in Sec. 4.10. First, however, it will be profitable to consider the possibility of a thermodynamic description of the transition which occurs at Tg. 

Unlike SSBR, the microstmcture of which can be modified to change the polymer s T, the T of ESBR can only be changed by a change in ratio of the monomers. Glass-transition temperature is that temperature where a polymer experiences the onset of segmental motion (7). 

A crystalline or semicrystalline state in polymers can be induced by thermal changes from a melt or from a glass, by strain, by organic vapors, or by Hquid solvents (40). Polymer crystallization can also be induced by compressed (or supercritical) gases, such as CO2 (41). The plasticization of a polymer by CO2 can increase the polymer segmental motions so that crystallization is kinetically possible. Because the amount of gas (or fluid) sorbed into the polymer is a dkect function of the pressure, the rate and extent of crystallization may be controUed by controlling the supercritical fluid pressure. As a result of this abiHty to induce crystallization, a history effect may be introduced into polymers. This can be an important consideration for polymer processing and gas permeation membranes. 

The melt temperature of a polyurethane is important for processibiUty. Melting should occur well below the decomposition temperature. Below the glass-transition temperature the molecular motion is frozen, and the material is only able to undergo small-scale elastic deformations. For amorphous polyurethane elastomers, the T of the soft segment is ca —50 to —60 " C, whereas for the amorphous hard segment, T is in the 20—100°C range. The T and T of the mote common macrodiols used in the manufacture of TPU are Hsted in Table 2. 

Because K is related to the polarizabiHty per unit volume, denser glasses generally have higher dielectric constants. The dielectric constant also increases with increasing temperature, because ionic motion becomes faster. Similarly, K is higher at lower frequencies, because the ions can foUow the oscillations more readily. 

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