12 Viscoelasticity of Glassy and Semicrystalline Polymers 12.1 General Considerations 454 12.2. Relaxations in the Frequency Domain at Temperatures Slightly Higher Than Ty, 457 12.3. Topology of the Dynamics in the Vicinity of the Glass Transition Temperature 460 12.4 Viscoelastic Functions for Glassy Systems in the Frequency Domain 463 12.5 Dispersions in the Glassy State and the Glass Transition 464 12.6 Molecular Cooperativity in the Glass Transition 468 12.7 Structural Recovery in the Glassy State: Aging 413 12.8 Memory Effects and Physical Aging 414 12.9 Influence of Physical Aging on the Viscoelastic Functions: Time-Aging Time Correspondence Principle 418 12.10 Nonlinear Behavior in Aging 482 12.11 Final Remarks on Aging Processes 483 12.12 Relaxation Behavior of Semicrystalline Polyme General Considerations 485 12.13. General Features of Crystalline Polymers 494 12.14 Time-Temperature Correspondence Principle 496 12.15 Modeling the Viscoelastic Behavior of Crystalline Polymers 496 Problem sets 498, References 507 12.1 GENERAL CONSIDERATIONS When an amorphous material in the liquid state is cooled, a temperature is reached in the vicinity of which a transition from the liquid state to the 454Glassy and Semicrystalline Polymers 455 glassy state occurs. The glassy state may also be formed if a molten crystal- line material is cooled at a heating rate high enough that the development of crystalline order is prevented. Low molecular weight organic substances, inorganic salts and oxides, polymers, etc. can develop the glassy state. As Eq. (6.33) indicates, the mean relaxation time of a liquid is given by (t) = Nod, where no and J? are, respectively, the viscosity and the steady-state compliance. The viscosity undergoes an anomalous increase with decreasing temperature as the temperature of the liquid comes closer to T,,, so the value of (t) becomes larger than the time scale of any available experiment. In this situation, the system falls out of equilibrium and the glassy state is formed. The temperature dependence of the viscosity of liquids led to their classification as fragile and strong liquids (1). For fragile liquids the varia- tion of the viscosity with temperature is described by the Vogel—Fulcher— Tammann-Hesse (VFTH) equation, while for strong liquids the viscosity follows Arrhenius behavior. As shown in Figure 12.1, the jumps in the specific heat at T, are much larger for fragile liquids than for strong ones. Examples of fragile liquids are organic liquids, polymers, and inorganic salts; fiquids like SiO, and GeO, are examples of strong liquids. It should be pointed out that polymeric materials are the most fragile liquids 10H propylene glycol Log (viscosity in poise) Log (viscosity in Pa-s) Figure 12.1 Variation of the viscosity and the specific heat (inset) with tempera- ture for various glasses. (From Ref. 1.)456 Chapter 12 identified to date. However, they cannot be accommodated in Figure 12.1 without modification, because the viscosity of a polymer liquid is largely controlled by its molecular weight. Let us analyze now the variation of the heat capacity of a molten crystalline substance with temperature. If the melt is slowly cooled, a tem- perature is reached at which a sharp decrease in the heat capacity C,, caused by the liquid + crystal transition, occurs. The variation of C, with tem- perature is shown in Figure 12.2. The heat capacity decrease with decreasing temperature at T < T,,, becoming zero at T=0 K. However, the heat capacity of a supercooled melt slowly decreases as the temperature declines, the difference C, (liquid)—C, (crystal) increasing as the temperature decreases. At the temperature at which the liquid > glass transition occurs, a sharp fall in C, takes place, and the value of C, at T, becomes only slightly higher than that of the crystal at the same temperature. The curves showing the variation of both the heat capacity and the entropy for the crystal and the supercooled liquid at T < T, indicate that a temperature Tx is reached, called the Kauzmann temperature, at which the crystal and the glassy liquid exhibit the same entropy (2). Because the structural entropy of the crystal is zero, one would expect that the value of this quantity also would be nil for a completely relaxed glass at the Kauzmann temperature. This reasoning Heat capacity ° Tk‘ Te ‘Temperature Figure 12.2 Variation of the heat capacity for fragile glass formers in crystal (C), supercooled liquid (L,.), equilibrium liquid (L,,) and glass (G) phases. T;, is the Kauzmann temperature.