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For amorphous polymers, the glass transition temperature, Tg, constitutes their most important mechanical property. In fact, upon synthesis of a new polymer, the glass transition temperature is among the rst properties measured. This chapter describes the behavior of amorphous polymers in the glass transition range, emphasizing the onset of molecular motions associated with the transition. Before beginning the main topic, two introductory sections are presented. The rst denes a number of mechanical terms that will be needed, and the second describes the mechanical spectrum encountered as a polymers temperature is raised.

8.1 SIMPLE MECHANICAL RELATIONSHIPS Terms such as glassy, rubbery, and viscous imply a knowledge of simple material mechanical relationships. Although such information is usually obtained by the student in elementary courses in physics or mechanics, the basic relationships are reviewed here because they are used throughout the text. More detailed treatments are available (14). 8.1.1 Modulus

8.1.1.1 Youngs Modulus Hooks law assumes perfect elasticity in a material body. Youngs modulus, E, may be written
E =s e (8.1)

where s and e represent the tensile (normal) stress and strain, respectively. Youngs modulus is a fundamental measure of the stiffness of the material. The higher its value, the more resistant the material is to being stretched. The tensile stress is dened in terms of force per unit area. If the samples initial length is L0 and its nal length is L, then the strain is e = (L - L0)/L0 (see Figure 8.1). The forces and subsequent work terms have some simple examples. Consider a postage stamp, which weighs about 1 g and is about 1 cm 1 cm in size. It requires about 1 dyne of force to lift it from the horizontal position to the vertical position, as in turning it over. One dyne of force through 1 cm gives 1 erg, the amount of work done. Modulus is usually reported in dynes/cm2, in terms of force per unit area. Frequently the Pascal unit of modulus is used, 10 dynes/cm2 = 1 Pascal.

8.1.1.2 Shear Modulus Instead of elongating (or compressing!) a sample, it may be subjected to various shearing or twisting motions (see Figure 8.1).
In more graphic language, the amount of stress applied is measured by the amount of grunting the investigator does, and the strain is measured by the samples groaning.

8.1

SIMPLE MECHANICAL RELATIONSHIPS

351

Figure 8.1 Mechanical deformation of solid bodies. (a) Triaxial stresses on a material body undergoing elongation. (b) Simple shear deformation.

The ratio of the shear stress, t, to the shear strain, g, denes the shear modulus, G: G= t g (8.2)

These and other mechanical terms are summarized in Table 8.1. (Note that different authors often use different symbols.) 8.1.2 Newtons Law The equation for a perfect liquid exhibiting a shear viscosity, h, may be written h = t ( dg dt ) (8.3)

where t and g represent the shear stress and strain, respectively, and t is the time. For simple liquids such as water or toluene, equation (8.3) reasonably describes their viscosity, especially at low shear rates. For larger values of h, ow is slower at constant shear stress. While neither equation (8.1) nor equation (8.3) accurately describes polymer behavior, they represent two important limiting cases.

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Table 8.1 Some mechanical terms

Term s e g t E G B D J n h l b

Denition Normal stress Normal strain Shear strain Shear stress Youngs modulus Shear modulus Bulk modulus Tensile compliance Shear compliance Poissons ratio Shear viscosity Elongational viscosity Compressibility

The basic denition of viscosity should be considered in terms of equation (8.3). Consider two 1-cm2 planes 1 cm apart imbedded in a liquid. If it takes 1 dyne of force to move one of the planes 1 cm/s relative to the other in a shearing motion, the liquid has a viscosity of 1 poise. Viscosity is also expressed in pascal-seconds, with 1 Pa s = 0.1 poise. 8.1.3 Poissons Ratio When a material body is elongated (or undergoes other modes of deformation), in general, the volume changes, usually increasing as elongational (normal) strains are applied. Poissons ratio, v, is dened as - ve x = e y = e z (8.4)

for very small strains, where the strain ex is applied in the x direction and the strains ey and ez are responses in the y and z directions, respectively (see Figure 8.1). Table 8.2 summarizes the behavior of v under several circumstances. For analytical purposes, Poissons ratio is dened on the differential scale. If V represents the volume, V = xyz Then d ln V d ln x d ln y d ln z = + + d ln x d ln x d ln x d ln x and (8.6) (8.5)

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Table 8.2 Values of Poissons ratio

Value 0.5 0.0 0.490.499 0.200.40

Interpretation No volume change during stretch No lateral contraction Typical values for elastomers Typical values for plastics

d ln y d ln z dy ==v=d ln x d ln x y0

dx x0

(8.7)

Since d ln x/d ln x = 1, for no volume change v = 0.5 (see Table 8.2). On extension, plastics exhibit considerable volume increases, as illustrated by the values of v in Table 8.2. The physical separation of atoms provides a major mechanism for energy storage and short-range elasticity. Poissons ratio is only useful for very small strains. Poissons ratio was originally developed for calculations involving metals, concrete, and other materials with limited extensibility. The approximations built into the theory make rubber elasticity results unrealistic. Glazebrook (5) presents a more general treatment of Poissons ratio. 8.1.4 The Bulk Modulus and Compressibility The bulk modulus, B, is dened as B = -V P V T (8.8)

where P is the hydrostatic pressure. Normally a body shrinks in volume on being exposed to increasing external pressures, so the term (P/V )T is negative. The inverse of the bulk modulus is the compressibility, b, b= 1 B (8.9)

which is strictly true only for a solid or liquid in which there is no timedependent response. Bulk compression usually does not involve long-range conformational changes but rather a forcing together of the chain atoms. Of course, materials ordinarily exist under a hydrostatic pressure of 1 atm (1 bar) at sea level. 8.1.5 Relationships among E, G, B, and n A three-way equation may be written relating the four basic mechanical properties:

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E = 3B(1 - 2v) = 2(1 + v)G

(8.10)

Any two of these properties may be varied independently, and conversely, knowledge of any two denes the other two. As an especially important relationship, when v @ 0.5, E @ 3G (8.11)

which denes the relationship between E and G to a good approximation for elastomers. Equation (8.10) can also be used to evaluate Poissons ratio for elastomers. Rearranging the two left-hand portions, we have 1 - 2v = E bE = 3B 3 (8.12)

Because the quantity 1 - 2v is close to zero for elastomers (but cannot be exactly so), exact evaluation of v depends on the evaluation of the right-hand side of equation (8.12). Values in the literature for elastomers vary from 0.49 to 0.49996 (2). Thus, in contrast to plastics, separation of the atoms in elastomers plays only a small role in the internal storage of energy. Instead, conformational changes in the chains come to the fore, the main subject of Chapter 9. 8.1.6 Compliance versus Modulus If the modulus is a measure of the stiffness or hardness of an object, its compliance is a measure of softness. In regions far from transitions, the elongational compliance, D, is dened as D 1 E (8.13)

For regions in or near transitions, the relationship is more complex. Likewise, the shear compliance, J, is dened as 1/G. Ferry has reviewed this topic (2).

8.1.7 Numerical Values for E Before proceeding with the description of the temperature behavior of polymers, it is of interest to establish some numerical values for Youngs modulus (see Table 8.3). Polystyrene represents a typical glassy polymer at room temperature. It is about 40 times as soft as elemental copper, however. Soft rubber, exemplied by such materials as rubber bands, is nearly 1000 times softer still. Perhaps the most important observation from Table 8.3 is that the modulus

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Table 8.3 Numerical values of Youngs modulus

Material Copper Polystyrene Soft rubber

E (dyne/cm2) 1.2 10 3 1010 2 107

12

E (Pa) 1.2 1011 3 109 2 106

varies over wide ranges, leading to the wide use of logarithmic plots to describe the variation of modulus with temperature or time. 8.1.8 Storage and Loss Moduli The quantities E and G refer to quasistatic measurements. When cyclical or repetitive motions of stress and strain are involved, it is more convenient to talk about dynamic mechanical moduli. The complex Youngs modulus has the formal denition E* = E + iE (8.14)

where E is the storage modulus and E is the loss modulus. Note that E = |E*|. The quantity i represents the square root of minus one. The storage modulus is a measure of the energy stored elastically during deformation, and the loss modulus is a measure of the energy converted to heat. Similar denitions hold for G*, D*, J*, and other mechanical quantities. 8.1.9 Elongational Viscosity The elongational viscosity, l, sometimes called the extension viscosity, refers to the thinning down of a column of liquid as it is being stretched. A simple example is the narrowing of a stream of water falling under gravity from a faucet. For a Newtonian uid, l = 3h (6). For entangled polymer melts, l may be many times h. An important example in polymer science and engineering is in the spinning of bers; see Section 6.10.

8.2 FIVE REGIONS OF VISCOELASTIC BEHAVIOR Viscoelastic materials simultaneously exhibit a combination of elastic and viscous behavior. While all substances are viscoelastic to some degree, this behavior is especially prominent in polymers. Generally, viscoelasticity refers to both the time and temperature dependence of mechanical behavior. The states of matter of low-molecular-weight compounds are well known: crystalline, liquid, and gaseous. The rst-order transitions that separate these states are equally well known: melting and boiling. Another well-known