6.

8 THERMODYNAMICS OF FUSION

299

at modest pressures, being metastable for larger dimensions, with 1/ltr * representing the boundary between the two phase regimes in T - 1/l space. For very high pressures, P > PQ (143), the h phase remains stable even for innite l, However, from a kinetic point of view, lateral growth in folded-chain crystals is thought to be faster than thickening growth, favoring the appearance of folded-chain morphologies under most circumstances. The o phase is much less mobile than the h phase, slowing down growth of the h phase in the presence of the o phase. There is a continuing connection with kinetics of crystallization in this arguo )o throughout ment. When region A is small, the polymer must be close to (Tm the region, hence at small supercoolings. Consequently crystallization in this region will be slow, and may be unrealizable. In this case, on cooling, crystallization will take place in region B, resulting in hexagonal crystallization. If region A is wide, however, the crystallization may start at the ultimately more stable orthorhombic state before it reaches TQ.

6.8

THERMODYNAMICS OF FUSION

In the previous sections it was shown that the formation of lamellae with folded chains was essentially a kinetically controlled phenomenon. This section treats the free energy of polymer crystallization and melting point depression. Melting is a rst-order transition, ordinarily accompanied by discontinuities of such functions as the volume and the enthalpy. Ideal and real melting in polymers is illustrated in Figure 6.39. Ideally polymers should exhibit the behavior shown in Figure 6.39a, where the volume increases a nite amount exactly at the melting (fusion) temperature, Tf. (The subscript M, for melting, is also in wide use. In this text, M represents mixing.) Note that the coefcient of thermal expansion also increases above Tf. Owing to the range of crystallite sizes and degrees of perfection in the real case, a range of melting temperatures is usually encountered, as shown experimentally in Figure 6.2. The

Figure 6.39 Dilatometric behavior of polymer melting.

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THE CRYSTALLINE STATE

classic melting temperature is usually taken where the last trace of crystallinity disappears, point A in Figure 6.39b. The free energy of fusion, DGf, is given by the usual equation, DG f = DH f - T DS f (6.36)

where DHf and DSf represent the molar enthalpy and entropy of fusion. At the melting temperature, DGf equals zero, and Tf = DH f DS f (6.37)

Thus a smaller entropy or a larger enthalpy term raises Tf. Thus, the relative changes in DHf and DSf in going from the amorphous state to the crystalline state determine the melting temperature of the polymer.

6.8.1

Theory of Melting Point Depression

The melting point depression in crystalline substances from the pure state Tf0 is given by the general equation (143) R 1 1 - 0 =ln a Tf Tf DH f (6.38)

where a represents the activity of the crystal in the presence of the impurity. The thermodynamics of melting in polymers was developed by Flory and his co-workers (145147). To a rst approximation, the melting point depression depends on the mole fraction of impurity, XB, the mole fraction of crystallizable polymer being XA. Substituting XA for a in equation (6.38), 1 1 R =ln X A DH f T f T f0 For small values of XB, - ln X A = - ln(1 - X B ) @ X B (6.40) (6.39)

In the following discussion, DHf is the heat of fusion per mole of crystalline mers. There are three important cases in which the melting temperature may be depressed. If XB represents the mole fraction of noncrystallizable comonomer incorporated in the chain, R 1 1 XB = T f T f0 DH f (6.41)

6.8

THERMODYNAMICS OF FUSION

301

The mer unit at the end of the chain must always have a different chemical structure from those of the mers along the chain. Thus end mers constitute a special type of impurity, and the melting point depends on the molecular weight. If M0 is the molecular weight of the end mer (and assuming that both ends are identical), the mole fraction of the chain ends is given approximately by 2M0/Mn. Thus 1 1 R 2 M0 - 0 = DH f M n Tf Tf (6.42)

which predicts that the highest possible melting temperature will occur at innite molecular weight. If a solvent or plasticizer is added, the case is slightly more complicated. Here, the molar volume of the solvent, V1, and the molar volume of the polymer repeat unit, Vu, cannot be assumed to be equal. Also, the interaction between the polymer and the solvent needs to be taken into account. The result may be written (147) R Vu 1 1 (v1 ) = T f T f0 DH f V1 (6.43)

where v1 represents the volume fraction of diluent. The quantity c1 has been interpreted in several ways (145,146). Principally it is a function of the energy of mixing per unit volume. For calculations involving plasticizers, the form using the solubility parameters d1 and d 2 is particularly easy to use (148) (see Section 3.3.2): c1 =

(d1 - d 2 ) V1
RT

(6.44)

Corresponding relations for the depression of the glass transition temperature, Tg, by plasticizer are given in Section 8.8.1. Corresponding equations for the dependence of the melting point on pressure were derived by Karasz and Jones (149). For a pressure Pf, Pf - Pf0 = RT f Vu (v1 ) DVf V1 (6.45)

where DVf is the volume change on fusion.

6.8.2

Example Calculation of Melting Point Depression

Suppose that we swell poly(ethylene oxide) with 10% of benzene. What will be the new melting temperature, if it melted at 66C dry?

302

THE CRYSTALLINE STATE

Equation (6.43) can be solved, with the aid of Tables 3.1, 3.2, 3.4, and 6.1. First, the molar volumes of the polymer and the solvent must be computed: for benzene, with six carbons and six hydrogens, M = 78 g/mol. Its density is 0.878 g/cm3. Division yields 88 cm3/mol. For poly(ethylene oxide), the mer molecular weight is 44 g/mol, and its density is 1.20 g/cm3, yielding a molar volume of 36.6 cm3/mol. Equation (6.43), with appropriate numerical values, is 1 R Vu 1 (v1 ) + 0 = DH f V1 Tf Tf 1 0.0083 kJ mol K 36.6 cm 3 mol 1 (0.1) + =+ 8.29kJ mol 88 cm 3 mol Tf 339 K T f = 334.3 K or 61.4C If room temperature is about 25C, then the crystallinity will not be destroyed by the benzene plasticizer. 6.8.3 Experimental Thermodynamic Parameters

The quantity Tf0 may be determined either directly on the pure polymer or by a plot of 1/Tf versus v1.The latter is very useful in the case where the polymer decomposes below its melting temperature. Once T 0 f is determined, equations (6.43) and (6.44) permit the calculation of both the Flory interaction parameter and the heat of fusion of the polymer from the slope and intercept of a plot of (1/Tf) - (1/Tf0) versus (1/Tf) (146). The heat of fusion determined in this way measures only the crystalline portion. If heat of fusion data are compared with corresponding data obtained by DSC (see Figure 6.3), which measures the heat of fusion for the whole polymer, the percent crystallinity may be obtained. 6.8.4 Entropy of Melting

In classical thermodynamics, the change in Gibbs free energy is zero at the melting point, DG f = DH f - T DS f = 0 (6.46)

where T = Tf. For polyethylene, per CH2 group, with DHf = 3.94 kJ/mol; see Table 6.1. Then DS f = DH f T f = 9.61 J mol K (6.47)

at a Tf of 410 K. Statistical thermodynamics asks how many conformational changes are involved in the melting process. If the polyethylene is crystallized in the all

6.8

THERMODYNAMICS OF FUSION

303

trans conformation, and two gauche plus the trans are possible in the melt (see Section 2.1.2), then the polymer goes from one possible conformation to three on melting (150,151). From equation (3.13), DS = R ln W = R ln 3 = 9.13 J mol K (6.48)

The agreement between the classical and statistical results, equations (6.47) and (6.48), is seen to be excellent, noting the approximations involved. A more general statistical thermodynamic theory can be obtained with the quasi-lattice models; see Figure 3.3. If a coordination number z of the lattice is assumed, then there are z - 1 choices of where to put the next bond in the chain. (This is a little smaller with excluded volume considered.) Then the entropy varies with dimensionality of the quasi-lattice according to 3-D: DS f = R ln 5 = 13.4 J mol K 2 -D: DS f = R ln 3 = 9.13 J mol K 1-D: DS f = R ln 1 = 0 (6.49) (6.50) (6.51)

If more than one group needs to be considered, the values are multiplicative, rather than additive. Taking two CH2 groups, for example, yields nine conformations, rather than six. The general equation can be written DS = R ln( Aa BbC c L) (6.52)

where A, B, C, . . . are the number of ways the various moieties can be arranged in space, and a, b, c, . . . are the number of appearances of the moiety in each mer. Values of entropy of fusion are shown in Table 6.9 (146).While the entropies per mer varied widely, as might be expected from the enormous differences in the sizes and structures of the units, values divided by the number of chain bonds about which free rotation is permitted gave more nearly uniform values. According to Flory (152), the congurational entropy of fusion per segment should be R ln(Z - 1), where Z is the coordination number of the lattice. Values of E.u./No. bonds permitting rotation in Table 6.9 are in rough agreement with Florys calculation. Based on equation (6.37), it is easy to understand why large heats of fusion produce high melting polymers (see Table 6.1). The quantity E.u. represents entropy units per mer. In experiments such as the above, heating and cooling are usually done very slowly. Therefore regime I structures may predominate. The melting temperature is higher under these conditions than when cooling or heating is rapid, in which case regime II and III kinetics apply.

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THE CRYSTALLINE STATE

Table 6.9

Entropies of fusion for various polymers (146)

Entropy of fusion, J/molK E.u./mol of Repeating Unit 8.37 25.9 145 57.3 E.u./No. Bonds Permitting Rotation 8.37 13.0 6.3 5.0

Polymer

Repeating Unit

Polyethylene CH2 Cellulose tributyrate C18H28O18 Poly(decamethylene sebacate) O(CH2)10OCO(CH2)8CO Poly(N,N-sebacoylpiperazine)

CH2CH2 N CH2CH2 N CO(CH2)8CO

6.8.5

The HoffmanWeeks Equilibrium Melting Temperature

There are several denitions of the equilibrium melting temperature currently in use. According to equation (6.42) the highest melting temperature (and presumably the equilibrium melting temperature) is reached at innite molecular weight. Another denition assumes innitely thick crystalline lamellae (153); see Section 6.7.4. According to Hoffman and Weeks (154) the equilibrium melting temperature of a polymer, T* f , is dened as the melting point of an assembly of crystals, each of which is so large that surface effects are negligible and that each such large crystal is in equilibrium with the normal polymer liquid. Furthermore the crystals at the melting temperature must have the equilibrium degree of perfection consistent with the minimum free energy at T* f. While this denition holds for most pure compounds, polymers as ordinarily crystallized tend to melt below T* f because the crystals are small and all too imperfect. Thus the temperature of crystallization, usually still lower because of supercooling (see Figure 6.3), has an important inuence on the experimentally observed melting point. Hoffman and Weeks (154) found the following relation to hold: T f* - T f = f (T f* - Tc ) (6.53)

where f represents a stability parameter that depends on crystal size and perfection. The quantity f may assume all values between 0 and 1, where f = 0 implies that Tf = T* f , whereas f = 1 implies that Tf = Tc. Therefore crystals are 1 most stable at f = 0 and inherently unstable at f = 1. Values of f near 2 are common. The experiment generally involves rapidly cooling the polymer from the melt to some lower temperature, Tc, where it is then crystallized isothermally.

6.9 EFFECT OF CHEMICAL STRUCTURE ON THE MELTING TEMPERATURE

305

Figure 6.40 Idealized Hoffman-Weeks plot, showing the extrapolation to Tf*.

For higher crystallization temperatures the polymer forms more perfect crystals; that is, it is better annealed. Hence its melting temperature increases. To determine T* f , a plot of Tc versus Tf is prepared (154) (Figure 6.40). A line is drawn where Tc = Tf. The experimental data are extrapolated to the intersection with the line. The temperature of intersection is T* f. 6.9 EFFECT OF CHEMICAL STRUCTURE ON THE MELTING TEMPERATURE The actual values of the enthalpy and entropy of fusion are, of course, controlled by the chemical structure of the polymer. The most important interand intramolecular structural characteristics include structural regularity, bond exibility, close packing ability, and interchain attraction (155,156). In general, high melting points are associated with highly regular structures, rigid molecules, close packing capability, strong interchain attraction, or several of these factors combined. The effect of structural irregularities can be illustrated by a study of polyesters (156) having the general structure O C O C O R O
n

(6.54)

when R is CH2CH2, the structure is Dacron. The melting temperature depends on the regularity of the group R. For aliphatic groups, the size and regularity of R are both important: R CH2 CH2 CH2 3 CH CH2 CH3 T f , C 265 220 Noncrystalline