6

THE CRYSTALLINE STATE

6.1 GENERAL CONSIDERATIONS

In the previous chapter the structure of amorphous polymers was examined. In this chapter the study of crystalline polymers is undertaken. The crystalline state is dened as one that diffracts X-rays and exhibits the rst-order transition known as melting. A rst-order transition normally has a discontinuity in the volume temperature dependence, as well as a heat of transition, DHf, also called the enthalpy of fusion or melting. The most important second-order transition is the glass transition, Chapter 8, in which the volumetemperature dependence undergoes a change in slope, and only the derivative of the expansion coefcient, dV/dT, undergoes a discontinuity. There is no heat of transition at Tg, but rather a change in the heat capacity, DCp. Polymers crystallized in the bulk, however, are never totally crystalline, a consequence of their long-chain nature and subsequent entanglements. The melting (fusion) temperature of the polymer, Tf, is always higher than the glass transition temperature, Tg. Thus the polymer may be either hard and rigid or exible. An example of the latter is ordinary polyethylene, which has a Tg of about -80C and a melting temperature of about +139C. At room temperature it forms a leathery product as a result. The development of crystallinity in polymers depends on the regularity of structure in the polymer (see Chapter 2). Thus isotactic and syndiotactic polymers usually crystallize, whereas atactic polymers, with a few exceptions

Introduction to Physical Polymer Science, by L.H. Sperling ISBN 0-471-70606-X Copyright 2006 by John Wiley & Sons, Inc.

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THE CRYSTALLINE STATE

Table 6.1 Properties of selected crystalline polymers (1)

Polymer Polyethylene Poly(ethylene oxide) it-Polystyrene Poly(vinyl chloride) Poly(ethylene terephthalate)b Poly(hexamethylene adipamide)c Cellulose tributyrate cis-Polyisoprened Polytetrauoroethylenee it-Polypropylene Poly(oxymethylene)f
a b

Tf, C 139 66 240 212 265 265 207 28 330 171 182

DHf,

kJ mol

7.87a 8.29 8.37 3.28 24.1 46.5 12.6 4.40 5.74 8.79 10.6

Per CH2CH2. Note that values for CH2 alone are sometimes reported. Dacron. c Nylon 66 or Polyamide 66. d Natural rubber. e Teon. f Delrin.

(where the side groups are small or highly polar), do not. Regular structures also appear in the polyamides (nylons), polyesters, and so on, and these polymers make excellent bers. Nonregularity of structure rst decreases the melting temperature and nally prevents crystallinity. Mers of incorrect tacticity (see Chapter 2) tend to destroy crystallinity, as does copolymerization. Thus statistical copolymers are generally amorphous. Blends of isotactic and atactic polymers show reduced crystallinity, with only the isotactic portion crystallizing. Under some circumstances block copolymers containing a crystallizable block will crystallize; again, only the crystallizable block crystallizes. Factors that control the melting temperature include polarity and hydrogen bonding as well as packing capability. Table 6.1 lists some important crystalline polymers and their melting temperatures (1). 6.1.1 Historical Aspects Historically the study of crystallinity of polymers was important in the proof of the Macromolecular Hypothesis, developed originally by Staudinger. In the early 1900s when X-ray studies were rst applied to crystal structures, scientists found that the cell size of crystalline polymers was of normal size (about several ngstoms on a side). This was long before they developed an understanding of the chain nature of polymers required to completely characterize the cell contents. In the case of ordinary sized organic molecules, each cell was

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GENERAL CONSIDERATIONS

241

found to contain only a few molecules. If polymers were composed of long chains, they asked Staudinger, how could they t into the small unit cells? The density of such a material would have to be 50 times lead! The answer, developed by Mark and co-workers (27), and others, was that the unit cell contains only a few mers that are repeated in adjacent unit cells. The molecule continues in the adjacent axial directions. Mark showed that the bond distances both within a cell and between cells were consistent with covalent bond distances (1.54 for carboncarbon bonds) and inconsistent with the formation of discrete small molecules. For these and many other advances (see Section 3.8), and a life-long leadership in polymers (he died at age 96 in 1992), Herman Mark was called the Father of Polymer Science. One of the rst structures to be determined was the natural polysaccharide cellulose. In this case the repeat unit is cellobiose, composed of two glucoside rings. In the 1980s, 13C NMR experiments established that native cellulose is actually a composite of a triclinic parallel-packed unit cell called cellulose Ia, and a monoclinic parallel-packed unit cell called cellulose Ib. Experimentally, the structures are only difcultly distinguishable via X-ray analysis (7a, 7b). Figure 6.1 (3) illustrates the general form of the cellulose unit cell. When vinyl, acrylic, and polyolen polymers were rst synthesized, the only microstructure then known was atactic. Most of these materials were amorphous. Scientic advancement waited until Zieglers work on novel catalysts (8), together with Nattas work on X-ray characterization of the stereospecic polymers subsequently synthesized (9), when isotactic and syndiotactic crystalline polymers became known. For this great pioneering work, Ziegler and Natta were jointly awarded the 1963 Nobel Prize in Chemistry (see Appendix 5.3). The general class of these catalysts are known today as ZieglerNatta catalysts. Of course, crystalline polymers constitute many of the plastics and bers of commerce. Polyethylene is used in lms to cover dry-cleaned clothes, and as water and solvent containers (e.g., wash bottles). Polypropylene makes a highly extensible rope, nding particularly important applications in the marine industry. Polyamides (nylons) and polyesters are used as both plastics and bers. Their use in clothing is world famous. Cellulose, mentioned above, is used in clothing in both its native state (cotton) and its regenerated state (rayon). The lm is called cellophane. 6.1.2 Melting Phenomena

The melting of polymers may be observed by any of several experiments. For linear or branched polymers, the sample becomes liquid and ows. However, there are several possible complications to this experiment, which may make interpretation difcult. First of all, simple liquid behavior may not be immediately apparent because of the polymers high viscosity. If the polymer is cross-linked, it may not ow at all. It must also be noted that amorphous polymers soften at their glass transition temperature, Tg, which is emphatically not

Figure 6.1 The crystalline structure of cellulose. (a) The unit cell of native cellulose, or cellulose I, as determined by X-ray analysis (2,10,11). Cellobiose units are not shown on all diagonals for clarity. The volume of the cell is given by V = abc sin b. (b) Unit cell dimensions of the four forms of cellulose. (c) Known pathways to change the crystalline structure of cellulose. The lesser known form of cellulose x is also included (10).

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GENERAL CONSIDERATIONS

243

a melting temperature but may resemble one, especially to the novice (see Chapter 8). If the sample does not contain colorants, it is usually hazy in the crystalline state because of the difference in refractive index between the amorphous and crystalline portions. On melting, the sample becomes clear, or more transparent. The disappearance of crystallinity may also be observed in a microscope, for example, between crossed Nicols. The sharp X-ray pattern characteristic of crystalline materials gives way to amorphous halos at the melting temperature, providing one of the best experiments. Another important way of observing the melting point is to observe the changes in specic volume with temperature. Since melting constitutes a rstorder phase change, a discontinuity in the volume is expected. Ideally, the melting temperature should give a discontinuity in the volume, with a concomitant sharp melting point. In fact, because of the very small size of the crystallites in bulk crystallized polymers (or alternatively, their imperfections), most polymers melt over a range of several degrees (see Figure 6.2) (12). The melting temperature is usually taken as the temperature at which the last trace of crystallinity disappears. This is the temperature at which the largest and/or

Figure 6.2 Specic volumetemperature relations for linear polyethylene. Open circles, specimen cooled relatively rapidly from the melt to room temperature before fusion experiments; solid circles, specimen crystallized at 130C for 40 days, then cooled to room temperature prior to fusion (12).

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THE CRYSTALLINE STATE

Figure 6.3 Differential scanning calorimetry of a commercial isotactic polypropylene sample, generously provided by Dr. S. J. Han of the Exxon Research and Engineering Company. Note the supercooling effect on crystallization, but the equal and opposite heats of melting and crystallization (13). Experiment by S. D. Kim.

most perfect crystals are melting. The volumetric coefcients of expansion in Figure 6.2 can be calculated from a = (1/V ) (dV/dT )p. Alternatively, the melting temperature can be determined thermally. Today, the differential scanning calorimeter (DSC) is popular, since it gives the heat of fusion as well as the melting temperature. Such an experiment is illustrated in Figure 6.3 for it-polypropylene (13). The heat of fusion, DHf, is given by the area under the peak. Further general studies of polymer fusion are presented in Sections 6.8 and 6.9, after the introduction of crystallographic concepts and the kinetics and thermodynamics of crystallization. 6.1.3 Example Calculation of Percent Crystallinity Exactly how crystalline is the it-polypropylene in Figure 6.3? The heat of fusion, DHf, of the whole sample, amorphous plus crystalline parts, is 97.2 J/g, determined by the area under the melting curve. Table 6.1 gives the heat of fusion for it-polypropylene as 8.79 kJ/mol.This latter value is for the crystalline component only. Noting that it-polypropylene has a mer molecular weight of 42 g/mol, 8790 J mol = 209 J g 42 g mol Then the percent crystallinity is given by 97.2 J g 100 = 46% crystallinity 209 J g

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245

Many semicrystalline polymers are between 40% and 75% crystalline. (See Section 6.5.4 for further information.)

6.2 6.2.1

METHODS OF DETERMINING CRYSTAL STRUCTURE A Review of Crystal Structure

Before beginning the study of the structure of crystalline polymers, the subject of crystallography and molecular order in crystalline substances is reviewed. Long before X-ray analysis was available, scientists had already deduced a great deal about the atomic order within crystals. The science of geometric crystallography was concerned with the outward spatial arrangement of crystal planes and the geometric shape of crystals. Workers of that day arrived at three fundamental laws: (a) the law of constancy of interfacial angles, (b) the law of rationality of indexes, and (c) the law of symmetry (14). Briey, the law of constancy of interfacial angles states that for a given substance, corresponding faces or planes that form the external surface of a crystal always intersect at a denite angle. This angle remains constant, independent of the sizes of the individual faces. The law of rationality of indexes states that for any crystal a set of three coordinate axes can be chosen such that all the faces of the crystal will either intercept these axes at denite distances from the origin or be parallel to some of the axes. In 1784 Hauy showed that it was possible to choose among the three coordinate axes unit distances (a, b, c) of not necessarily the same length. Furthermore, Hauy showed that it was possible to choose three coefcients for these three axesm, n, and pthat are either integral whole numbers, innity, or fractions of whole numbers such that the ratio of the three intercepts of any plane in the crystal is given by (ma: nb: pc). The numbers m, n, and p are known as the Weiss indexes of the plane in question. The Weiss indexes have been replaced by the Miller indexes, which are obtained by taking the reciprocals of the Weiss coefcients and multiplying through by the smallest number that will express the reciprocals as integers. For example, if a 1 plane in the Weiss notation is given by a : b : 4 c, the Miller indexes become a : 0b : 4c, thus more simply written (104), which is the modern way of expressing the indexes in the Miller system of crystal face notation. The third law of crystallography states that all crystals of the same compound possess the same elements of symmetry. There are three types of symmetry: a plane of symmetry, a line of symmetry, and a center of symmetry (14). A plane of symmetry passes through the center of the crystal and divides it into two equal portions, each of which is the mirror image of the other. If it is possible to draw an imaginary line through the center of the crystal and then revolve the crystal about this line in such a way as to cause the crystal to appear unchanged two, three, four, or six times in 360 of revolution, then the crystal