248

THE CRYSTALLINE STATE

2. By measuring the polarized infrared spectra of oriented semicrystalline polymers, information about both the molecular and crystal structure can be obtained. Both uniaxially and biaxially oriented samples can be studied. 3. The regular arrangement of polymer molecules in a crystalline region can be treated theoretically, utilizing the symmetry properties of the chain or crystal. With the advent of modern computers, the normal modes of vibrations of crystalline polymers can be calculated and compared with experiment. 4. Deuteration of specic groups yields information about the extent of the contribution of a given group to specic spectral bands. This aids in the assignment of the bands as well as the identication of bands owing to the crystalline and amorphous regions. 6.2.5 Raman Spectra

Although Raman spectra have been known since 1928, studies on high polymers and other materials became popular only after the development of efcient laser sources. According to Tadokoro (18), some of the advantages of Raman spectra are the following: 1. Since the selection rules for Raman and infrared spectra are different, Raman spectra yield information complementary to the infrared spectra. For example, the SS linkages in vulcanized rubber and the C=C bonds yield strong Raman spectra but are very weak or unobservable in infrared spectra. 2. Since the Raman spectrum is a scattering phenomenon, whereas the infrared methods depend on transmission, small bulk, powdered, or turbid samples can be employed. 3. On analysis, the Raman spectra provide information equivalent to very low-frequency measurements, even lower than 10 cm-1. Such lowfrequency studies provide information on lattice vibrations. 4. Polarization measurements can be made on oriented samples. Of course, much of the above is widely practiced by spectroscopists on small molecules as well as big ones. Again, it must be emphasized that polymer chains are ordinary molecules that have been grown long in one direction.

6.3

THE UNIT CELL OF CRYSTALLINE POLYMERS

When polymers are crystallized in the bulk state, the individual crystallites are microscopic or even submicroscopic in size. They are an integral part of the solids and cannot be isolated. Hence studies on crystalline polymers in the

6.3

THE UNIT CELL OF CRYSTALLINE POLYMERS

249

bulk were limited to powder diagrams of the Debye-Scherrer type, or ber diagrams of oriented materials. It was only in 1957 that Keller (19) and others discovered a method of preparing single crystals from very dilute solutions by slow precipitation. These too were microscopic in size (see Section 6.4). However, X-ray studies could now be carried out on single crystals, with concomitant increases in detail obtainable. Of course a major difference between polymers and low-molecular-weight compounds relates to the very existence of the macromolecules long chains. These long chains traverse many unit cells. Their initial entangled nature impedes their motion, however, and leaves regions that are amorphous. Even the crystalline portions may be less than perfectly ordered. This section describes the structure of the unit cell in polymers, principally as determined by X-ray analysis. The following sections describe the structure and morphology of single crystals, bulk crystallized crystallites, and spherulites and develops the kinetics and thermodynamics of crystallization. 6.3.1 Polyethylene

One of the most important polymers to be studied is polyethylene. It is the simplest of the polyolens, those polymers consisting only of carbon and hydrogen, and polymerized through a double bond. Because of its simple structure, it has served as a model polymer in many laboratories. Also polyethylenes great commercial importance as a crystalline plastic has made the results immediately usable. It has been investigated both in the bulk and in the single-crystal state. The unit cell structure of polyethylene was rst investigated by Bunn (20). A number of experiments were reviewed by Natta and Corradini (21). The unit cell is orthorhombic, with cell dimensions of a = 7.40, b = 4.93, and c = 2.534 . The unit cell contains two mers (see Figure 6.5) (22). Not unexpectedly, the unit cell dimensions are substantially the same as those found for the normal parafns of molecular weights in the range 300 to 600 g/mol.The chains are in the extended zigzag form; that is, the carboncarbon bonds are trans rather than gauche. The zigzag form may also be viewed as a twofold screw axis. The single-crystal electron diffraction pattern shown in Figure 6.5 was obtained by viewing the crystal along the c-axis.Also shown is the single-crystal structure of polyethylene, which is typically diamond-shaped (see below). The unit cell is viewed from the c-axis direction, perpendicular to the diamonds. 6.3.2 Other Polyolen Polymers

Because of the need for regularity along the chain, only those vinyl polymers that are either isotactic or syndiotactic will crystallize. Thus isotactic

250

THE CRYSTALLINE STATE

Figure 6.5 A study of polyethylene single-crystal structure. (a) A single crystal of polyethylene, precipitated from xylene, as seen by electron microscopy. (b) Electron diffraction of the same crystal, with identical orientation. (c) Perspective view of the unit cell of polyethylene, after Bunn. (d ) View along chain axis. This latter corresponds to the crystal and diffraction orientation in (a) and (b) (22). Courtesy of A. Keller and Sally Argon.

polypropylene crystallizes well and is a good ber former, whereas atactic polypropylene is essentially amorphous. The idea of a screw axis along the individual extended chains needs developing. Such chains may be viewed as having an n/p-fold helix, where n is the number of mer units and p is the number of pitches within the identity period. Of course, n/p will be a rational number. Some of the possible types of helices for isotactic polymers are illustrated in Figure 6.6 (23). Group I of Figure 6.6 has a helix that makes one complete turn for every three mer units, so n = 3 and p = 1. Group II shows seven mer units in two turns, so n = 7 and p = 2. Group III shows four mer units per turn. Of course, both left- and right-handed helices are possible. The isotactic hydrocarbon polymers in question occur as enantiomorphic pairs that face each other, a closer packing being realized through the operation of a glide plane with translation parallel to the ber axis. The enantiomorphic crystal structure of polybutene-1 is illustrated in Figure 6.7 (21). Note that better packing is achieved through the chains having the opposite sense of helical twist.

6.3

THE UNIT CELL OF CRYSTALLINE POLYMERS

251

Figure 6.6

Possible types of helices for isotactic chains, with various lateral group (23).

Figure 6.7 Enantiomorphous mode of packing polybutene-1 chains in a crystal (21).

252

THE CRYSTALLINE STATE

6.3.3

Polar Polymers and Hydrogen Bonding

The hydrocarbon polymers illustrated above are nonpolar, being bonded together only by van der Waalstype attractive forces. When the polymers possess polar groups or hydrogen bonding capability, the most energetically favored crystal structures will tend to capitalize on these features. Figure 6.8 (24) illustrates the molecular organization within crystallites of a polyamide, known as polyamide 66 or nylon 66. The chains in the crystallites are found to occur as fully extended, planar zigzag structures. X-ray analysis reveals that poly(ethylene terephthalate) (Dacron) belongs to the triclinic system (25). The cell dimensions are a = 4.56, b = 5.94, c = 10.75 , with the angles being a = 98.5, b = 118, g = 112. Both the polyamides and the aromatic polyesters are high melting polymers because of hydrogen bonding in the former case and chain stiffness in the latter case (see Table 6.1). As is well known, both of these polymers make excellent bers and plastics.

Figure 6.8 (24).

The hydrogen-bonded structure of polyamide 66. The unit cell face is shown dotted

6.3

THE UNIT CELL OF CRYSTALLINE POLYMERS

253

The polyethers are a less polar group of polymers. Poly(ethylene oxide) will be taken as an example (26). Four (7/2) helical molecules pass through a unit cell with parameters a = 8.05, b = 13.04, c = 19.48 , and b = 125.4 with the space group P21/a - C2h. [Space groups are discussed by Tadokoro (27,28). These symbols represent the particular one of the 230 possible space groups to which poly(ethylene oxide) belongs; see Section 6.2.] Table 6.2 (27) summarizes the crystallographic data of some important polymers. Several polymers have more than one crystallographic form. Polytetrauoroethylene (Teon), for example, undergoes a rst-order crystal crystal transition at 19C. 6.3.4 Polymorphic Forms of Cellulose

A few words have already been said about the crystalline structure of cellulose (see Figure 6.1). The monoclinic unit cell structure illustrated for cellulose I was postulated many years ago by Meyer et al. (36) and has been conrmed many times. The b axis is the ber direction, and the cell belongs to the space group P2, containing four glucose residues. The triclinic structure is also known. Note that the structure shown in Figure 6.1a illustrates the chains running in alternating directions, up and down, now not thought true for most celluloses. The assumption of all one way or of alternating opposite directions is very important in the development of crystalline models (see below). As shown further in Figure 6.1b, c, four different polymorphic forms of crystalline cellulose exist. Cellulose I is native cellulose, the kind found in wood and cotton. Cellulose II is made either by soaking cellulose I in strong alkali solutions (e.g., making mercerized cotton) or by dissolving it in the viscose process, which makes the labile but soluble cellulose xanthate. The regenerated cellulose II products are known as rayon for the ber form and cellophane for the lm form. Cellulose III can be made by treating cellulose with ethylamine. Cellulose IV may be obtained by treatment with glycerol or alkali at high temperatures (29,30). Going from the polymorphic forms of cellulose back to cellulose I is difcult but can be accomplished by partial hydrolysis. The subject of the polymorphic forms of cellulose has been reviewed (10,11). 6.3.5 Principles of Crystal Structure Determination

Through the use of X-ray analysis, electron diffraction, and the supporting experiments of infrared absorption and Raman spectroscopy, much information has been collected on crystalline polymers. Today, the data are analyzed through the use of computer techniques. Somewhere along the line, however, the investigator is required to use intuition to propose models of crystal structure. The proposed models are then compared to experiment. The models are gradually rened to produce the structures given above. It must be

254 Crystal System, Space Group, Lattice Constants, and Number of Chains per Unit Cella Planar zigzag (2/1) Planar zigzag (2/1) 1.00 0.998 Molecular Conformation Crystal Density (g/cm3) 2.35 2.30 2.55 Planar zigzag (2/1) 2.74 0.936 0.922 0.939 1.13 Stable form, orthorhombic, Pnam-D 16 2h , a = 7.417 , b = 4.945 , c = 2.547 , N = 2 Metastable form, monoclinic, C2/m - C 3 2h, a = 8.09 , b (f.a.) = 2.53 , c = 4.79 , b = 107.9, N = 2 High-pressure form, orthohexagonal (assumed), a = 8.42 , b = 4.56 , c (f.a.) has not been determined Below 19C, pseudohexagonal (triclinic), a = b = 5.59 , c = 16.88 , g = 119.3, N = 1 Above 19C, trigonal, a = 5.66 , c = 19.50 , N = 1 Helix (13/6) 163.5 Helix (15/7) 165.8 Planar zigzag (2/1) High-pressure form I12, orthorhombic, Pnam-D16 2h, a = 8.73 , b = 5.69 , c = 2.62 , N = 2 High-pressure form II,193 monoclinic, B2/m-C2h,3 a = 9.50 , b = 5.05 , c = 2.62 , g = 105.5, N = 2 4 a-Form, monoclinic, C2/c-C6 2h of Cc-C s, a = 6.65 , b = 20.96 , c = 6.50 , b = 9920, N = 4 b-Form, hexagonal, a = 19.08 , c = 6.49, N = 9
6 g-Form, trigonal, P3121-D4 3 or P3221-D 3, a = 6.38 , c = 6.33 , N = 1 6 Trigonal, R3c-C6 3v or R3c-D 3d, a = 21.90 , c = 6.65 , N = 6

Table 6.2

Selected crystallographic data (27)

Polymer

Polyethylene

CH2

CH2

Polytetrauoroethylene

CF2

CF2

it-Polypropylene

CH

CH2

CH3

it-Polystyrene

CH

CH2

Helix (3/1) (TG)3 Helix (3/1) (TG)3 Helix (3/1) (TG)3 Helix (3/1) (TG)3

C6H5

cis-1,4-Polyisoprene
CH2
n

-cis-S TS, (2/0) cis-STS Planar zigzag Planar zigzag (2/1) Planar zigzag (2/1)

1.02 1.42 1.11 1.23 1.17 1.24

CH2

C(CH3)

CH

Poly(vinyl chloride)

CHCl

CH2

Polytetrahydrofuran

(CH2)4

Polyamide 6

(CH2)5

CONH

Polyamide 66
CO
n

Helix (2/1) )2 (T4STS Planar zigzag (1/0) Planar zigzag (1/0) Helix (7/2) Planar zigzag (2/1) Planar zigzag (1/0) Nearly planar

NH

(CH2)6NHCO

(CH2)4

1.248 1.228 1.197 1.196 1.455

Poly(ethylene oxide)

CH2

CH2

Poly(ethylene terephthalate)
CO
n

(CH2)2

CO

Monoclinic, P21/a-C5 2h, a = 12.46 , b = 8.89 , c = 8.10 , b = 92, N = 4 Orthorhombic, Pcam-D11 2h, a = 10.6 , b = 5.4 , c = 5.1 , N = 2 Monoclinic, C2/c-C6 2h, a = 5.59 , b = 8.90 , c = 12.07 , b = 134.2, N = 2 a-Form, monoclinic, P21-C 2 2, a = 9.56 , b (f.a.) = 17.2 , c = 8.01 , b = 67.5, N = 4 g-Form, monoclinic, P21/a-C5 2h, a = 9.33 , b (f.a.) = 16.88 , c = 4.78 , b = 121, N = 2 -C1 a-Form, triclinic, P1 i, a = 4.9 , b = 5.4 , c = 17.2 , a = 48.5, b = 77, g = 63.5, N = 1 -C1 b-Form, triclinic, P1 i, a = 4.9 , b = 8.0 , c = 17.2 , a = 90, b = 77, g = 67, N = 2 Form I, monoclinic, P21/a-C5 2h, a = 8.05 , b = 13.04 , c = 19.48 , b = 125.4, N = 4 -C1 Form II, triclinic, P1 i, a = 4.17 , b = 4.44 , c = 7.12 , a = 62.8, b = 93.2, g = 111.4, N = 1 -C1 b-Form, triclinic, P1 i, a = 4.9 , b = 8.0 , c = 22.4 , a = 90, b = 77, g = 67, N = 2 -C1 Triclinic, P1 i, a = 4.56 , b = 5.94 , c = 10.75 , a = 98.5, b = 112, N = 1

255

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THE CRYSTALLINE STATE

emphasized, that the experiments do not yield the crystal structure; only researchers imagination and hard work yield that. However, it is possible to simplify the task. Natta and Corradini (23) postulated three principles for the determination of crystal structures, which introduce considerable order into the procedure. These are: 1. The Equivalence Postulate. It is possible to assume that all mer units in a crystal occupy geometrically equivalent positions with respect to the chain axis. 2. The Minimum Energy Postulate. The conformation of the chain in a crystal may be assumed to approach the conformation of minimum potential energy for an isolated chain oriented along an axis. 3. The Packing Postulate. As many elements of symmetry of isolated chain as possible are maintained in the lattice, so equivalent atoms of different mer units along an axis tend to assume equivalent positions with respect to atoms of neighboring chains. The equivalence postulate is seen in the structures given in Figure 6.6. Here, the chain mers repeat their structure in the next unit cell. Energy calculations made for both single molecules and their unit cells serve three purposes: (a) they clarify the factors governing the crystal and molecular structure already tentatively arrived at experimentally, (b) they suggest the most stable molecular conformation and its crystal packing starting from the individual mer chemical structure, and (c) they provide a collection of reliable potential functions and parameters for both intra- and intermolecular interactions based on well-dened crystal structures (27). An example of intermolecular interactions is hydrogen bonding in the polyamide structures described in Figure 6.8. The packing postulate is seen at work in Figure 6.7, where enantiomorphic structures pack closer together in space than if the chains had the same sense of helical twist. Last, one should not neglect the very simple but all important density. The crystalline cell is usually about 10% more dense than the bulk amorphous polymer. Signicant deviations from this density must mean an incorrect model. Because of the importance of polymer crystallinity generally, and the unit cell in particular, the subject has been reviewed many times (17,21,27,3141). 6.4 6.4.1 STRUCTURE OF CRYSTALLINE POLYMERS The Fringed Micelle Model

Very early studies on bulk materials showed that some polymers were partly crystalline. X-ray line broadening indicated that the crystals were either very