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METHODS OF DETERMINING CRYSTAL STRUCTURE

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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 The Weiss indexes have been replaced by the Miller indexes, which are obtained by taking the reciprocals of the Weiss coefcients and multiplying through by the smallest number that will express the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

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is said to possess a line of symmetry. Similarly, a crystal possesses a center of symmetry if every face has an identical atom at an equal distance on the opposite side of this center. On the basis of the total number of plane, line, and center symmetries, it is possible to classify the crystal types into six crystal systems, which may in turn be grouped into 32 classes and nally into 230 crystal forms. The scientists of the preX-ray period postulated that any macroscopic crystal was built up by repetition of a fundamental structural unit composed of atoms, molecules, or ions, called the unit crystal lattice or space group. This unit crystal lattice has the same geometric shape as the macroscopic crystal. This line of reasoning led to the 14 basic arrangements of atoms in space, called space lattices. Among these are the familiar simple cubic, hexagonal, and triclinic lattices. There are four basic methods in wide use for the study of polymer crystallinity: X-ray diffraction, electron diffraction, infrared absorption, and Raman spectra. The rst two methods constitute the fundamental basis for crystal cell size and form, and the latter two methods provide a wealth of supporting data such as bond distances and intermolecular attractive forces. These several methods are now briey described. 6.2.2 X-Ray Methods

In 1895 X-rays were discovered by Roentgen. The new X-rays were rst applied to crystalline substances in 1912 and 1913, following the suggestion by Von Laue that crystalline substances ought to act as a three-dimensional diffraction grating for X-rays. By considering crystals as reection gratings for X-rays, Bragg (15) derived his now famous equation for the distance d between successive identical planes of atoms in the crystal: d= nl 2 sin q (6.1)

where l is the X-ray wavelength, q is the angle between the X-ray beam and these atomic planes, and n represents the order of diffraction, a whole number. It turns out that both the X-ray wavelength and the distance between crystal planes, d, are of the order of 1 . Such an analysis from a single crystal produces a series of spots. However, not every crystalline substance can be obtained in the form of macroscopic crystals. This led to the DebyeScherrer (16) method of analysis for powdered crystalline solids or polycrystalline specimens. The crystals are oriented at random so the spots become cones of diffracted beams that can be recorded either as circles on a at photographic plate or as arcs on a strip of lm encircling the specimen (see Figure 6.4) (17). The latter method permits the study of back reections as well as forward reections.

6.2 METHODS OF DETERMINING CRYSTAL STRUCTURE

247

Figure 6.4 The DebyeScherrer method for taking powder photographs. The angle RSX is 2q, where q is the angle of incidence on a set of crystal planes (17).

Basically the intensity of the diffraction spot or line depends on the scattering power of the individual atoms, which in turn depends on the number of electrons in the atom. Other quantities of importance include the arrangement of the atoms with regard to the crystal planes, the angle of reection, the number of crystallographically equivalent sets of planes contributing, and the amplitude of the thermal vibrations of the atoms. Both the intensities of the spots or arcs and their positions are required to calculate the crystal lattice, plus lots of imagination and hard work. The subject of X-ray analysis of crystalline materials has been widely reviewed (14,17). 6.2.3 Electron Diffraction of Single Crystals

Electron microscopy provides a wealth of information about the very small, including a view of the actual crystal cell size and shape. In another mode of use, the electrons can be made to diffract, using their wavelike properties. In this regard they are made to behave like the neutron scattering considered earlier. In the case of X-ray studies, the polymer samples are usually uniaxially oriented and yield ber diagrams that correspond to single-crystal rotation photographs. Electron diffraction studies utilize single crystals. Since the polymer chains in single crystals are most often oriented perpendicular to their large at surface, diffraction patterns perpendicular to the 001 plane are common. Tilting of the sample yields diffraction from other planes. The interpretation of the spots obtained utilizes Braggs law in a manner identical to that of X-rays. 6.2.4 Infrared Absorption

Tadokoro (18) summarized some of the specialized information that infrared absorption spectra yield about crystallinity: 1. Infrared spectra of semicrystalline polymers include crystallizationsensitive bands. The intensities of these bands vary with the degree of crystallinity and have been used as a measure of the crystallinity.

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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