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the full curve in g. 5.1. The sharp peaks are due to the crystalline material and the broad background to the amorphous material. Various methods can be used to estimate the shape of the amorphous contribution under the peaks, shown by the dotted line. The ratio of the total scattered intensity within the sharp rings to that within the amorphous halos is then easily calculated, provided that the sample is not oriented, and in principle gives the ratio of crystalline to amorphous material. In practice a number of corrections must be made, one of which is that the observed intensity must be multiplied by an angular factor that takes account of the polarisation of the scattered X-rays at dierent angles 2. This is important because the crystalline and amorphous contributions are dierent at dierent angles. Other corrections that must be made include a correction for incoherent scattering, which is independent of the crystalline or amorphous nature of the material, and a correction for crystal imperfections, including thermal vibrations. For oriented samples it is necessary to perform three-dimensional scans.

5.3 Crystallites
The most obvious question that needs to be answered about polymer crystallites is question (i) of section 5.1, How can long molecules give rise to small crystallites?. Two principal types of answer have been given; they lead to the fringed-micelle model and the chain-folded model for polymer crystallites. A further type of crystallite, the chain-extended crystal, can also occur when samples are prepared in special ways. These three types of crystallite are considered in the following sections.

Fig. 5.1 Determination of crystallinity from X-ray scattering. The full curve shows the observed X-rayscattering intensity as a function of 2, where  is the Bragg angle and 2 is the angle between the incident and scattered Xray beams. The dashed curve indicates the estimated contribution of the amorphous material. (Adapted by permission of IUCr.)

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Example 5.1 Calculate the volume and mass crystallinities of a sample of polypropylene of density 910 kg m3 assuming that the densities of the crystalline and amorphous regions are 936 and 853 kg m3 , respectively. Solution Equation (5.2) shows that v s a 910 853 57 0:69 c a 936 853 83

and equation (5.1) shows that m c 936 57  0:71 s v 910 83

5.3.1 The fringed-micelle model

The fringed-micelle model was an early attempt to inter-relate long molecules, small crystals and a sea of amorphous material. It was proposed in 1930, by Hermans and others, to explain the structure of gelatin and was subsequently applied to natural rubber. It is now believed to be incorrect as the basic model for polymer crystallites, but it is worth describing for historical reasons and because it may be a good approximation to the true structure in special cases. The essentials of the model are illustrated in g. 5.2. The model suggests the occurrence of brillar crystallites, which can grow both parallel and perpendicular to the chain axes. Each chain
Fig. 5.2 A schematic diagram showing fringed-micelle crystallites.

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typically passes through several crystallites and small crystallites can thus be reconciled with long chains.

5.3.2 Chain-folded crystallites

This type of crystallisation was rst suggested by Storks in 1938. He made lms of gutta percha 27 nm thick by evaporation from solution. Electron diraction showed that the lms were composed of large crystallites with the chain axes normal to the plane of the lm. The only possibility was that the chains folded back and forth upon themselves, so that adjacent segments were parallel and in crystal register. This idea lay dormant until the early 1950s, but then very small single crystals of polymers were produced from dilute solutions. These crystals were regularly shaped and of lateral dimensions up to 0.3 mm, but their thicknesses were only about 12 nm. When they were rotated between crossed polarisers in the polarising microscope, they gave uniform extinction, i.e. darkness, at a certain angle, which proved that they were indeed single crystals. Studies by Keller and his group using electron diraction showed that the chain axes were parallel to the thickness direction of these lamellar crystals and, once again, the only possibility was chain folding. Figure 5.3 shows examples of solution-grown crystals of polyethylene. Shortly afterwards (in 1957) Fischer showed by electron microscopy that the crystallites in melt-grown spherulites of polyethylene and nylon were most likely to be lamellar rather than brillar, as would be expected from the fringed-micelle model. It is now accepted that chain-folded lamellar crystallites play an important part in the structure of most ordinary

Fig. 5.3 Electron micrographs of single crystals of polyethylene crystallised from dilute solution in xylene: (a) diamond-shaped crystals and (b) truncated crystals. (Reprinted by permission of John Wiley & Sons, Inc.)

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crystalline polymers. Figure 5.4(a) shows schematically how the chains fold in a perfect chain-folded crystallite. The following topics are now considered briey: (i) (ii) (iii) (iv) the production of single crystals from solution, the description of solution-grown crystals, the nature of the chain folds and the crystal surfaces and the reason for the observed form of solution-grown crystals of polyethylene.

Discussion of the reason for chain folding is deferred until section 5.6.3. (i) Production of single crystals from solution They form in super-cooled dilute solution, e.g. 0.01% of linear polyethylene in p-xylene at 70 8C, and appear as a suspension, which can be sedimented and examined by optical or electron microscopy. The rst systematic observations were on linear polyethylene, but many other polymer single crystals have now been obtained in a similar way. (ii) Description of solution-grown crystals of polyethylene When they are grown at sucient dilution, the crystallites approximate to lamellae with a uniform thickness of about 12 nm, the precise value depending on the temperature of growth. Electron diraction shows that the chain axes are approximately perpendicular to the planes of the lamellae. The crystals are not exactly at, but have a hollow-pyramidal structure, with the chain axes parallel to the pyramid axis. This pyramidal structure is seen clearly in g. 5.5, which shows a single crystal of polyethylene oating in solution. This should be compared with g. 5.3(b), which shows similar crystals attened on an electron-microscope grid. The dark lines on the crystals in g. 5.3(b) show where the pyramid has broken when the crystal attened. When crystals are grown at low temperature their outlines are bounded by straight (planar) growth faces, in the simplest cases (110)-type faces, as shown in g. 5.3. When the growth temperature is higher, the faces can

Fig. 5.4 Schematic diagrams showing (a) regular chain folding with adjacent re-entry, as envisaged for a perfect chain-folded crystallite; and (b) the switchboard model.

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Fig. 5.5 A single crystal of polyethylene floating in solution, showing the pyramidal form. (Reprinted with permission from Elsevier Science.)

become curved, leading to a shape rather like an ellipse but pointed at the ends of the long axis. (iii) The nature of chain folds and of crystal surfaces Three questions arise. (a) Are the folds loose or sharp? (b) Is adjacent reentry the main mechanism for folding? (c) Are all fold lengths the same, i.e. is the fold surface smooth? Keller originally suggested that solution-grown crystals exhibited regular sharp folding with adjacent re-entry (see g. 5.4(a)). A later model with irregular re-entry, the switchboard model, was proposed by Flory and is illustrated in g. 5.4(b). (The name arises from the similarity in the appearance of the crystal surface in this model to the criss-crossing of the wires on an old-fashioned manual telephone switchboard.) Evidence for the nature of the chain folding has been obtained from experiments using selective degradation of the crystalline material by nitric acid, from infrared-absorption measurements and from neutron-scattering experiments. On treatment of the crystalline polymer with fuming nitric acid the chains are cut at the crystal surface, because the acid rst dissolves the amorphous material at the surface and then attacks the surface itself but cannot readily penetrate the bulk of the crystallites. Gel-permeation chromatography of the degraded material gives the resultant distribution of chain lengths. The results showed that there were several well-dened lengths for solution-grown crystals, which could be interpreted as showing that they were formed by sharp folding with adjacent re-entry. Melt-grown crystallites gave much less clear results. The infrared-absorption spectra of mixed crystals of ordinary polyethylene, CH2 n , and fully deuterated polyethylene, CD2 n , yielded information about adjacent re-entry through correlation splitting, which is due to the in- and out-of-phase vibration of the two chains in the unit cell, as

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discussed in section 4.3. The results are dicult to analyse, but the principle is that correlation splitting is seen only if the two chains in the unit cell are identical. This will happen more frequently for mixed crystals if adjacent re-entry is the rule, giving adjacent chains of the same type, rather than random re-entry, for which adjacent chains are likely to be of dierent types. For solution-grown crystals adjacent re-entry was found to predominate, with a probability of about 0.75 for folding along (110) planes (the predominant growth faces), whereas for melt-grown crystals adjacent reentry probably occurs quite frequently, but much less regularly. Mixtures of short-chain parans exhibit a random arrangement of the molecules containing hydrogen or deuterium. These results are consistent with those from nitric-acid-etching experiments and data from neutron-scattering experiments also support them. Figure 5.6 shows photographs of a model of a possible sharp chain fold in polyethylene involving four gauche bonds. Various pieces of evidence suggest that the fold surfaces are not perfectly regular, particularly for melt-crystallised materials. Buried folds exist up to 2.5 nm below the surface, but the number of sharp folds increases as the overall surface is reached and there are many folds near the mean lamellar

Fig. 5.6 A model of a polyethylene chain folded using four gauche bonds, as suggested by Frank. Upper, view normal to the plane of folding; lower, view along the plane of folding. (Reprinted by permission from John Wiley & Sons Limited.)

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surface. Outside this there are loose chain ends and long loops (nonadjacent re-entry). In melt-crystallised material tie molecules pass from one lamella to adjacent ones in the multi-layer stacks that are generally found in such material. There is thus an amorphous layer between the crystal lamellae. As the molar mass increases chain folding becomes less regular and the degree of crystallinity also falls, because the freedom of the chains to rearrange themselves on crystallisation decreases. There is evidence from neutron-scattering experiments that lamellar crystallisation from the melt can occur without signicant change of overall molecular dimensions, such as the radius of gyration. A model that ts this evidence and incorporates the ideas described above is shown in g. 5.7. Lamellar stacks are discussed further in section 5.4.3. (iv) The reason for the pyramidal form of solution-grown crystals of polyethylene Figure 5.8 shows schematically the arrangement of the chains within a solution-grown single crystal. When the chains fold back and forth parallel to the (110)-type faces, they can be imagined to produce at ribbons of folded chains, which in the various sectors of the crystal are at angles to one another determined by the angles between the dierent sets of (110)type planes. If the fold lies slightly out of the plane of the ribbon, as suggested in the lower part of g. 5.6, the close packing of these folded ribbons within a sector will require an oset of one ribbon with respect to the previous ribbon in the direction of the chain axes. This accounts for the hollow-pyramidal form of the crystallites and shows that the chain axes will lie parallel to the axis of the pyramid. Packing of adjacent folds within one folded ribbon may also require a displacement within the plane of the ribbon in order to obtain close packing, so that the length of the ribbon is not normal to the chain axes. In this case the base of the pyramid will not be at, unlike that of the pyramid shown in g. 5.8.

Fig. 5.7 The solidification model of the crystallisation process, showing how a chain can be incorporated into a lamellar structure without significant change of overall shape. (Reproduced by permission of IUPAC.)

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Fig. 5.8 A schematic diagram of chain folding in a solution-grown single crystal of polyethylene. (Reproduced from The Vibrational Spectroscopy of Polymers by D. I. Bower and W. F. Maddams. # Cambridge University Press 1989.)

As the chain folds it must twist through 908 so that the chains are in correct crystal register (see g. 4.17(b)) and, although the various sectors of the crystal grow by chain folding in dierent planes, there is no discontinuity of crystal structure across the sector boundaries, as is shown most simply by uniform extinction in the polarising microscope.

5.3.3 Extended-chain crystallites

Extended, or fully extended, chain crystallites contain straight chains at least 200 nm long and have been obtained for only a few polymers, such as polytetrauoroethylene (PTFE), polyethylene and polychlorotriuoroethylene, using special crystallisation techniques. Extended-chain polytetrauoroethylene can be obtained by slow crystallisation from the melt; the other two are obtained by crystallisation from the melt under elevated pressure. Solution crystallisation has so far not been shown to give rise to extended-chain crystals. These materials tend to be very brittle because, although they are highly crystalline, there are few inter-crystalline linking molecules. Figure 5.9 shows an electron micrograph of a replica of a fracture surface of extended-chain crystalline material of polychlorotriuoroethylene. The lamellae are about 12 mm thick and there appears to be no limit on the lateral dimensions of the crystallites except space and availability of material.

5.4 Non-crystalline regions and polymer macroconformations 5.4.1 Non-crystalline regions

The non-crystalline regions of polymers are usually called amorphous, but they may sometimes have some kind of organisation and they may certainly be oriented, as discussed in chapters 10 and 11. They are the