Spherulitic

Figure 4.12 Spherulites of poly( 1-propylene oxide) observed through crossed Polaroid filters by optical microscopy. See text for significance of Maltese cross and banding in these images. [From J. H. MaGill, Treatise on Materials Science and Technology, Vol. lOA, J. M. Schultz (Ed.), Academic, New York, 1977, with permission.]...

They possess spherical symmetry around a center of nucleation. This symmetry projects a perfectly circular cross section if the development of the spherulite is not stopped by contact with another expanding spherulite. 

A system of mutually impinging spherulites develop into an array of irregular polyhedra, the dimensions of which can be as large as a centimeter or so. 

The individual spherulite shows up by the characteristic Maltese cross optical pattern under crossed Polaroids, although the Maltese cross is truncated in the event of impinging spherulites. 

Spherulites have been observed in organic and inorganic systems of synthetic, biological, and geological origin, including moon rocks, and are therefore not unique to polymers. 

A larger number of smaller spherulites are produced at larger undercoolings, a situation suggesting nucleation control. Various details of the Maltese cross pattern, such as the presence or absence of banding, may also depend on the temperature of crystallization. 

The molecular chain folding is the origin of the Maltese cross which identifies the spherulite under crossed Polaroids. The Maltese cross is known to arise from a spherical array of birefringent particles through the following considerations ... 

The ordered polymer chains are consistently oriented perpendicularly to the radius of the spherulite. 

Figure 4.13 Schematic illustration of the leading edge of a lathlike crystal within a spherulite.

Items (1) and (2) mean that the refractive index in the tangential direction of the spherulite is generally greater than that along the radius. 

If the Polaroid filters are held fixed and the sample rotated between them, the Maltese cross remains fixed because of the symmetry of the spherulite. 

The presence of spherulites or smaller crystallites is comparable to cross-linking and affects not only the moduli and compliances, but also the ultimate properties such as yield strength and ultimate elongation. 

Practical appHcations have been reported for PVP/ceUulosics (108,119,120) and PVP/polysulfones (121,122) in membrane separation technology, eg, in the manufacture of dialysis membranes. Electrically conductive polymers of polyaruline are rendered more soluble and hence easier to process by complexation with PVP (123). Addition of small amounts of PVP to nylon 66 and 610 causes significant morphological changes, resulting in fewer but more regular spherulites (124). 

Figure 3.6). This theory known as the fringed mieelle theory or fringed crystallite theory helped to explain many properties of crystalline polymers but it was difficult to explain the formation of certain larger structures such as spherulites which could possess a diameter as large as 0.1 mm. 

The properties of a given polymer will very much depend on the way in which crystallisation has taken place. A polymer mass with relatively few large spherulitic structures will be very different in its properties to a polymer with far more, but smaller, spherulites. It is thus useful to consider the factors affecting the formation of the initial nuclei for crystallisation (nucleation) and on those which affect growth. 

Polymers below the glass transition temperature are usually rather brittle unless modified by fibre reinforcement or by addition of rubbery additives. In some polymers where there is a small degree of crystallisation it appears that the crystallines act as knots and toughen up the mass of material, as in the case of the polycarbonates. Where, however, there are large spherulite structures this effect is more or less offset by high strains set up at the spherulite boundaries and as in the case of P4MP1 the product is rather brittle. 

The greater the percentage crystallinity the higher the yield point and tensile modulus. It has also been shown that by raising the quench temperature the spherulite size is increased and that this greatly decreases the impact toughness. 

In the case of the polycrystalline polyester thermoplastic rubbers the simple domain theory does not seem to apply. With these rubbers it would appear that they contain spherulitic structures consisting of 4GT radial lamellae with inter-radial amorphous regions that are mixtures of PTMEG soft segments and noncrystalline hard segments. 

The polymer is liable to depolymerisation at temperatures just above T. In the case of pure polymer there is a tendency for the few spherulites to grow to sizes up to 1mm diameter. Spherulite size may be reduced by the use of nucleating agents and by fast cooling. 

Amorphous stereotactic polymers can crystallise, in which condition neighbouring chains are parallel. Because of the unavoidable chain entanglement in the amorphous state, only modest alignment of amorphous polymer chains is usually feasible, and moreover complete crystallisation is impossible under most circumstances, and thus many polymers are semi-crystalline. It is this feature, semicrystallinity, which distinguished polymers most sharply from other kinds of materials. Crystallisation can be from solution or from the melt, to form spherulites, or alternatively (as in a rubber or in high-strength fibres) it can be induced by mechanical means. This last is another crucial difference between polymers and other materials. Unit cells in crystals are much smaller than polymer chain lengths, which leads to a unique structural feature which is further discussed below. 

Figure 8.1. (a) Spherulites growing in a thin film of isotactic polystyrene, seen by optical microscopy with crossed polars (from Bassett 1981, after Keith 196.3). (b) A common sequence of forms leading to sphertililic growth (after Bassett 1981). The fibres consist of zigzag polymer chains. 

Spherulites are to be distinguished from dendrimers, which also have spherical form. A dendrimer is a single molecule of a special kind of polymer which spreads from a nucleus by repeated branching. 

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