Plastics spherulites

In this study the influence of plasticizer content on the rate of crystallization was briefly investigated. The time needed for the first spherulites to appear on heating the plasticized polymer at 190°C. was used as a rough indication of the crystallization tendency. 

Previous work hod shown that low temperature coke is formed from cools hooted to between 450° and 500° C. by a process of nudeation and growth of spherical bodies in the plastic vitrinite. An essentially similar process has now been found to occur with coke-oven and petroleum pitches, with polyvinyl chloride, and with some polynuclear hydrocarbons, all of which yield carbons which grophitize readily at high temperatures. The process is probably general for the initial stages of formation of such carbons from the liquid phase. Some control of the solidification process has been achieved on the laboratory scale, and the physical and chemical structure of the spherulites has been investigated. 

Another technique used for obtaining macroscopically polar films involves mechanical extension of the material. Uniaxial plastic deformation induces a destruction of the original spherulitic structure into an array of crystallites in which the molecules are oriented in the deformation direction. In case of PVF2 when such deformation takes place below 90 °C the original tg+ tg chains are forced into their most extended possible conformation which is all-trans [32]. 

Such information offers an opportunity to study details of the fibrillation mechanism. The fibers formed by stretching the spherulitic polymer representing nothing other than ribbon formations plastically deformed and oriented towards the mechanical stress that is released by comparatively weak mutual interconditions existing in an earlier formation (Figure 3). This behavior points to the existence of some weak surfaces in the crystalline polymers. Elements of the super-molecular structure detached by action of the external mechanical forces can slide on the weak surfaces. Evidence for the strain-destruction relationship must come from studies of the modification of the contact surfaces of two neighboring spherulites under mechanical stress. 

Rupture occurs without important plastic deformation when the ribbons of some neighboring spherulitic formations show a parallel orientation in the contact zone. Conversely, considerable elongation occurs when the orientation is normal at the contact limit because of plastic deformation of the ribbons (Figures 4 through 6). 

Deformation of the spherulites in the material between the crazes into a highly stretched, ellipsoidal shape (rig. 13b in a tensile test of a bulk PP specimen this internal deformation condition is found at nominal plastic strains of more than... 

Looking at the structure of these crack tip plastic zones in more detail, it is found that the individual crazes are less straight compared to the low temperature crazes (Fig. 21). This indicates a more pronounced influence of the crystalline microstructure on craze formation. Figure 21a and b demonstrate for fine spherulitic, highly isotactic PP the interaction between the crazes and the microstructural features. Most of the... 

As pointed out above, the semicrystalline polymer can be considered as a two-phase composite of amorphous regions sandwiched between hard crystalline lamellae (Fig. 4.2(a)). Crystal lamellae ( c) are normally 10-25 nm thick and have transverse dimensions of 0.1-1 pm while the amorphous layer thickness, a, is 5-10 nm. As mentioned in the previous section, melt-crystallized polymers generally exhibit a spherulitic morphology in which ribbon-like lamellae are arranged radially in the polycrystalline aggregate (Bassett, 1981). Since the indentation process involves plastic yielding under the stress field of the indenter, microhardness is correlated to the modes of deformation of the semicrystalline polymers (see Chapter 2). These... 

---