Crystalline polymers cold-drawing

Polymers <100% crystalline Regularity of structure needed for high crystallinity Stretching Cold drawing... 

Dilatometric studies have demonstrated the negative thermal expansivity for many oriented crystalline polymers 64,170 176). The results of these experimental studies may be summarized as follows. Cold-drawing of PE below Tm 172) and solid-state extrusion under elevated pressure 170 1711 lead to a monotonous decrease of the positive thermal expansion coefficient with increasing draw ratio. At a certain degree of orientation, dependent on temperature, PM becomes negative with Pi < Pell (Fig. 16). This is the second way of reaching negative expansivity applied, e.g. to POM (w = 63 % Tdr = 423 K) 173>. 

An oriented crystalline polymer usually has a much higher tensile strength than the unoriented polymer. Cold drawing is an important step in the production of synthetic fibers. 

As noted in Fig. 14.1 (a), commercial fibers of semicrystallme polymers are always cold-drawn after spinning to achieve further structuring through further macromolecular orientation and crystalline morphological changes, many of which are retained because of the low temperature of the cold-drawing processes. A typical stress-strain curve for a polycrystalline polymer at a temperature Tg < T < Tm appears in Fig. 14.6. 

Let s start by looking at a simple polymer, polyethylene, that has a lot going on in its stress/strain plots (Figure 13-38). Flexible, semi-crystalline polymers such as this (where the T of the amorphous domains is below room temperature) usually display a considerable amount of yielding or cold-drawing, as long as they are not stretched too quickly. For small deformations, Hookean elastic-type behavior (more or less) is observed, but beyond what is called the yield point irreversible deformation occurs. 

Orientation of semicrystalline polymers below the melting point is often referred to as "cold drawing." Although some stress crystallization does occur, the process primarily involves the transformation of existing crystalline structures. A widely accepted model of the deformation mechanism is that provided by Peterlin (Figure 5) (41). Prior to necking, the crystal lamellae which... 

The break-up of crystallites and the reformation of the lamellar fragments into microfibrUs is the basis of a theory for the cold-drawing of isotropic semi-crystalline polymers due to Peterlin. " (See also Hosemann et and Robertson .) Both Peterlin and Hosemann assert that the main mechanism is the break-up of each crystallite into approximately twenty smaller units which lie like pearls on a string with their chain axes parallel to the IDD. Many aspects of these theories would seem to be relevant to the deformation of oriented polymers of modest draw ratios. 

The orientation in the direction of applied stress occurs also in amorphous materials. The amorphous polymers, like the crystalline ones, also exhibit increased strength in the direction of orientation. If there is a small amount of crystallinity in polymers, the crystallinity often increases as a result of cold drawing. 

---