Polypropylene lamellae

Polypropylene molecules repeatedly fold upon themselves to form lamellae, the sizes of which ate a function of the crystallisa tion conditions. Higher degrees of order are obtained upon formation of crystalline aggregates, or spheruHtes. The presence of a central crystallisation nucleus from which the lamellae radiate is clearly evident in these stmctures. Observations using cross-polarized light illustrates the characteristic Maltese cross model (Fig. 2b). The optical and mechanical properties ate a function of the size and number of spheruHtes and can be modified by nucleating agents. Crystallinity can also be inferred from thermal analysis (28) and density measurements (29). 

Figure 19.4 Parallel stacks of lamellae in beta crystalline isotactlc polypropylene... 

The beta crystalline form of isotactic polypropylene differs from the alpha form by having a lower crystalline density and lower melting point. The beta form is metastable to the alpha form and will rearrange to the alpha structure when heated to approximately 100 °C or placed under strain. Beta lamellae form parallel stacks as shown in Fig. 19.4. 

The shape of macromolecules within a folded lamella is not the same for all polymers. In crystalline polyethylene, for example, the chains assume a planar zigzag conformation, but in some other polymers like polypropylene and polyoxymethylene the chains prefer a helical shape, as in proteins. The helix might have three, four, or five monomer units per turn, i.e., the helices are three-, four-, or five-fold (Fig. 1.12)... 

The structure of crystalline polymers may be significantly modified by the introduction of fillers. All aspects of the structure change on filling, crystallite and spherulite size, as well as crystallinity, are altered as an effect of nucleation [9]. A typical example is the extremely strong nucleation effect of talc in polypropylene [10,11], which is demonstrated also in Fig. 2. Nucleating effect is characterized by the peak temperature of crystallization, which increases significantly on the addition of the filler. Elastomer modified PP blends are shown as a comparison crystallization temperature decreases in this case. Talc also nucleates polyamides. Increasing crystallization temperature leads to an increase in lamella thickness and crystallinity, while the size of the spherulites decreases on... 

Spherulites. As a polymer melt solidifies, several folded chain lamellae spherulites form which are up to 0.1 mm in diameter. A typical example of a spherulitic structure is shown in Fig. 1.15. The spherulitic growth in a polypropylene melt is shown in Fig. 1.16. 

The chemical structure of a polymer determines whether it will be crystalline or amorphous in the solid state. Both tacticity (i.e., syndio-tactic or isotactic) and geometric isomerism (i.e., trans configuration) favor crystallinity. In general, tactic polymers with their more stereoregular chain structure are more likely to be crystalline than their atactic counterparts. For example, isotactic polypropylene is crystalline, whereas commercial-grade atactic polypropylene is amorphous. Also, cis-pol3nsoprene is amorphous, whereas the more easily packed rans-poly-isoprene is crystalline. In addition to symmetrical chain structures that allow close packing of polymer molecules into crystalline lamellae, specific interactions between chains that favor molecular orientation, favor crystallinity. For example, crystallinity in nylon is enhanced because of... 

Fig. 3.21 Tapping mode AFM phase image left) and height image right) of cross-hatched lamellae of iPP in elastomeric polypropylene and isotactic PP, respectively. The angles of 80° agree well with the theoretically predicted and experimentally confirmed value [53]. Reproduced with permission from [51]. Copyright 2002. American Chemical Society, and [54]...

Fig. 3 Epitaxial growth of high-density polyethylene on oriented polypropylene. Polyethylene lamellae aligns at a 40° angle with the direction of orientation of the polypropylene. The orientation direction of polypropylene in the micrograph is along the horizontal. (From Ref...

When polypropylene is water-quenched under eertain conditions, a difference in crystalline order is obtained. In air-quench systems, yarns with a crystallinity of around 55% are obtained. The crystals are usually distributed throughout the yarn as lamellae and are normally in the monoclinic a-form. In the rapidly cooling water-quench process, a less-ordered smectic or paracrystalline structure is produced with a morphology that is basically fibrillar. Under certain drawing conditions, these smectic structures lead to high-strength fibers. 

---