Structural disorder in the alpha form of isotactic polypropylene

A detailed analysis of the Bragg as well as of the diffuse X-ray diffractio n scattering of isotactic polypropylene (i-PP) fiber samples, suitably crys tallized in the ct form under different conditions, is reported. A limit-or dered (alpha (2) form) and a limit-disordered (alpha (1) form) model struct ure have been described to account for the features of the experimental Xra y diffraction profiles of i-PP samples prepared in the a form. The disorder consists of the statistical occupation of the lattice sites of isomorphous helices having opposite up/down orientations. Depending on the conditions of crystallization, intermediate-disordered modifications between the Limit -ordered and the limit-disordered, can be obtained. The analysis of the Bra gg contribution to the X-ray diffraction scattering of isotactic polypropyl ene samples crystallized in the ct form provides direct quantitative inform ation regarding the amount of up/down disorder, whereas the analysis of the diffuse scattering subtending the Bragg reflections in the case of oriente d samples may provide detailed information on the development of the up/dow n disorder within the unit cell. Fiber samples annealed at high temperature s (similar to 170 degreesC), hence recrystallized slowly, and thus nearer t o thermodynamic equilibrium, show X-ray diffraction patterns very close to that of the ideal limit-ordered model structure for the ex form (alpha (2) form). Almost perfect order is maintained inside the bilayers, as in the li mit-ordered structural model, and only 5-10% of defects in the relative ori entation (up or down) of the helices belonging to adjacent bilayers along b is probably present. The presence of this Bind of defect is consistent wit h the chain-folding scheme proposed in past literature. In the case of unan nealed fiber samples, a large amount of up/down disorder is also present wi thin the bilayers, giving rise, in the case of samples crystallized at lowe r temperatures, to situations very close to the limit-disordered model stru cture. We assume that the chain folding might not develop according to the scheme proposed in the Literature for kinetic reasons.