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Background  The Fourier space (reciprocal space) image of bulk polyethylene consists of lines superimposed on the coherent diffuse background. The mixed character of the image indicates the complex nature of these compounds. The inability in detecting full images of reciprocal space of polymeric substances without Compton radiation and the other undesirable diffuse scatterings has misled the structural analysis (structural characterisation) of these materials.    Principal Findings  We propose the use of anomalous diffractometry where, it is possible to obtain a real image of reciprocal space without Compton radiation and other undesirable scatterings. By using classical diffractometry techniques this procedure is not possible. This methodology permitted us to obtain the “Direct Delta function”, in the case of polycrystalline substances that was not previously detected. A new procedure was proposed to interpret the image of reciprocal space of bulk polyethylene. The results show the predominance of the geometry of local order determination compared to the crystal unit cell. The analysis of x-ray diffraction images illustrates that the elementary structural unit is a tetrahedron. This structural unit illustrates the atoms in the network scatter in a coherent diffuse manner. Moreover, the interference function derived from the coherent diffuse scattering dampens out quickly and the degree of randomness is superior to a liquid state. The radial distribution function derived from this interference function shows bond shortening in the tetrahedron configuration. It is this particular effect, which stabilises polyethylene.    Conclusion  Here we show by anomalous diffractometry that the traditional concept of the two-phase or the crystal-defect model is an oversimplification of the complex reality. The exploitation of anomalous diffractometry has illustrated that polyethylene has an intermediate ordered structure.

The Structural Dilemma of Bulk Polyethylene: An Intermediary Structure