Comparative study of size and distribution of lamellar thicknesses and long periods in polyethylene with a shish-kebab structure

This study contains a combined application of three different techniques for the study of injection moulded polyethylene (PE), showing an oriented shish-kebab structure: small angle X-ray scattering (SAXS), low frequency Raman spectroscopy (LAM) and transmission electron microscopy (TEM). A series of linear PEs and molecular weights in the range 51 000-478 000 has been investigated and two injection temperatures have been used (T-m = 144 and 210 degrees C). SAXS patterns from the highly oriented regions show the presence of either one axial long period (L(1)) or two (L(1) and L(2)) depending on molecular weight ((M) over bar(w)) and T-m. It is shown that L(1) and L(2) increase with (M) over bar(w) up to a given critical molecular weight (M) over bar(c). Above (M) over bar(c), L(1) and L(2) remain constant. Raman results qualitatively confirm the existence of two separate distributions of straight-length chain segments for those samples having molecular weights above the critical value. Shorter segments are shown to be more abundant than the longer ones. In the lowest molecular weight sample, results from SAXS, TEM and Raman spectroscopy seem to be consistent with each other, although in some cases a tilted molecular arrangement within the lamellae has to be invoked. On the other hand, in case of the highest molecular weight sample, the length of the short straight-chain segments derived from Raman spectroscopy agrees well with the double periodicity obtained from SAXS. On the contrary, long periods measured from TEM only correspond to the shorter SAXS periodicity. This result is discussed by assuming the occurrence of crystalline bridges among adjacent lamellae.