Non Linear Rheology for Long Chain Branching characterization, comparison of two methodologies : Fourier Transform Rheology and Relaxation.

In this study we compare three rheological ways for Long Chain Branching (LCB) characterization of a broad variety of linear and branched polyethylene compounds. One method is based on dynamical spectrometry in the linear domain and uses the van Gurp Palmen plot. The two other methods are both based on non linear rheology (Fourier Transform Rheology (FTR) and chain orientation/relaxation experiments). FTR consists in the Fourier analysis of the shear stress signal due to large oscillatory shear strains. In the present work we focus on the third and the fifth harmonics of the shear stress response. Chain orientation/relaxation experiment consists in the analysis of the polymer relaxation after a large step strain obtained by squeeze flow. In this method, relaxation is measured by dynamical spectrometry and is characterized by two relaxation times related to LCB. All methods distinguish clearly the group of linear polyethylene from the group of branched polyethylene. However, FTR and Chain orientation/relaxation experiments show a better sensitivity than the van Gurp Palmen plot. Non linear experiments seem suitable to distinguish long branched polyethylene between themselves.