The Challenges Facing the Current Paradigm Describing Viscoelastic Interactions in Polymer Melts
Authors: IBAR Jean Pierre 
Published: September 2023

Staudinger taught us that macromolecules were made up of the covalently bonded monomer repeat units chaining up as polymer chains. The chemical nature of the monomer directed the type of covalent bonds conferring most of the specific properties of the polymer. The more the number of repeat units the longer the chains and the more the possibility for the chains to assume a variety of shapes, from an extended elongated one to a more compact coiled one. Also, the chemical process that resulted in the synthesis of macromolecules produced many chains, often not with the same shape or size. The properties of the polymers improved when the chains became longer but it was more difficult to process them: their viscosity increased with molecular weight; viscosity was no longer an intensive property like it was for small liquids.

The main question raised in polymer physics remains: how do these long chains interact and move as a group when submitted to shear deformation at high temperature when they are viscous liquids? This question is debated in a field of polymer physics called RHEOLOGY, whose purpose is to understand the viscoelastic aspects of polymer melts deformation.

The current consensus is that we need to distinguish two cases: the deformation of “un-entangled chains” for macromolecules with molecular weight, M, smaller than Me, “the entanglement molecular weight”, and the deformation of “entangled” chains for M &gt; Me.

Several eminent scientists have extensively studied these 2 cases over the last 70 years. Paul J. Flory, in 1974, and Pierre-Gilles de Gennes, in 1991, have been awarded the Nobel Price in Chemistry and Physics, respectively, for their significant theoretical contribution to understand these challenging problems. For both of these authors the properties of polymers derive from the statistical characteristics of the macromolecule itself, the designated statistical system that defines the thermodynamic state of the polymer. Me, the molecular weight between entanglements, is defined from the rubber elasticity theory and is known to be equal to Mc/2 where Mc is the molecular weight for the entanglements when viscosity measurements are made. The current paradigm is that the viscoelasticity of un-entangled melts ( M &lt; Mc) is well described by the Rouse model and that the entanglement issues raised by the impact of the increase of the length of the macromolecules on the melt viscoelasticity, when M &gt; Mc, are well understood by the reptation model introduced by de Gennes and co-workers. Both models can be classified in the category of “chain dynamics statistics”.

In this paper we examine in details the failures and the current challenges facing the current paradigm of polymer rheology: the Rouse model for M &lt; Mc, the reptation model for M &gt; Mc, the time-temperature superposition principle, the strain induced time dependence of viscosity, shear-refinement and sustained-orientation. The basic failure of the current paradigm and its inherent inability to fully describe the experimental reality is documented in this paper.

In the discussion and conclusion of the paper we suggest that a different solution to explain the viscoelasticity of polymer chains and of their “entanglement” is needed. This requires a change of paradigm to describe the dynamics of the interactions within the chains and across the chains. A brief description of our currently proposed open dissipative statistical approach, “the Grain-Field Statistics”, is presented.