Melt blending of commercial linear polyethylene with low-entangled ultra-high molecular weight polyethylene: From dispersion compatibility to viscoelastic scaling laws

Abstract

This study investigates the dispersion and compatibility of low-entangled “dis-entangled” UHMWPE (dis-UH) in a high-density polyethylene (HDPE) matrix using solvent-free melt-blending conditions and compares it with entangled UHMWPE (eUH) in the same matrix. The findings reveal that dis-UH/HDPE exhibits a significantly lower viscosity ratio than eUH/HDPE (1 and 4, respectively), indicating a lower critical capillary number (Ca_critical), thus enhanced dispersion and compatibility. Blends with varying dis-UH content up to 20 wt% show homogeneity, evidenced by DSC and SEM analysis, and demonstrate improved mechanical properties by 36 % in the maximum stress (σ_max) and 39 % in Young's modulus (E). Linear viscoelasticity assessments reveal that higher dis-UH content slow the dynamics and increase the apparent weight average molecular weight (M_w), consistent with previous reports for linear entangled PE. The zero-shear viscosity (${\eta }_0)$ scaling with M_w (η₀ $\propto$ M ⁿ) is adjusted for high polydispersity, yielding a transitional point in the scaling exponent (n) from 3.6 to 3 at a reptation number of entanglement segments (M_r/M_e) of ∼287, in line with theoretical predictions. To rationalize the success of the homogenization process, we propose a qualitative molecular picture inspired from the constraint release Rouse mechanism involved in the disorientation process of bi-disperse linear polymers. In the case of dis-UH/HDPE blends, with initially lower density of long-long entanglements within dis-UH, and the highest density of short-short entanglements within HDPE matrix, the formation of long-short entanglements between dis-UH and HDPE is facilitated, which results in successful homogenization process. In the contrary, the establishment of long-short entanglements in eUH/HDPE blends will require unwinding of the long-long entanglements, which holds a higher kinetic barrier compared to dis-UH/HDPE blends, leading to unsuccessful homogenization.