Computation of Shear Viscosity by a Consistent Method in Equilibrium Molecular Dynamics Simulations: Applications to 1-Decene Oligomers

Author(s)

Mercier Franco, Luis Fernando ; Firoozabadi, Abbas

• Document type: Journal article
• Source: Journal of Physical Chemistry B; v. 127, n. 46, p. 9-pg., 2023-11-09.

Abstract

Accurate computation of shear viscosity is fundamental for describing fluid flow and designing and developing new processes. Poly-alpha-olefins (PAO's), particularly from 1-decene, have been applied to a variety of industrial processes. Recently, these molecules have been applied as carbon dioxide thickeners, enhancing carbon dioxide viscosity, which is important in carbon dioxide injection, either for enhanced oil recovery or sequestration in geological formations. For these applications, knowledge of the pure oligomer viscosity is crucial to design and operate the oligomer upstream pipelines before mixing them with carbon dioxide. Using Green-Kubo formalism with equilibrium molecular dynamics simulations, two methods are presented in the literature to generate the traceless, symmetric pressure tensor. In this work, we show that these two methods provide different values of shear viscosity, from the analysis of how the diagonal components of the traceless, symmetric pressure tensor are computed in each method. Then, we examine the consistency and correctness of each method: one is found to be consistent. The other is corrected by scaling the fluctuations of the diagonal components. Shear viscosities of supercritical carbon dioxide, vapor and liquid n-pentane, and liquid n-decane are computed to illustrate the analysis. We also apply the consistent method to compute the viscosity of 1-decene oligomers, including for the first time larger-than-dimer oligomers (trimer, tetramer, hexamer, and decamer). (AU)

• FAPESP's process: 18/02713-8 - Molecular dynamics of confined fluids: equilibrium and transport properties
• Grantee: Luís Fernando Mercier Franco
• Support Opportunities: Research Grants - Young Investigators Grants