Polynomial functions for direct calculation of the surface free energy developed from the Neumann Equation of State method

TL;DR

This paper develops polynomial functions for direct calculation of surface free energy from contact angle measurements using the Neumann Equation of State, simplifying and improving the accuracy of such calculations.

Contribution

It introduces polynomial fits to the EQS for direct and general calculation of surface free energy, addressing discrepancies and sensitivity issues in existing methods.

Findings

Discrepancies among three EQS versions are significant at high contact angles.

Polynomial fits enable quick, accurate calculations with low error margins.

Sensitivity to contact angle uncertainty varies with probe liquid and surface energy.

Abstract

The Neumann Equation of State (EQS) allows obtaining the value of the surface free energy of a solid ${\gamma}_{SV}$ from the contact angle $({\theta})$ of a probe liquid with known surface tension ${\gamma}_{LV}$. The value of ${\gamma}_{SV}$ is obtained by numerical methods solving the corresponding EQS. In this work, we analyzed the discrepancies between the values of ${\gamma}_{SV}$ obtained using the three versions of the EQS reported in the literature. The condition number of the different EQS was used to analyze their sensitivity to the uncertainty in the ${\theta}$ values. Polynomials fit to one of these versions of EQS are proposed to obtain values of ${\gamma}_{SV}$ directly from contact angles $({\gamma}_{SV} ({\theta}))$ of particular probe liquids. Finally, a general adjusted polynomial is presented to obtain the values of ${\gamma}_{SV}$ not restricted to a particular probe liquid $({\gamma}_{SV}({\theta},{\gamma}_{LV}))$. Results showed that the three versions of EQS present non-negligible discrepancies, especially at high values of ${\theta}$. The sensitivity of the EQS to the uncertainty in the values of ${\theta}$ is very similar in the three versions and depends on the probe liquid used (greater sensitivity at higher ${\gamma}_{LV})$ and on the value of ${\gamma}_{SV}$ of the solid (greater sensitivity at lower ${\gamma}_{SV})$. The discrepancy of the values obtained by numerical resolution of both the fifth-order fit polynomials and the general fit polynomial was low, no larger than ${\pm}0.40\,mJ/m^{2}$. The polynomials obtained allow the analysis and propagation of the uncertainty of the input variables in the determination of ${\gamma}_{SV}$ in a simple and fast way.