Polynomial functions for direct calculation of the surface free energy developed from the Neumann equation of state method

Abstract

The Neumann Equation of State (EQS) allows obtaining the value of the surface free energy of a solid (γSV) from the contact angle (θ) of a probe liquid with known surface tension (γLV). The value of γSV is obtained by numerical methods solving the corresponding EQS. In this work, we analyzed the discrepancies between the values of γSV 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 θ values. Polynomials fit to one of these versions of EQS are proposed to obtain values of γSV directly from contact angles (γSV(θ)) of particular probe liquids. Finally, a general adjusted polynomial is presented to obtain the values of γSV not restricted to a particular probe liquid (γSV(θ,γLV)). Results showed that the three versions of EQS present non-negligible discrepancies, especially at high values of θ. The sensitivity of the EQS to the uncertainty in the values of θ is very similar in the three versions and depends on the probe liquid used (greater sensitivity at higher γLV) and on the value of γSV of the solid (greater sensitivity at lower γSV). 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 ±0.40 mJ/m2. The polynomials obtained allow the analysis and propagation of the uncertainty of the input variables in the determination of γSV in a simple and fast way.