Thermodynamic Characterization of Grease Oxidation–Thermal Stability via Pressure Differential Scanning Calorimetry

Abstract

This study investigates and characterizes, via thermodynamic laws, a widely employed standard for measuring oxidation-thermal stability of lubricating greases—ASTM 5483—based on first-order chemical kinetics, using pressure differential scanning calorimetry (PDSC). Steps and active mechanisms in the controlled test are analyzed and modeled using energy and entropy transformations. Applying the degradation-entropy generation (DEG) theorem, oxidation induction time is related to accumulated oxidation entropy and entropy transfer by mass flow to obtain characteristic degradation coefficients. These DEG coefficients are calibrated using available measured data from the literature and subsequently used to predict induction times at various temperatures. DEG elements—trajectories, planes, and domain—presented here consistently characterized all greases studied. Results show that the high-pressure entropy transfer by oxygen mass flow in the final step of the ASTM 5483 procedure is the primary contributor to oxidation induction time, verifying the significance of this process in accelerating antioxidant depletion, which would otherwise take months to years under atmospheric conditions. DEG-predicted induction times at various temperatures are compared to induction times predicted by the first-order chemical kinetics model, revealing a close match. The new DEG model is also herein used to predict induction times at atmospheric pressure, whereas the first-order kinetics model is independent of pressure and limited to the specific conditions in ASTM 5483. The DEG approach has useful implications for the accelerated and unaccelerated evaluation of grease oxidation stability and grease useful life.