Revisiting the measurements and interpretations of DLVO forces

TL;DR

This paper critically re-examines DLVO force measurements, identifying widespread anomalies caused by misunderstandings and systematic errors, and calls for careful re-analysis to advance colloid and interface science.

Contribution

It provides a comprehensive explanation for anomalous DLVO force results and emphasizes the need for re-evaluation considering systematic errors and proper EDL theory understanding.

Findings

Anomalous fitted potentials often exceed theoretical limits.

Measured van der Waals forces vary greatly across studies.

Systematic errors and misunderstandings cause pervasive anomalies.

Abstract

The DLVO theory and electrical double layer (EDL) theory are the foundation of colloid and interface science. With the invention and development of surface forces apparatus (SFA) and atomic force microscope (AFM), the measurements and interpretations of DLVO forces (i.e., mainly measuring the EDL force (electrostatic force) FEDL and van der Waals force FvdW, and interpreting the potential {\psi}, charge density {\sigma}, and Hamaker constant H) can be greatly facilitated by various surface force measurement techniques, and would have been very promising in advancing the DLVO theory, EDL theory, and colloid and interface science. However, although numerous studies have been conducted, pervasive anomalous results can be identified throughout the literature, main including: (1) the fitted {\psi}/{\sigma} is normally extremely small ({\psi} can be close to or (much) smaller than {\psi}{\zeta} (zeta potential)) and varies greatly; (2) the fitted {\psi}/{\sigma} can exceed the allowable range of calculation; and (3) the measured FvdW and the fitted H vary greatly. Based on rigorous and comprehensive arguments, we have reasonably explained the pervasive anomalous results in the literature and further speculated that, the pervasive anomalous results are existing but not noticed and questioned owing to the two important aspects: (1) the pervasive unreasonable understandings of EDL theory and (2) the commonly neglected systematic errors. Consequently, we believe that the related studies have been seriously hampered. We therefore call for re-examination and re-analysis of related experimental results and theoretical understandings by careful consideration of the EDL theory and systematic errors. On these bases, we can interpret the experimental results properly and promote the development of EDL theory, colloid and interface science, and many related fields.