How to measure a solid-solid surface energy?

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I have done some searching and found out that there is a technique that has been around for roughly 10 years already and it is surprisingly simple (if you have the right, expensive, equipment). It can be found in this JCIS paper (which is also freely available here).

The technique works as follows: an atomic force microscope (AFM) with a well-defined spherical tip made out of solid 1 is brought into contact with solid 2. Then the tip is pulled of the surface again and the work of adhesion is measured. Based on the pull-off force and theoretical contact mechanics models (for details see the paper) you can calculate the surface energy $\gamma$ between the two solids from the following equation: $$ \gamma = \frac{F}{2\pi c R} $$ where $F$ is the pull-off force, $R$ is the tip radius and $c$ is a constant between 1.5 and 2 depending on the details of the contact model. The paper explains how to choose which model is appropriate for the type of measurement you do.

Some conditions (assumptions) for the theoretical models apply:

  1. deformations of materials are purely elastic, described by classical continuum elasticity theory
  2. materials are elastically isotropic
  3. both Young’s modulus and Poisson’s ratio ofmaterials remain constant during deformation
  4. the contact diameter between particle and substrate is small compared to the diameter of particle
  5. a paraboloid describes the curvature of the particle in the particle–substrate contact area
  6. no chemical bonds are formed during adhesion
  7. contact area significantly exceeds molecular/atomic dimensions

The paper explains in quite some details how deviations from these conditions are often source of error, but also how they can be met to get an appropriate measurement.

So to conclude: the surface energy of a solid-solid system can be measured using AFM when taking into account that the assumptions of models used in data processing are thoroughly met.

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Updated on March 08, 2020

Comments

  • Michiel
    Michiel over 3 years

    Many techniques exist to measure the surface energy between a liquid and a liquid or a liquid and a gas (see e.g. the wiki page).

    Methods to measure the surface energy between a solid and a fluid are rare, but still there is a method developed by Zisman (see e.g. here) that allows you to at least estimate it by extrapolation for solid/gas or solid/liquid, depending on the environment that you use in your experiment

    What I wonder: is there a method to measure the surface energy between two non-elastic solids?

    One option I could think of is that you could melt one of the solids and then use the technique of Zisman, but this will limit your knowledge to high temperature surface energy, whereas the ones at low temperature are the thing you are typically interested in.

    EDIT: just for future reference, this is a study on surface energies between 2 solids, but with 1 being highly elastic

    • Luboš Motl
      Luboš Motl over 10 years
      Just a terminological issue that may actually be more than terminological: we never speak of surface tension involving solids. en.wikipedia.org/wiki/Surface_tension Surface tension only applies to liquids; the notion of "surface energy" is more general and may appear for solids, too. But because the surface isn't trying to reshape and "stretch" for solids, because it's solid, and it's doing it for liquids, surface tension is a term for liquids only.
    • Michiel
      Michiel over 10 years
      That is actually a good point. I normally use the terms somewhat interchangeable, but I agree that in case of solids it doesn't make much sense to talk about surface tension
    • Mark Rovetta
      Mark Rovetta over 10 years
      Think about high-temperature creep experiments using very fine-grained polycrystalline samples to measure the thermal activation energy of pure diffusion creep. You might be able to estimate the average inter-granular surface energy using a diffusion-creep law.
    • Michiel
      Michiel over 10 years
      I don't really understand how that would work. Could you expand a bit?! And doesn't this have the same issue as melting the material, i.e. you get the surface energy at way to high temperatures?
    • Michiel
      Michiel over 10 years
      @MarkRovetta could you explain this creep experiment?!
    • Mark Rovetta
      Mark Rovetta over 10 years
      This was just a thought. At small grain sizes, the rate of grain-growth and diffusion creep, might be determined by the creation or annihilation of "vacancies and interstitials" near moving grain-boundary. Thermally activated rate (Arrhenius law) and rate measurements of the process might estimate the effective activation energy. A model of the process it might estimate an average formation energy for grain boundary. At best an estimate of an average, grain-boundary energy for a multi-phase polycrystal. See Diffusion creep