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A method based on the Gibbs' adsorption isotherm is developed to calculatethe decrease in interfacial free energy resulting from solute segregation at aninternal interface, built on measured concentration profiles. Utilizingatom-probe tomography (APT), we first measure a concentration profile of therelative interfacial excess of solute atoms across an interface. To accomplishthis we utilize a new method based on J. W. Cahn's formalism for thecalculation of the Gibbs interfacial excess. We also introduce a method tocalculate the decrease in interfacial free energy that is caused by thesegregating solute atoms. This method yields a discrete profile of the decreasein interfacial free energies, which takes into account the measuredconcentration profile and calculated Gibbsian excess profile. We demonstratethat this method can be used for both homo- and hetero-phase interfaces andtakes into account the actual distribution of solute atoms across an interfaceas determined by APT. It is applied to the case of the semiconducting systemPbTe-PbS 12 mol.%-Na 1 mol.%, where Na segregation at the PbS/PbTe interface isanticipated to reduce the interfacial free energy of the {100} facets. We alsoconsider the case of the nickel-based Alloy 600, where B and Si segregation aresuspected to impede inter-granular stress corrosion cracking (IGSCC) at homo-(GB) and hetero-phase metal carbide (M7C3) interfaces. The concentrationprofiles associated with internal interfaces are measured by APT using anultraviolet (wavelength = 355 nm) laser to dissect nanotips on an atom-by-atomand atomic plane-by-plane basis.

An integral method for the calculation of the reduction in interfacial free energy due to interfacial segregation