This paper reviews the fundamental concepts and the terminology of wetting. In particular, it focuses on high temperature wetting phenomena of primary interest to materials scientists. We have chosen to split this review into two sections: one related to macroscopic (continuum) definitions and the other to a microscopic (or atomistic) approach, where the role of chemistry and structure of interfaces and free surfaces on wetting phenomena are addressed. A great deal of attention has been placed on thermodynamics. This allows clarification of many important features, including the state of equilibrium between phases, the kinetics of equilibration, triple lines, hysteresis, adsorption (segregation) and the concept of complexions, intergranular films, prewetting, bulk phase transitions versus “interface transitions”, liquid versus solid wetting, and wetting versus dewetting.

/pdf/a-review-of-wetting-versus-adsorption-complexions-and-2rni10tbod.pdf

A review of wetting versus adsorption, complexions, and related phenomena: the rosetta stone of wetting

The abbreviation “nano-Calphad” stands for “Calculation of Phase Diagrams for nano-systems.” Nano-systems contain at least one phase or at least one interface layer (film, complexion) with at least one of its dimensions being below 100 nm. The essential task of nano-Calphad is to introduce correctly the surface term into the equation for the Gibbs energy. In view of the controversy between the Kelvin and Gibbs equations, even this task does not have an obvious solution (in the present paper, the Gibbs method is preferred). However, there are many further questions to be addressed when the Calphad method is converted into the nano-Calphad method. This paper attempts to give an as full as possible list of all those problems, such as: (i) the definition of a new, independent thermodynamic variable, (ii) the extended phase rule, (iii) the curvature dependence of the interfacial energies, (iv) the dependence of interfacial energies on the separation between interfaces (including the problem of surface melting), (v) the role of the shapes and relative arrangement of phases, (vi) the role of the substrate (if such exists), and (vii) the role of segregation, taking into account its effect on the mass balance within multi-component nano-phases and its surface phase transition and complexion. It is also shown that the well-known meaning of the tie line in binary two-phase fields is lost in nano-systems. The issues related to the size limits of materials thermodynamics and the need for a more complete databanks on molar volumes and interfacial energies are discussed.

/pdf/nano-calphad-extension-of-the-calphad-method-to-systems-with-3xfzxww1ks.pdf

Nano-Calphad: extension of the Calphad method to systems with nano-phases and complexions

Microstructure and wear behaviour of aluminium alloys containing embedded nanoscaled lead dispersoids

Al–Pb ribbons containing 1 at.% Pb have been produced by melt-spinning and subsequently investigated by high-resolution transmission electron microscopy. It is shown that the lattice mismatch of about 22% between the nanometre-sized Pb inclusions and the surrounding Al matrix is accommodated by a periodic array of misfit dislocations at the Al–Pb interface. The closing failures of Burgers circuits drawn around misfit dislocations on {111} and {100} facets identify the corresponding Burgers vectors as (a 0/4)⟨ 211 ⟩ and (a 0/2)⟨ 110⟩, respectively. The Burgers vector of (a 0/4)⟨ 211⟩ corresponds to the projected edge part of a 60° (a 0/2)⟨ 110⟩ dislocation. The Pb inclusions themselves appear to be free of defects.

HRTEM observation of interfacial dislocations at faceted Al–Pb interfaces

Wetting of single-crystal surfaces of metallic solids and oxides by liquid metals and alloys is anisotropic because of the anisotropy of the energies of solid surfaces and of their interfaces with liquids. To provide a basis for a discussion of wetting anisotropy, we review first the literature on surface and interfacial energies in metal-metal and metal-ceramic systems. We then summarize the relevant literature on the anisotropy of the energies of solid surfaces and of solid-liquid interfaces. These energies are then used in conjunction with the Young equation to estimate the expected anisotropy of wetting. Some serious discrepancies are found between these estimates and the experimental anisotropy of wetting. We show that under certain experimental conditions the wetting angles that have been determined are not Young contact angles.

Anisotropy of Wetting

Al–Pb alloys are monotectic and characterized by a large miscibility gap in the liquid phase area and extremely limited mutual solubility in the solid phase. Due to the extent of the miscibility gap the alloys are difficult to make in conventional processing. However, alloys with relatively homogeneous microstructures of fine Pb inclusions in an Al matrix can be made by metastable processing such as rapid solidification, ion implantation, ball milling and physical vapor deposition. The first two techniques have been employed to make alloys of Al with 0.5–3 at.% Pb. The alloys contain fine dispersions of nanoscale Pb inclusions with sizes in the range from 1 to about 20 nm after ion implantation and from about 10–500 nm after rapid solidification. Inclusions embedded in the Al matrix are single crystalline, and they grow in parallel cube alignment with the matrix. They have cuboctahedral shape with atomically smooth {1 1 1} and {1 0 0} facets determined from a minimization of the interface energy. Using high resolution TEM, two types of deviations from the classical Wulff construction which alter the shape of the inclusions, have been studied. The smallest inclusions, less than about 20 nm in size, adopt a series of magic sizes that can be related to the occurrence of periodic minima in the residual strain energy. Likewise, in this size range, the energy contribution from the cuboctahedral edges becomes non-negligible leading to an increase in the aspect ratio of the inclusions with decreasing size. Inclusions located in grain boundaries in general adopt a single crystal morphology where one part is faceted and grows in parallel cube alignment with the matrix grain, while the other part has a shape approximating a spherical cap. In special cases such as twin boundaries and {1 1 1} twist boundaries, the inclusions are bicrystalline where each part is aligned with the respective grain and the two parts are separated by a boundary similar to that of the matrix. These shapes can be explained using the Cahn–Hoffman ξ-vector construction, which generalizes the Wulff construction to determine equilibrium shapes at anisotropic interfaces and their junctions.

Shapes and sizes of nanoscale Pb inclusions in Al

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Shapes and sizes of nanoscale Pb inclusions in Al