Surface segregation chemical mechanism

Figure 16. Plausible mechanism of surface segregation through vacancies. Reprinted with permission from Ref Copyright (2008) American Chemical Society.

Surface segregation, which is also a common phenomenon in other materials, has received limited attention and most of the studies applied this concept for the control of the surface chemical composition. Moreover, surface segregation has been typically considered as a non-desirable effect. This is particularly true in the case of materials with precise bulk properties provided by the presence of different additives such as plasticizers or UV-absorbers. The segregation of these additives towards the interface modifies the bulk properties and can provoke large variatiOTis on their mechanical behavior. Several contributions have explored this phenomenon in order to reduce the amount of oligomers/polymeric additives that bloom to polymer surfaces [13]. However, in many other applications it is desirable to have surface properties that vary to a large extent from those found in the bulk. For example, to favor adhesion or increase the wettability, or the opposite, i.e., increase the hydrophobicity, to improve the biocompatibility of commercial polymers or to enhance the chemical resistance. 

Two of this year s articles discuss the fluid-mechanical aspects of systems where material transfer may occur, accompanied by chemical reaction or heat transfer. Fulford analyzes thin-film flow in terms of the flow regimes and of surface disturbances, and relates recent experimental findings to the theoretical framework. Rietema discusses segregation phenomena in heterogeneous reactions, in relation to conditions of flow and of mass transfer. 

Alloy stability is always of concern in heterogeneous catalysis, but in electrocatalysis there are new mechanisms for destabilizing alloys, namely electrochemical dissolution or corrosion. Greeley and Norskov developed an intuitive and simple thermodynamic framework for estimating the stability of alloy surfaces in electrochemical environments. " Their scheme is essentially an extension of an atomistic thermodynamic approach that uses chemical potentials to determine stability to one that uses electrochemical potentials to determine stability. They estimate the electrochemical potentials using total energies calculated within DFT and ideal solution behavior of the ions to consider concentration and pH effects. Within this formalism they are able to estimate the dissolution potential of metals in alloys. They further compared the trends in dissolution behavior to trends in segregation behavior and... 

Knipping et al. (2000) used a box model to simulate the experiment of Oum et al. (1998a) and concluded that conventional chemical and physical processes do not explain the experimental observations. Molecular dynamics simulations of NaCl solutions showed that CP anions are segregated to the surface, facilitating surface reactions involving chloride. They suggested that reactions on the particle surface would be responsible for the release of CI2. According to their box model, the contribution of the interfacial mechanism is 40% of the total chlorine release at a pH of 4 its relative importance increases for less acidic particles (see Section 4.02.4.1 for a discussion of sea salt pH). 

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