Materials solid/liquid interfaces

In recent years, advances in experimental capabilities have fueled a great deal of activity in the study of the electrified solid-liquid interface. This has been the subject of a recent workshop and review article [145] discussing structural characterization, interfacial dynamics and electrode materials. The field of surface chemistry has also received significant attention due to many surface-sensitive means to interrogate the molecular processes occurring at the electrode surface. Reviews by Hubbard [146, 147] and others [148] detail the progress. In this and the following section, we present only a brief summary of selected aspects of this field. 

Cavitation damage is a fonn of deterioration associated with materials in rapidly moving liquid environments, due to collapse of cavities (or vapour bubbles) in the liquid at a solid-liquid interface, in the high-pressure regions of high flow. If the liquid in movement is corrosive towards the metal, the damage of the metal may be greatly increased (cavitation corrosion). 

While characterization of the electrode prior to use is a prerequisite for a reliable correlation between electrochemical behaviour and material properties, the understanding of electrochemical reaction mechanisms requires the analysis of the electrode surface during or after a controlled electrochemical experiment. Due to the ex situ character of photoelectron spectroscopy, this technique can only be applied to the emersed electrode, after the electrochemical experiment. The fact that ex situ measurements after emersion of the electrode are meaningful and still reflect the situation at the solid liquid interface has been discussed in Section 2.7. 

When a drop of liquid is placed on the surface of a solid, it may spread to cover the entire surface, or it may remain as a stable drop on the solid. There is a solid-liquid interface between the two phases. In the case of liquids that do not spread on the solid, the bare surface of the solid adsorbs the vapor of the liquid until the fugacity of the adsorbed material is equal to that of the vapor and the liquid. 

Several excellent reviews of liquid-phase epitaxy have appeared in the literature over the past 15 years (1-12). The discussion in this chapter will be limited in scope but will supplement the material discussed in previous reviews. In particular, issues that can be analyzed by traditional methods of chemical engineering are addressed for this chemical process. Because the growing solid-liquid interface is near equilibrium, the calculation of multicomponent compound-semiconductor phase diagrams will be emphasized. 

Similar to the molecular photosensitizers described above, solid semiconductor materials can absorb photons and convert light into electrical energy capable of reducing C02. In solution, a semiconductor will absorb light, and the electric field created at the solid-liquid interface effects the separation of photo-excited electron-hole pairs. The electrons can then carry out an interfacial reduction reaction at one site, while the holes can perform an interfacial oxidation at a separate site. In the following sections, details will be provided of the reduction of C02 at both bulk semiconductor electrodes that resemble their metal electrode counterparts, and semiconductor powders and colloids that approach the molecular length scale. Further information on semiconductor systems for C02 reduction is available in several excellent reviews [8, 44, 104, 105],... 

In bulk semiconductor electrodes, the electric field at the solid-liquid interface causes the electrons and holes to move in opposite directions within the material. Then, depending on the type of material, n-type or p-type, the electrons or holes... 

Once a solid metal or material with simple molecules (e.g., water) has been nucleated, the freezing rate (velocity of the liquid-solid interface) is controlled almost entirely by the rate of heat removal. The temperature of the solid-liquid interface remains very near the equilibrium freezing temperature. Even if there is substantial undercooling before nucleation, the temperature will rise rapidly back to Tm as freezing occurs because the latent heat, Hf, is large and its release will heat the undercooled liquid. 

Some of the very interesting applications of these layered intercalates are in material design [3], ion exchange [4], catalysis [5], in the study of quantum-sized semiconductor particles [6], assembly of molecular multilayers at solid-liquid interfaces [7], designer electrode surfaces [8], preparation of low-dimensional conducting polymers [9], and so forth. 

Radium may be transported in the atmosphere in association with particulate matter. It exists primarily as a divalent ion in water, and its concentration is usually controlled by adsorption-desorption mechanisms at solid-liquid interfaces and by the solubility of radium-containing minerals. Radium does not degrade in water other than by radioactive decay at rates that are specific to each isotope. Radium may be readily adsorbed by earth materials consequently, it is usually not a mobile constituent in the environment. It may be bioconcentrated and bioaccumulated by plants and animals, and it is transferred in food chains from lower trophic levels to humans. 

In this review, we introduce another approach to study the multiscale structures of polymer materials based on a lattice model. We first show the development of a Helmholtz energy model of mixing for polymers based on close-packed lattice model by combining molecular simulation with statistical mechanics. Then, holes are introduced to account for the effect of pressure. Combined with WDA, this model of Helmholtz energy is further applied to develop a new lattice DFT to calculate the adsorption of polymers at solid-liquid interface. Finally, we develop a framework based on the strong segregation limit (SSL) theory to predict the morphologies of micro-phase separation of diblock copolymers confined in curved surfaces. 

Interestingly, protein adsorption is also a field of biological interfacial chemistry which parallels that of synthetic materials at the solid - liquid interface. A number of spectroscopic advances have been made which allow FT-IR to be used in kinetic monitoring of protein adsorption on metals and "biocompatible" polymers. In addition to providing in - situ measurements of total adsorbed protein, FT-IR can also yield information about perturbation of protein secondary structure in adsorbed layers. 

Surfactants at Interfaces. Somewhat surprisingly, the successes described above in the in-situ studies of protein adsorption have not inspired extensive applications to the study of the adsorption of surfactants. The common materials used in the fabrication of IREs, thalliumbromoiodide, zinc selenide, germanium and silicon do, in fact, offer quite a range in adsorption substrate properties, and the potential of employing a thin layer of a substance as a modifier of the IRE surface which is presented to a surfactant solution has also been examined in the studies of proteins. Based on the appearance of the studies described below, and recent concerns about the kinetics of formation of self-assembled layers, (108) it seems likely that in-situ ATR studies of small molecules at solid - liquid interfaces ("wet" solids), will continue to expand in scope. 

In this chapter we discuss preparative routes for inorganic materials in three basic types of systems involving the presence of a distinct solid-liquid interface those in which the liquid and solid phases are of the same chemical identity (solidification and vitrification processes), those in which the liquid and solid phases are not of the same chemical identity (crystallization, precipitation), and the special case in which the liquid phase is a pure ionic liquid or molten salt. Ionic liquids can serve as the solvent as well as a templating agent, and the liquid components may or may not become incorporated into the final solid product. We also discuss two areas where the distinct solid-liquid interface becomes somewhat blurred namely, sol-gel and solvothermal processes. 

When the solid-liquid interface moves too fast to maintain equilibrium, it results in a chemical composition gradient within each grain, a condition known as coring (Figure 4.6b). Without solid-state diffusion of the solute atoms in the material... 

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