Thermodynamics stable film formation

Before considering the principles of this method, it is useful to distinguish between anodic protection and cathodic protection (when the latter is produced by an external e.m.f.). Both these techniques, which may be used to reduce the corrosion of metals in contact with electrolytes, depend upon the electrochemical mechanisms that result from changing the potential of a metal. The appropriate potential-pH diagram for the Fe-H20 system (Section 1.4) indicates the magnitude and direction of the changes in the potential of iron immersed in water (pH about 7) necessary to make it either passive or immune in the former case the stability of the metal depends on the formation of a protective film of metal oxide (passivation), whereas in the latter the metal itself is thermodynamically stable and egress of metal ions from the lattice into the solution is thus prevented. 

Anodic oxidation often involves the formation of films on the surface, i.e. of a solid phase formed of salts or complexes of the metals with solution components. They often appear in the potential region where the electrode, covered with the oxidation product, can function as an electrode of the second kind. Under these conditions the films are thermodynamically stable. On the other hand, films are sometimes formed which in view of their solubility product and the pH of the solution should not be stable. These films are stabilized by their structure or by the influence of surface forces at the interface. 

The growth of vanadium oxide overlayers on Rh(l 11) converges after a number of intermediate stages to the formation of a three-dimensional bulk-like epitaxial V203 film [90], which is oriented with the (0 0 01) plane of its corundum structure parallel to the Rh(l 1 1) substrate surface. The V203 phase is the thermodynamically stable... 

Besides the effect of the electrode materials discussed above, each nonaqueous solution has its own inherent electrochemical stability which relates to the possible oxidation and reduction processes of the solvent,the salts, and contaminants that may be unavoidably present in polar aprotic solutions. These may include trace water, oxygen, CO, C02 protic precursor of the solvent, peroxides, etc. All of these substances, even in trace amounts, may influence the stability of these systems and, hence, their electrochemical windows. Possible electroreactions of a variety of solvents, salts, and additives are described and discussed in detail in Chapter 3. However, these reactions may depend very strongly on the cation of the electrolyte. The type of cation present determines both the thermodynamics and kinetics of the reduction processes in polar aprotic systems [59], In addition, the solubility product of solvent/salt anion/contaminant reduction products that are anions or anion radicals, with the cation, determine the possibility of surface film formation, electrode passivation, etc. For instance, as discussed in Chapter 4, the reduction of solvents such as ethers, esters, and alkyl carbonates differs considerably in Li or in tetraalkyl ammonium salt solutions [6], In the presence of the former cation, the above solvents are reduced to insoluble Li salts that passivate the electrodes due to the formation of stable surface layers. However, when the cation is TBA, all the reduction products of the above solvents are soluble. 

Ruckenstein [19] also analyzed the stabilities of small crystallites relative to film formation. They showed that there is a minimum crystallite radius rm above which the crystallite state is thermodynamically more stable than a film. This minimum radius depends on the contact angle and hence, on the degree of wetting of the support by the active phase ... 

Noncrystalline solids formation needs to be clarified by reference to the natnre of the final product. Several methods lead to amorphous fine particles, for instance, in solution by controlled precipitation. Through gel formation, poorly crystalline Ti02 can be obtained according to the process Ti(OR)4 -I- H2O Ti(OH)4 gel amorphous Ti02 + H2O. In this case, the compound obtained is thermodynamically stable, as when amorphous films are obtained by chemical vapor deposition, sputtering, flash evaporation, and so on. 

A microemulsion is a thermodynamically stable isotropic dispersion of two relatively immiscible liquids, consisting of microdomains of one or both liquids stabilized by a interfacial film of surface-active molecules. In practice, one often identifies the microemulsion by the formation of a clear isotropic mixture of the two immiscible liquids in the presence of appropriate emulsifiers. In a phase diagram, such region is referred as the microemulsion phase. It has been shown that microemulsion regions consist of different microstructures (1,2), e.g., water-in-oil (W/0), oil-in-water (0/W),... 

The phototuning of BPs can also be fabricated in a pure material system [147]. Das et al. reported a light-induced stable blue phase in photoresponsive diphen-ylbutadiene based mesogen 37. This compound was found to exhibit SmA and N during heating. When the temperature was kept at 118 °C, the photoisomerization induced an isothermal phase transition from SmA to N. Photoirradiation of the SmA film held at a higher temperature (124 °C) for 100 s resulted in transition to a phase with a characteristic classical BP texture showing in Fig. 5.30. The BP was thermodynamically stable and could be maintained at this state for several hours. The characteristic sharp reflection bands compared to the rather broad reflection bands observed for the chiral nematic phase confirmed the formation of BP. The photoinduced formation of the BP exhibited a reflection centered at 510 nm. Subsequent irradiation led to the blue shift to 480 nm in the reflection band. 

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