Oxide film, electric field

Highly protective layers can also fonn in gaseous environments at ambient temperatures by a redox reaction similar to that in an aqueous electrolyte, i.e. by oxygen reduction combined with metal oxidation. The thickness of spontaneously fonned oxide films is typically in the range of 1-3 nm, i.e., of similar thickness to electrochemical passive films. Substantially thicker anodic films can be fonned on so-called valve metals (Ti, Ta, Zr,. ..), which allow the application of anodizing potentials (high electric fields) without dielectric breakdown. 

Flaws in the anodic oxide film are usually the primary source of electronic conduction. These flaws are either stmctural or chemical in nature. The stmctural flaws include thermal crystalline oxide, nitrides, carbides, inclusion of foreign phases, and oxide recrystaUi2ed by an appHed electric field. The roughness of the tantalum surface affects the electronic conduction and should be classified as a stmctural flaw (58) the correlation between electronic conduction and roughness, however, was not observed (59). Chemical impurities arise from metals alloyed with the tantalum, inclusions in the oxide of material from the formation electrolyte, and impurities on the surface of the tantalum substrate that are incorporated in the oxide during formation. 

Oxide films formed at low temperatures are initially continuous and amorphous, but may undergo local crystallisation with the incorporation of the oxide islands , a process that is facilitated by water, heat, high electric fields and mechanical stress... 

This is the general expression for film growth under an electric field. The same basic relationship can be derived if the forward and reverse rate constants, k, are regarded as different, and the forward and reverse activation energies, AG are correspondingly different these parameters are equilibrium parameters, and are both incorporated into the constant A. The parameters A and B are constants for a particular oxide A has units of current density (Am" ) and B has units of reciprocal electric field (mV ). Equation 1.114 has two limiting approximations. 

Transduction in an Oscillating Field Electric Breakdown in Anodic Oxide Films 23... 

We found that the increase of film conductivity observed without magnetic field disappeared immediately after the field tum-on and did not appear again until the filed was turned off again. This result seems to confirm the earlier supposition of electric activity being present only if the surface of a semiconductor film is covered with silver atoms. We used the method of physical development of an oxide film alter sufficiently long exposition of the film to the beam of silver particles, with the magnetic field turned on, in order to be sure that particles of silver... 

Abstract In the last decade, the sonoelectrochemical synthesis of inorganic materials has experienced an important development motivated by the emerging interest in the nanostructures production. However, other traditional sonoelectrochemical synthesis such as gas production, metal deposits and metallic oxide films have also been improved with the simultaneous application of both electric and ultrasound fields. In this chapter, a summary of the fundamental basis, experimental set-up and different applications found in literature are reported, giving the reader a general approach to this branch of Applied Sonoelectrochemistry. 

In the above considerations, the O/S interface was taken to be a clear-cut boundary between the oxide and the electrolyte. In reality, however, the outer part of the oxide is likely to be hydrated and penetrated by the electrolyte. Hence, the true O/S interface is likely to be withdrawn from the surface to a sufficient depth such that some oxide is left without any electric field imposed across it. This is especially true of thick porous oxide layers, but it can occur with compact layers as well. For example, Hurlen and Haug35 found a duplex film in acetate solution (pH 7-10), composed of a dry barrier-type part and a thicker hydrated part consisting of A1203 H20. Although the hydrated part becomes thinner with decreasing pH and seems to practically vanish at low pH, even a thickness of less than a nanometer is sufficient for the surface oxide to stay outside the electrochemical double layer. 

An answer to the first question may be found in noting that the electric field in a thin oxide film is different from that in a thick one and that weakening of electrostatic repulsion which prevents hydration and withdrawal of the O/S interface from the surface is a prerequisite for chemical dissolution. 

There are several difficulties in the application of this technique to the analysis of sodium barrier properties of these polyimide films. First, as we have seen above, large shifts in the surface potential characteristics of MPOS structures can be associated with electronic conduction in the polyimide and charging of the polyimide-oxide interface. These shifts are not readily separable from any that might be caused by the inward drift of sodium ions. Second, the effect of the electronic charging process is to buck out the electric field in the polyimide which is needed to drive the ion drift mechanism. As seen in Figure 6, the electric field is reduced to very small values in a matter of minutes or less, particularly at the higher temperatures where ion drift would normally be measured. 

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