Metal-oxygen interface

The initial rate of oxide formation is determined by the reactions at the metal/oxygen interface. Thus, MxOy forms as a thin layer. 

The logaritlrmic law is also observed when the oxide him is an electrical insulator such as AI2O3. The transport of elecuons tlrrough the oxide is mainly due to a space charge which develops between tire metal-oxide interface and the oxide-gas interface. The incorporation of oxygen in the surface of tire oxide requhes the addition of electrons, and if this occurs by a charging process... 

An important consequence of ion migration is the formation of cells where the coated surface acts as a cathode and the exposed metal at the damage acts as an anode (see Section 4.3). The reason for this is that at the metal/coating interface, the cathodic partial reaction of oxygen reduction according to Eq. (2-17) is much less restricted than the anodic partial reaction according to Eq. (2-21). The activity of such cells can be stimulated by cathodic protection. 

At elevated temperatures where titanium alloys could be the adherend of choice, a different failure mechanism becomes important. The solubility of oxygen is very high in titanium at high temperatures (up to 25 at.%), so the oxygen in a CAA or other surface oxide can and does dissolve into the metal (Fig. 12). This diffusion leaves voids or microcracks at the metal-oxide interface and embrittles the surface region of the metal (Fig. 13). Consequently, bondline stresses are concentrated at small areas at the interface and the joint fails at low stress levels [51,52]. Such phenomena have been observed for adherends exposed to 600°C for as little as 1 h or 300°C for 710 h prior to bonding [52] and for bonds using... 

Before electron transfer can occur the oxygen in the atmosphere must be transported to the metal/solution interface, and this involves the following steps... 

Fig. 1.84 Surface of a Cu-IONi alloy after oxidation in oxygen at 500°C, showing blistering, probably associated with CuO formation over voids at the metal/oxide interface (courtesy Central Electricity Research Laboratories)...

Access of air and water will also affect the corrosion rate. Metal inserts in corrosive plastics are most actively attacked at the plastic/metal/air interfaces with certain metals, notably aluminium titaniumand stainless steel, crevice effects (oxygen shielding and entrapment of water) frequently accelerate attack. Acceleration of corrosion by bimetallic couples between carbon-fibre-reinforced plastics and metals presents a problem in the use of these composites. 

SRB, a diverse group of anaerobic bacteria isolated from a variety of environments, use sulfate in the absence of oxygen as the terminal electron acceptor in respiration. During biofilm formation, if the aerobic respiration rate within a biofilm is greater than the oxygen diffusion rate, the metal/biofilm interface can become anaerobic and provide a niche for sulfide production by SRB. The critical thickness of the biofilm required to produce anaerobie conditions depends on the availability of oxygen and the rate of respiration. The corrosion rate of iron and copper alloys in the presence of hydrogen sulfide is accelerated by the formation of iron sulfide minerals that stimulate the cathodic reaction. 

Neoalkoxy zirconates also provide novel opportunities for the adhesion of fluorinated polymers to metal substrates because the introduction of a zirconate at the interface results in a metal oxygen zirconium VI organo fluoride. 

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