Passive film polarisation

Electroplating passive alloys Another application of strike baths reverses the case illustrated in the previous example. The strike is used to promote a small amount of cathode corrosion. When the passivation potential of a substrate lies below the cathode potential of a plating bath, deposition occurs onto the passive oxide film, and the coating is non-adherent. Stainless steel plated with nickel in normal baths retains its passive film and the coating is easily peeled off. A special strike bath is used with a low concentration of nickel and a high current density, so that diffusion polarisation (transport overpotential) depresses the potential into the active region. The bath has a much lower pH than normal. The low pH raises the substrate passivation potential E pa, which theoretically follows a relation... 

Figure 2. Polarisation curve recorded on Ni in 0.05M H2SO4 at 0.28 mV/sec. The insert shows the model of the passive film deduced from XPS measurements. Reproduced with permission from reference (5).

On the other hand, on the positive side, the opportunity may be taken to include corrosion inhibitors, such as strontium chromate, into the polymeric adhesive, or primer, layer. Such inhibitors will slowly leach out and are especially selected to retard the rate of the electrochemical-corrosion mechanism. They typically achieve this by increasing the polarisation of the anodic sites by reaction with the ions of the corroding metallic substrate to produce (a) thin passive films, or (b) salt layers of limited solubility which coat the anodic sites [34]. 

It is convenient to consider three stages of anode polarisation with regard to temperature effects, (a) under film-free conditions, (b) under film-forming conditions and (c) at the active-passive transition. 

The general form of the anodic polarisation curve of the stainless steels in acid solutions as determined potentiostaticaiiy or potentiodynamically is shown in Fig. 3.14, curve ABCDE. If the cathodic curve of the system PQ intersects this curve at P between B and C only, the steel is passive and the film should heal even if damaged. This, then, represents a condition in which the steel can be used with safety. If, however, the cathodic curve P Q also intersects ED the passivity is unstable and any break in the film would lead to rapid metal solution, since the potential is now in the active region and the intersection at Q gives the stable corrosion potential and corrosion current. 

Tin when made anodic shows passive behaviour as surface films are built up but slow dissolution of tin may persist in some solutions and transpassive dissolution may occur in strongly alkaline solutions. Some details have been published for phosphoric acid with readily obtained passivity, and sulphuric acid " for which activity is more persistent, but most interest has been shown in the effects in alkaline solutions. For galvanostatic polarisation in sodium borate and in sodium carbonate solutions at 1 x 10" -50 X 10" A/cm, simultaneous dissolution of tin as stannite ions and formation of a layer of SnO occurs until a critical potential is reached, at which a different oxide or hydroxide (possibly SnOj) is formed and dissolution ceases. Finally oxygen is evolved from the passive metal. The nature of the surface films formed in KOH solutions up to 7 m and other alkaline solutions has also been examined. 

The simplest and most thoroughly studied solutions are those based on phosphoric acid at low temperatures (<35°C) which alone can fulfil all three requirements of acid solvent, film former (as metal phosphate) and diffusion agent by virtue of its viscosity. Thus copper and its main alloys of brasses and bronzes can be very effectively electropolished in 60-70% orthophos-phoric acid with the temperature maintained below 35°C under other conditions copper passivates or dissolves freely under mass transfer controlled conditions, but by varying the conditions appropriately polishing can be continued under mild agitation. An annotated polarisation curve is given in Fig. 11.7 readers are referred to recent studies for more detailed 2ispects " . 

A close connection has been found to exist between passivity and photo-electric behaviour. Thus dry, active iron is found to exhibit a considerably higher photo-electric activity than the metal rendered passive by immersion in concentrated nitric acid or by anodic polarisation in dilute sulphuric acid and this is regarded as supporting the gaseous film theory.6... 

Although most metals display an active or activation controlled region, when polarised anodically from the equilibrium potential, many metals and perhaps even more so alloys developed for engineering applications, produce a solid corrosion product. In many examples the solid is an oxide that is the stable phase rather than the ion in solution. If this solid product is formed at the metal surface and has good intimate contact with the metal, and features low ion-conductivity, the dissolution rate of the metal is limited to the rate at which metal ions can migrate through the film. The layer of corrosion product acts as a barrier to further ion movement across the interface. The resistance afforded by this corrosion layer is generally referred to as the passivity. Alloys such as the stainless steels, nickel alloys and metals like titanium owe their corrosion resistance to this passive layer. 

The technique may be understood in terms of metallic passivity, i.e. the loss of chemical activity experienced by certain metals and alloys under particular environmental conditions as a result of surface film formation. Equations 15.2 and 15.3 suggest that the application of an anodic current to a metal should tend to increase metal dissolution and decrease hydrogen production. Metals that display passivity, such as iron, nickel chromium, titanium and their alloys respond to an anodic current by shifting their polarisation potential into the passive regon. Current densities required to initiate passivity are relatively high [Uhlig and Revie 1985] but the current density to maintain passivity are low, with a consequent reduction in power costs [Scully 1990]. 

A1 alloys PPy Galvanostatic activation and Galvanostatic deposition Single-cycle anodic polarisation and subsequent re-passivation Monitoring of OCP in 0.6 M NaCl. The nature of the substrate influences the structure and morphology of PPy films. The performance of PPy films depends on the corrosion test used. [16]... 

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