Anodised film

Sheet aluminium can be given a colour by a similar process. The aluminium is first made the anode in a bath of chromic acid (p. 377) when, instead of oxygen being evolved, the aluminium becomes coated with a very adherent film of aluminium oxide which is very adsorbent. If a dye is added to the bath the oxide film is coloured, this colour being incorporated in a film which also makes the remaining aluminium resistant to corrosion. This process is called anodising aluminium. 

Similar considerations also apply to the dielectric films formed on the metal surface during anodising, and, for example, in the case of the valve metals (Al, Ti, Ta, Nb, etc.) IR drops of hundreds of volts may be produced by the anodic oxide film formed on the metal surfaces. Paint films applied to a metal surface also exert resistance control see Section 14.3). 

On the other hand, metals such as Ta, Nb, Ti, Zr, Al, etc. (the valve metals ) do not exhibit transpassive behaviour, and in appropriate electrolyte solutions film growth at high fields rather than corrosion and/or oxygen evolution is the predominant reaction thus aluminium can be anodised to 500 V or more in an ammonium borate buffer titanium can be anodised to about 400 V in formic acid and tantalum can be anodised to high voltages in most acids, including hydrochloric acid. 

Strazzi has reviewed methods of sealing oxide films and Omata etal. find that adhesion of paint films to anodised layers depends on penetration... 

It is somewhat less corrosion resistant than tantalum, and like tantalum suffers from hydrogen embrittlement if it is made cathodic by a galvanic couple or an external e.m.f., or is exposed to hot hydrogen gas. The metal anodises in acid electrolytes to form an anodic oxide film which has a high dielectric constant, and a high anodic breakdown potential. This latter property coupled with good electrical conductivity has led to the use of niobium as a substrate for platinum-group metals in impressed-current cathodic-protection anodes. 

Galvanic effects If niobium is cathodic in a galvanic couple the results can prove disastrous because of hydrogen embrittlement. If niobium is the anode in such a couple it anodises so readily that no damage occurs and the galvanic current drops to a very low value due to the formation of an anodic oxide film. 

Anodic passivation also allows titanium to be employed as a Jig for aluminium anodising baths ", because the protective anodic film formed on titanium allows passage of electronic current to the metal contact while virtually suppressing flow of ionic current through the anodically-formed surface film. This aspect is discussed in more detail in relation to special applications. 

By a mechanism similar to that discussed in relation to platinum coating, titanium can function as a conducting jig to support aluminium components and assemblies in conventional anodising baths. In this application the exposed titanium acquires the insulating film, but allows current to pass to the aluminium at the points of contact . 

Because of its good performance in mineral acids, there is little need or incentive to invoke anodic passivation techniques for zirconium. The metal can be anodised in sulphuric acid, but, again in contrast to the behaviour of titanium, it does not form a stable anodic film in chloride solutions, and even in neutral sodium chloride, zirconium rapidly corrodes if an anodic potential of 2 V is applied. 

Alloys are generally of the Al-Mg-Si type with additions of copper and chromium or manganese. Colour varies with the particular alloy and the film thickness. For optimum control of colour, the alloy must be carefully produced with strict attention to composition, homogenisation and heat-treatment, where appropriate, and the anodising conditions must be maintained within narrow limits. It is usual to arrange matters, preferably with automatic control, such that current density is held constant with rising... 

Decorative self-coloured films can also be produced in sulphuric acid under conditions intermediate between normal and hard anodising. 

The more or less regular pattern of pores imposes a cellular structure on the film, with the cells approximating in plan to hexagons, each with a central pore, while the bases which form the barrier-layer, are rounded. The metal surface underlying the film, therefore, consists of a close-packed regular array of nearly hemispherical depressions which increase in size with the anodising voltage. The thickness of the individual cell walls is approximately equal to that of the barrier-layer... 

Density Owing to the variable degree of porosity of the anodic film, it is only possible to determine the apparent density, which varies with the anodising conditions and also with the film thickness. 

Fig. 15.2, taken from a paper by Lenz , shows the variation in density with thickness for steam-sealed anodic films produced in sulphuric acid on aluminium of 99-99 7o and 99-5% purity. A mean figure of 2-7 g/cm for sealed, and 2-5 g/cm for unsealed films is accepted by the British Standard for anodised aluminium... 

The hardness of the film is markedly affected by the conditions of anodising. By means of special methods involving dilute electrolytes at low temperatures and relatively high voltages , with or without superimposed alternating current, it is possible to produce compact abrasion-resistant films with thicknesses of 50-75/im and hardnesses of 200-500 VPN, for special applications. 

Flexibility The normal anodic film begins to crack if subjected to an extension exceeding about 0 - 5%. Thinner films up to 5 nm in thickness appear to withstand a greater degree of deformation without obvious failure, and are often used for dyed coatings on continuously anodised strip from which... 

Thermal expansion The thermal expansion of the film is only about one-fifth that of aluminium, and cracking or crazing is observed when anodised aluminium is heated above 80°C. The fine hair-cracks produced do not seem to impair the protective properties of the coating if anodising conditions have been correct. 

Emissivity Table 15.5 shows the total heat emissivity of various aluminium surfaces, as a percentage of that of a black body. The figures have been recalculated from the data of Hase. The emissivity of anodised aluminium rises rapidly with film thickness up to 3 fim after which the rate of increase diminishes. 

Friction The coefficient of friction of the sealed anodic film is 0 76, falling to 0-19 after impregnation with silicone oil . These results were obtained with anodised wire. 

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