Aluminium colouring

Aluminium oxide occurs naturally as emery (an impure form) and as corundum. Corundum is a crystalline form which may be coloured by traces of impurity, for example as ruby (red) and sapphire (blue). Small synthetic rubies and sapphires have been made by heating alumina with the colouring oxide in an oxy-hydrogen flame. 

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. 

Evidence for the solvated electron e (aq) can be obtained reaction of sodium vapour with ice in the complete absence of air at 273 K gives a blue colour (cf. the reaction of sodium with liquid ammonia, p. 126). Magnesium, zinc and iron react with steam at elevated temperatures to yield hydrogen, and a few metals, in the presence of air, form a surface layer of oxide or hydroxide, for example iron, lead and aluminium. These reactions are more fully considered under the respective metals. Water is not easily oxidised but fluorine and chlorine are both capable of liberating oxygen ... 

Pigments for finishes are selected on the basis of their colour, but special attention must be paid to inertness in the chosen binder and stability and light fastness under the conditions of application and exposure. Flake pigments such as aluminium and micaceous iron oxide give finishes of lower moisture-vapour permeability than conventional pigments, and consequently contribute to better protection. 

The finishes produced have very good light fastness and corrosion resistance, and, unlike integral colour finishes, the shade is largely independent of the aluminium alloy and the anodic film thickness used. The whole range of shades can be produced on films as thin as 5 /im, so the finishes are also being used in trim applications. Many patents and publications in the electrolytic colouring field now exist and they have been reviewed by many authors . 

The chromate sealing treatment imparts to the anodic film a distinct yellow to brown colour, which is probably due to a basic aluminium chromate or alkali chromate adsorbed on to aluminium hydroxide. The film gives appreciable protection against marine exposure. 

Discussion. Iron(III) (50-200 fig) can be extracted from aqueous solution with a 1 per cent solution of 8-hydroxyquinoline in chloroform by double extraction when the pH of the aqueous solution is between 2 and 10. At a pH of 2-2.5 nickel, cobalt, cerium(III), and aluminium do not interfere. Iron(III) oxinate is dark-coloured in chloroform and absorbs at 470 nm. 

Direct EDTA titrations of Bi, Th, Zn, Cd, Pb, Co, etc., are readily carried out and the colour change is sharp. Iron(III) and, to a lesser extent, aluminium interfere. By appropriate pH adjustment certain pairs of metals may be titrated successfully in a single sample solution. Thus bismuth may be titrated at pH =1-2, and zinc or lead after adjustment to pH = 5 by addition of hexamine. 

Pipette 25 mL of an aluminium ion solution (approximately 0.01 M) into a conical flask and from a burette add a slight excess of 0.01 M EDTA solution adjust the pH to between 7 and 8 by the addition of ammonia solution (test drops on phenol red paper or use a pH meter). Boil the solution for a few minutes to ensure complete complexation of the aluminium cool to room temperature and adjust the pH to 7-8. Add 50 mg of solochrome black/potassium nitrate mixture [see Section 10.50(C)] and titrate rapidly with standard 0.01 M zinc sulphate solution until the colour changes from blue to wine red. 

After standing for a few minutes the fully titrated solution acquires a reddish-violet colour due to the transformation of the zinc dye complex into the aluminium-solochrome black complex this change is irreversible, so that over-titrated solutions are lost. 

Discussion. Minute amounts of beryllium may be readily determined spectrophotometrically by reaction under alkaline conditions with 4-nitrobenzeneazo-orcinol. The reagent is yellow in a basic medium in the presence of beryllium the colour changes to reddish-brown. The zone of optimum alkalinity is rather critical and narrow buffering with boric acid increases the reproducibility. Aluminium, up to about 240 mg per 25 mL, has little influence provided an excess of 1 mole of sodium hydroxide is added for each mole of aluminium present. Other elements which might interfere are removed by preliminary treatment with sodium hydroxide solution, but the possible co-precipitation of beryllium must be considered. Zinc interferes very slightly but can be removed by precipitation as sulphide. Copper interferes seriously, even in such small amounts as are soluble in sodium hydroxide solution. The interference of small amounts of copper, nickel, iron and calcium can be prevented by complexing with EDTA and triethanolamine. 

The procedure utilises eriochrome blue black RC (also called pontachrome blue black R Colour Index No. 15705) at a pH of 4,8 in a buffer solution. Beryllium gives no fluorescence and does not interfere iron, chromium, copper, nickel, and cobalt mask the fluorescence fluoride must be removed if present. The method may be adapted for the determination of aluminium in steel. 

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