Aluminium chromate

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. 

Aluminium Chromate.—The normal salt is not knowm. Aluminium hj droxide is soluble in chromic acid solutions, but the nature of the mixture varies with the temperature and the concentration of the chromic acid solution. A yellow floceulent precipitate of a basic aluminium chromate, AljO3.CrO3.7H2O, is produced by adding potassium chromate to a solution of alum. 

Filiform corrosion is characterised by the formation of a network of threadlike filaments of corrosion products on the surface of a metal coated with a transparent lacquer or a paint him, as a result of exposure to a humid atmosphere. This phenomenon first attracted attention because of its formation on lacquered steel, and for this reason it is sometimes referred to as underfilm corrosion, but although it is most readily observed under a transparent lacquer it can also occur under an opaque paint film or on a bare metal surface. Filiform corrosion has been observed on steel, zinc, magnesium and aluminium coated with lacquers and paints, and with aluminium foil coated with paper. Surface treatment of the metal by phosphating or chromating lessens the tendency for filiform corrosion to occur, but it is not completely... 

Low-carbon and chromium-nickel steels, certain copper, nickel and aluminium alloys (which are all widely used in marine and offshore engineering) are liable to exhibit stress-corrosion cracking whilst in service in specific environments, where combinations of perhaps relatively modest stress levels in material exposed to environments which are wet, damp or humid, and in the presence of certain gases or ions such as oxygen, chlorides, nitrates, hydroxides, chromates, nitrates, sulphides, sulphates, etc. 

The processes are dealt with fully in Chapters 11, 14 and 15. Because many paint systems include an initial surface pretreatment, e.g. chromated aluminium or phosphated steel, BS4479 1990, Part 3 deals with conversion coatings and should be consulted by designers. Whatever the method of treatment, liquids must be able to drain quickly and freely from the surfaces. Crevices where liquids can become entrapped are best avoided. The surface configuration needs to be such that active solutions can be washed away, leaving the surface to be painted completely free from unreacted pretreatment solution. Failure to achieve the requisite level of freedom from the surplus chemicals causes paint failure, e.g. osmotic blistering. 

Aluminium coatings exposed as sprayed show remarkable protective properties and in many cases the only evidence of age is the appearance of small hard nodules of aluminium oxide, and these do not appear to be deleterious. However, the dead white of the sprayed surface soon becomes discoloured by dirt and so a paint covering is usual. A chromate inhibitor is not essential and two coats of a simple vinyl-based sealing paint have given remarkable results in the tests of the American Welding Society over periods of 12 and 15 years. 

The anodic oxidation of magnesium does not normally produce a film that has sufficient corrosion resistance to withstand exposure without further protection by painting, and the solutions used are complex mixtures containing phosphates, fluorides and chromates. In the case of aluminium, a relatively simple treatment produces a hard, compact, strongly adherent film of oxide, which affords considerably increased protection against corrosive attack . 

Phosphate solutions containing fluorides are used for processing steel, zinc and aluminium when assembled together, but chromate solutions are generally preferred when aluminium is treated alone. The increasing use of cathodic electrophoretic painting on steel, however, has led to a reassessment of the basic processes and formulations that might be most effective. 

Aluminium and its alloys (a) Alkaline dip Alkaline chromate Oxide/hydroxide with perhaps some chromate... 

The Stability of the natural oxide film reinforced by the chromate ion determines the conditions of pH, ratio of activating anion to chromate, and temperature at which the oxide is broken down and a chromate film deposited. Thus magnesium alloys can be chromate-treated in nearly neutral solutions, whereas aluminium alloys can be treated only in solutions of appreciable acidity or alkalinity. 

Several immersion treatments using solutions containing chromates have been developed for aluminium. It is not always clear to what extent the films formed can properly be called chromate films, i.e. films containing a substantial amount of a slightly soluble chromium chromate, but even if the film consists largely of aluminium oxide or hydroxide or other salt with chromate physically absorbed, it will still provide a reservoir of soluble chromate at the metal surface. Treatments fall into two classes alkaline and acid. The latter are of more recent development. 

Acid treatments The principal acid processes were developed in the USA under the name Alodine, and are marketed in the UK as Alocrom and under other names. The original solutions were based on acid solutions containing phosphate, chromate and fluoride ions. Immersion for up to 5 min in the cold or warm solution leads to the deposition of a greenish film containing the phosphates of chromium and aluminium, and possibly some hexavalent chromate. The more recent Alocrom 1 200 process uses an acid solution containing chromate, fluoride and nitrate. Room-temperature immersion for 15 s to 3 min deposits golden-brown coatings which contain chromate as a major constituent. 

Acid pickles Some of the acid pickles used to clean and etch aluminium alloy surfaces and remove oxide and anodic films, such as the chromic/ sulphuric acid pickle (method O of DEF STAN 03-2) and other chromic-acid bearing pickles (App. Foi DEF-151) probably leave on the surface traces of absorbed or combined chromate which will give at least some protection against mild atmospheres. 

Medium acid baths, pH 4-5 At this acidity a dichromate solution plus sulphate ion as activator is sufficient to deposit chromate films in 30 min or so at room temperature or in a few minutes at boiling point. Unfortunately, a solution of alkali dichromate and alkali sulphate is quite unbuffered, and other substances must be added to give the bath a useful life over the working pH range. Acetates have been used successfully, but salts of aluminium, chromium, manganese and zinc have been more commonly employed. The pH of the solution rises slowly during use until basic chromates or sulphates begin to precipitate. The solution can then be rejuvenated by the addition of chromic or sulphuric acid or acid salts. 

Alkaline chromate treatments for tin, e.g. the Protecta-Tin processes, have been developed by the Tin Research Institute. The solutions resemble the M.B.V. compositions for treating aluminium, but are more alkaline. Thin invisible films which resist staining by heat and sulphur-bearing compounds and give protection against humid atmospheres at pores are deposited. 

Treverton, J. A. and Davies N. C. XPS Studies of a Ferricyanide Accelerated chromate Paint PretreatmenI Film on an Aluminium Surface , Surf. Interfacial Ana ., 3, 194-200 (1981)... 

Conversion coating Conversion coatings are chemical solutions which react with the metal surface to create a corrosion-resistant layer onto which the coating can bond. For mild steel iron phosphate is used to attain good adhesion, but it does not give the underfilm corrosion resistance which can be obtained using zinc phosphate. Zinc coatings can be treated with either zinc phosphate or chromate. Aluminium is usually treated with chromate... 

Locomotive diesels As larger volumes of coolant are required in railway locomotives than in road vehicles, the cost of inhibition is proportionally greater. An additional factor is the possibility of cavitation attack of cylinder liners. These considerations place a restriction on the choice of inhibitors. In the past, chromates have been used at concentrations of up to 0-4%, but their use presents handling and disposal problems. Chromates cannot be used with ethanediol antifreeze solutions. A IS I borate-metasilicate at a concentration of 1 % has been used in the UK. Nitrate is added to this to improve inhibition of aluminium alloy corrosion. Tannins and soluble oils are also used, but probably to a lesser extent than in the past. The benzoate-nitrite formulation (formerly BS 3151) is effective and has been used by continental railways . ... 

When aluminium is immersed in water, the air-formed oxide film of amorphous 7-alumina initially thickens (at a faster rate than in air) and then an outer layer of crystalline hydrated alumina forms, which eventually tends to stifle the reaction In near-neutral air-saturated solutions, the corrosion of aluminium is generally inhibited by anions which are inhibitive for iron, e.g. chromate, benzoate, phosphate, acetate. Inhibition also occurs in solutions containing sulphate or nitrate ions, which are aggressive towards iron. Aggressive anions for aluminium include the halide ions F ,... 

Discussion. This method is based upon the precipitation of lead chlorofluoride, in which the chlorine is determined by Volhard s method, and from this result the fluorine content can be calculated. The advantages of the method are, the precipitate is granular, settles readily, and is easily filtered the factor for conversion to fluorine is low the procedure is carried out at pH 3.6-5.6, so that substances which might be co-predpitated, such as phosphates, sulphates, chromates, and carbonates, do not interfere. Aluminium must be entirely absent, since even very small quantities cause low results a similar effect is produced by boron ( >0.05 g), ammonium (>0.5 g), and sodium or potassium ( > 10g) in the presence of about 0.1 g of fluoride. Iron must be removed, but zinc is without effect. Silica does not vitiate the method, but causes difficulties in filtration. 

Urea possesses negligible basic properties (Kb = 1.5 x 10 l4), is soluble in water and its hydrolysis rate can be easily controlled. It hydrolyses rapidly at 90-100 °C, and hydrolysis can be quickly terminated at a desired pH by cooling the reaction mixture to room temperature. The use of a hydrolytic reagent alone does not result in the formation of a compact precipitate the physical character of the precipitate will be very much affected by the presence of certain anions. Thus in the precipitation of aluminium by the urea process, a dense precipitate is obtained in the presence of succinate, sulphate, formate, oxalate, and benzoate ions, but not in the presence of chloride, chlorate, perchlorate, nitrate, sulphate, chromate, and acetate ions. The preferred anion for the precipitation of aluminium is succinate. It would appear that the main function of the suitable anion is the formation of a basic salt which seems responsible for the production of a compact precipitate. The pH of the initial solution must be appropriately adjusted. 

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