Aluminium surface oxidation

In tenns of an electrochemical treatment, passivation of a surface represents a significant deviation from ideal electrode behaviour. As mentioned above, for a metal immersed in an electrolyte, the conditions can be such as predicted by the Pourbaix diagram that fonnation of a second-phase film—usually an insoluble surface oxide film—is favoured compared with dissolution (solvation) of the oxidized anion. Depending on the quality of the oxide film, the fonnation of a surface layer can retard further dissolution and virtually stop it after some time. Such surface layers are called passive films. This type of film provides the comparably high chemical stability of many important constmction materials such as aluminium or stainless steels. 

Experimental values for tire sputtering efficiency tend to show lower values of a for elements, such as aluminium and mngsten which form stable oxides, compared with the metals such as gold and platinum which do not under normal experimental conditions. This is probably due to the presence of a surface oxide, since industrial sources of argon, which are used as a source of ions for example, usually contain at least 1 ppm of oxygen, which is more than enough to oxidize aluminium and tungsten. 

Contact with steel, though less harmful, may accelerate attack on aluminium, but in some natural waters and other special cases aluminium can be protected at the expense of ferrous materials. Stainless steels may increase attack on aluminium, notably in sea-water or marine atmospheres, but the high electrical resistance of the two surface oxide films minimises bimetallic effects in less aggressive environments. Titanium appears to behave in a similar manner to steel. Aluminium-zinc alloys are used as sacrificial anodes for steel structures, usually with trace additions of tin, indium or mercury to enhance dissolution characteristics and render the operating potential more electronegative. 

In its resistance to liquid metals, titanium shows variable behaviour, the rate of attack often depending upon temperature and increasing with rise in temperature. By thickening the surface film of oxide, resistance to attack is enhanced, and, for example, repeated repair of the surface film renders titanium resistant, on a limited-time basis, to molten zinc in galvanising baths. A surface-oxide thickening technique also enables titanium to be employed in contact with molten aluminium. Titanium equipment is also used in applications involving lead-tin solders, and it is resistant to mercury, at least up to 150 C. 

That carbon monoxide could be oxidised in a facile reaction at cryogenic temperature (100 K) was first established in 1987 by XPS at an aluminium surface.21 The participation of reactive oxygen transients O 1 (s) was central to the mechanism proposed, whereas the chemisorbed oxide O2 state present at 295 K was unreactive. This provided a further impetus for the transient concept that was suggested for the mechanism of the oxidation of ammonia at a magnesium surface (see Chapter 2). Of particular relevance, and of crucial significance, was Ertl s observation by STM in 1992 that oxygen chemisorption at Al(lll) resulted in kinetically hot adatoms (Figures 4.1 and 4.7). 

The Natural Passivation and Corrosion of Metals and Alloys XPS studies of the air-formed natural passive layer on aluminium surfaces have identified a number of hydroxides as well as alumina (Barr, 1977). The oxidation of pure iron and of stainless steels and other iron alloys have also been extensively... 

Finely divided aluminium powder or dust forms highly explosive dispersions in air [1], and all aspects of prevention of aluminium dust explosions are covered in 2 recent US National Fire Codes [2], The effects on ignition properties of impurities introduced by recycled metal used to prepare dust were studied [3], Pyrophoricity is eliminated by surface coating aluminium powder with polystyrene [4], Explosion hazards involved in arc and flame spraying of the powder are analysed and discussed [5], and the effect of surface oxide layers on flammability was studied [6], The causes of a severe explosion in 1983 in a plant producing fine aluminium powder are analysed, and improvements in safety practices discussed... 

Films of polyolefins, polyamides and poly(vinylidene dichloride) are made using this technique. As most of the films are used for flexible packaging, further down-stream surface treatments are usually applied to improve performance. For example, aqueous polymer emulsions, e.g., poly(vinylidene dichloride), or delaminated clay particles improve the barrier properties as will metallising with aluminium vapour. Corona discharge, causing slight surface oxidation, improves printability. 

Cohen et al. [361] studied, amongst other things, the influence of heat on monolayers of OTS and of arachidic acid adsorbed on surfaces of aluminium oxide formed on aluminium surfaces. They used wetting studies and infrared spectroscopy and concluded that, whereas arachidic acid layers deteriorated in an irreversible manner at about 100°C, OTS layers survived intact to about 140°C. This result is attributed by these authors to polymerisation of the latter material but could also be due to a rather different bonding mechanism between the organic material and the aluminium oxide. 

In PE/aluminium laminates, which are used for packaging, the bond strength can be improved by surface oxidation of the polymer. An alternative to surface oxidation is to use copolymers of ethylene and monomers containing polar groups that can provide stronger bonds to metal thus increasing adhesion [24,25]. The effects of three functional groups in ethylene copolymers, namely EVS [polyethylene-co-vinyl trimethoxy silane], EBA [polyethylene-co-butyl acrylate], EAA [polyethylene-co-acrylic acid) on the adhesion was studied [25]. The interface in polymer/metal laminates has been analysed by FT-IR... 

Shen, J., Kobe, J. M., Chen, Y. and Dumesic, J. A. (1994). Synthesis and surface acid/base properties of magnesium-aluminium mixed oxides obtained from hydrotalcites. Langmuir 10, 3902. 

A great advantage of aluminium is the ability of its oxide film to absorb dyes, this leads to its use in decorative articles such as pen cases, cigarette lighters, etc. The oxide layer is thickened by "anodising , thus producing a porous structure in the oxide film. The dye is absorbed into the pores which are then sealed by hydrolysing the surface oxide. 

Self-assembled monolayers (SAMs) of long-chain alkylthiols on gold, silver and copper (bound as surface thiolates) and of fatty acids (bound as carboxy-lates to surface oxides) on silver, copper and aluminium produced well-... 

Explosion hazards involved in arc and flame spraying of the powder are analysed and discussed [5], and the effect of surface oxide layers on flammability was studied [6]. The causes of a severe explosion in 1983 in a plant producing fine aluminium powder are analysed, and improvements in safety practices discussed... 

Do T, McIntyre NS, Application of parallel factor analysis and X-ray photoelectron spectroscopy to the initial stages in oxidation of aluminium, Surface Science, 1999, 435, 136-141. 

In Fig. 3, the images of the surface and cross-section of porous aluminium anodic oxide films obtained in the HA mode in 4 % orthophosphoric acid aqueous solution, are presented. It is evident that the oxide film has the regular structure. These films can be used as a porous matrix for selective deposition of magnetic materials. 

Conversely, for several aluminium alloys, pit initiation can be accepted under many circumstances. This is so because numerous pits are usually formed, and the oxide is insulating and has therefore low cathodic ability, so that the corrosion rate is under cathodic control. However, if the cathodic reaction can occur on a different metal because of a galvanic connection or for instance deposition of Cu on the aluminium surface, the pitting rate may be very high. Since we in other respects can accept pit initiation, the time dependence of pit growth and pit depths is important, and we shall consider this more quantitatively. 

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