Oxide scales

Saunders S R J, Evans FI E and Stringer J A (eds) Workshop on Mechanical Properties of Protective Oxide Scales. Materials at High Temperatures vo 12 (Teddington)... 

HCl gas reacts with metal oxides to form chlorides, oxychlorides, and water. Therefore, all the steel equipment should be pickled to remove the oxide scales before it is put in service. Because oxidi2ing agents in the HCl gas such as oxygen or chlorine significantly affect the corrosion rate, it is essential that the operating temperature of the steel equipment be kept below the temperature (316°C) at which ferric chloride is vapori2ed from the metal surface. 

Metal Treatment. After rolling, the oxide scale on sheet steel is removed by acid treatment (pickling) (see Metal surface treatments). Phosphoric acid, a good pickling agent, leaves the steel coated with a thin film of iron phosphates. This process improves mst resistance but presents a problem if the steel is to be electroplated. 

A good summary of the behavior of steels in high temperature steam is available (45). Calculated scale thickness for 10 years of exposure of ferritic steels in 593°C and 13.8 MPa (2000 psi) superheated steam is about 0.64 mm for 5 Cr—0.5 Mo steels, and 1 mm for 2.25 Cr—1 Mo steels. Steam pressure does not seem to have much influence. The steels form duplex layer scales of a uniform thickness. Scales on austenitic steels in the same test also form two layers but were irregular. Generally, the higher the alloy content, the thinner the oxide scale. Excessively thick oxide scale can exfoHate and be prone to under-the-scale concentration of corrodents and corrosion. ExfoHated scale can cause soHd particle erosion of the downstream equipment and clogging. Thick scale on boiler tubes impairs heat transfer and causes an increase in metal temperature. 

Directed Oxidation of a Molten Metal. Directed oxidation of a molten metal or the Lanxide process (45,68,91) involves the reaction of a molten metal with a gaseous oxidant, eg, A1 with O2 in air, to form a porous three-dimensional oxide that grows outward from the metal/ceramic surface. The process proceeds via capillary action as the molten metal wicks into open pore channels in the oxide scale growth. Reinforced ceramic matrix composites can be formed by positioning inert filler materials, eg, fibers, whiskers, and/or particulates, in the path of the oxide scale growth. The resultant composite is comprised of both interconnected metal and ceramic. Typically 5—30 vol % metal remains after processing. The composite product maintains many of the desirable properties of a ceramic however, the presence of the metal serves to increase the fracture toughness of the composite. 

Sulfur Corrosion Chromium is the most important material in imparting resistance to sulfidation (formation of smfidic scales similar to oxide scales). The austenitic alloys are generally used because of their superior mechanical properties and fabrication qualities, despite the fact that nickel in the alloy tends to lessen resistance to sulfidation somewhat. 

The reaction of CH4 with hydrogen, at the odrer end of die oxidation scale, produces mainly acetylene, C2H2, edrylene C2H4 and ethane, C2H6. These reactions are favoured by operating at high temperatures. In fact the production of acetylene is most efficient if die gas mixmre is passed drrough an arc struck between carbon electrodes, which probably produces a reaction temperature in excess of 2500 K. 

Find the depth of metal lost from the surface of a mild steel tie bar in a furnace at 500°C after 1 year. You may assume that the oxide scale is predominantly FeO. The atomic weight and density of iron are 55.9 kg kmoL and 7.87Mgm" the atomic weight of oxygen is 16 kg kmol F What would be the loss at 600°C ... 

To fully understand the formation of the N13S2 scale under certain gas conditions, a brief description needs to be given on the chemical aspects of the protective (chromium oxide) Ci 203/(nickel oxide) NiO scales that form at elevated temperatures. Under ideal oxidizing conditions, the alloy Waspaloy preferentially forms a protective oxide layer of NiO and Ci 203 The partial pressure of oxygen is such that these scales are thermodynamically stable and a condition of equilibrium is observed between the oxidizing atmosphere and the scale. Even if the scale surface is damaged or removed, the oxidizing condition of the atmosphere would preferentially reform the oxide scales. 

Oxide scales Oxide scale on alloyed steel 4.218... 

These steels resist oxidation scaling up to 825°C but are difficult to weld and, thus, are used mainly for items that do not involve welded joints [17]. They are thermally hardened and useful for items that require cutting edges and abrasion resistance in mildly corrosive situations. However, they should not be tempered in the temperature range of 450 to 650°C. This reduces the hardness and wear resistance and also lowers the corrosion resistance because of the depletion of chromium in solution through the formation of chromium carbides. 

Atmospheric exposure at temperatures in excess of 480°C, because of oxide scaling ... 

Fortunately the oxidation of many metals takes place by the diffusion of the metal cation . This flux is outwards through the oxide layer, and the work of adhesion" enables the loss of metal to be compensated for by a drift of the oxide towards the metal (Fig. 1.81). Thus the stresses set up in the maintenance of oxide/metal contact are compressive and, as such, can be more readily withstood by most oxides. Nevertheless, it is these general movements of the oxide scale which are ultimately responsible for discontinuities in the majority of cases and it is appropriate to discuss transport-induced flows before proceeding any further. 

If the PBR is less than unity, the oxide will be non-protective and oxidation will follow a linear rate law, governed by surface reaction kinetics. However, if the PBR is greater than unity, then a protective oxide scale may form and oxidation will follow a reaction rate law governed by the speed of transport of metal or environmental species through the scale. Then the degree of conversion of metal to oxide will be dependent upon the time for which the reaction is allowed to proceed. For a diffusion-controlled process, integration of Pick s First Law of Diffusion with respect to time yields the classic Tammann relationship commonly referred to as the Parabolic Rate Law ... 

In some circumstances, the reaction rates may not be exactly parabolic, and even initially parabolic rates may be influenced by changes within the oxide scale with time. As an oxide scale grows, the build-up of inherent growth stresses, externally applied strains and chemical changes to either oxide scale or metal may all compromise the initial protection offered by the scale, leading to scale breakdown and ultimately partial or complete loss of protection paralinear, or linear kinetics may ensue. In other circumstances, as will be seen later in this chapter, very small additions of contaminants to... 

Since Mn is both soluble in iron oxides and mobile to the same extent as Fe, the addition of Mn to steels has little effect on the overall scaling rate in air or oxygen. Jackson and Wallwork have shown that between 20% and 40% manganese must be added to steel before the iron oxides are replaced by manganese oxides. However, Mn supresses breakaway oxidation in CO/CO2 possibly by reducing the coalescence of pores in the oxide scale. 

As indicated earlier, protective oxide scales typically have a PBR greater than unity and are, therefore, less dense than the metal from which they have formed. As a result, the formation of protective oxides invariably results in a local volume increase, or a stress-free oxidation strain" . If lateral growth occurs, then compressive stresses can build up, and these are intensified at convex and reduced at concave interfaces by the radial displacement of the scale due to outward cation diffusion (Fig. 7.7) . 

Under thermal cycling conditions, the principal source of stress within the oxide scale is the temperature change . Christl et have noted that, when cooling 2.25%Cr-l%Mo steel from 600°C in air, compressive stresses build up in the haematite, whilst tensile stresses build up in the magnetite and spinel layers. This arises because the thermal expansion coefficients of the individual oxide layers increase in the order a metal < a spinel < a magnetite < a haematite . ... 

Since the paper by Pilling and Bedworth in 1923 much has been written about the mechanism and laws of growth of oxides on metals. These studies have greatly assisted the understanding of high-temperature oxidation, and the mathematical rate laws deduced in some cases make possible useful quantitative predictions. With alloy steels the oxide scales have a complex structure chromium steels owe much of their oxidation resistance to the presence of chromium oxide in the inner scale layer. Other elements can act in the same way, but it is their chromium content which in the main establishes the oxidation resistance of most heat-resisting steels. 

Barrett and his colleagues , and Kosakhave summarised existing information on the scales formed on nickel-chromium alloys. Up to about 10% Cr, the thick black scale is composed of a double layer, the outer layer being nickel oxide and the inner porous layer a mixture of nickel oxide with small amounts of the spinel NiO CrjOj. Internal oxidation causes the formation of a subscale consisting of chromium oxide particles embedded in the nickel-rich matrix. At 10-20% Cr the scale is thinner and grey coloured and consists of chromium oxide and spinel with the possible presence of some nickel oxide. At about 25-30% Cr a predominantly chromium oxide scale is... 

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