Sulphate corrosion

Salt solutions When a zinc sheet is immersed in a solution of a salt, such as potassium chloride or potassium sulphate, corrosion usually starts at a number of points on the surface of the metal, probably where there are defects or impurities present. From these it spreads downwards in streams, if the plate is vertical. Corrosion will start at a scratch or abrasion made on the surface but it is observed that it does not necessarily occur at all such places. In the case of potassium chloride (or sodium chloride) the corrosion spreads downwards and outwards to cover a parabolic area. Evans explains this in terms of the dissolution of the protective layer of zinc oxide by zinc chloride to form a basic zinc chloride which remains in solution. 

Copper and brass may be included in the plant material of construction subject to corrosive aqueous environments. In general these metals have good corrosion resistance but under certain conditions, e.g. high pH and in the presence of high concentrations of chlorides and sulphates, corrosion of copper and dezincification of brass can occur. Under these conditions it is possible to use various heterocyclic compounds for example the sodium salt of 2-mercaptobenzothiazoleor benzotrizole, to limit corrosion by the formation of an insoluble chemical complex at the anodic areas. 

In the opinion of experts, expressed during the workshop on the sulphate corrosion resistance, a low permeability of concrete is more important than the use of high sulphate resistant cement, in the case of sulphate corrosion hazard [65]. Therefore the w/c ratio maintained on a low level, together with higher cement content and proper curing of concrete at the early age of hardening, are of basic significance. 

This classification has a long tradition and reflects rather the problems to be resolved by the specialists in the field of cement chemistry, with aim to improve the durability of concrete in the more fiequently occurring aggressive enviromnents. The sulphate corrosion is here a typical, common example, which led to the invention of calcium aluminate cement by Bied (ciment fondu). The deterioration of concrete by de-icers, used in millions tons (for example in the USA in winter 1966/1967 6.3 milliont [62]), became a serious problem. The cost of bridges repairs in USA in 1975 was 200 million [63]. 

In reality the mechanism of concrete deterioration as a consequence of acid corrosion, if it is sulphuric acid, is the same as in case of sulphate corrosion. For this reason in both environments the matrix based on Portland cement with reduced Cj A content is more resistant. This example shows the imperfection of kind of corrosion classification, presented above. 

As a result of sulphate corrosion the major changes of concrete microstructure occurs. In the absence of any corrosion processes, cement matrix in concrete shows some specific features the most important ones are listed below (Fig. 6.63) [261] ... 

The destruction of concrete due to the formation of thaumasite replacing the C-S-H phase is a special case of sulphate corrosion. This process is promoted by the simultaneous intensive carbonation, or by use of limestone Portland cement, together with the low temperature. In Poland the destruction of concrete stractures due to the thaumasite formation has not been reported, however, this ean arise from the multicomponent paste composition of damaged concrete and very similar XRD pattern of thaumasite and ettringite. 

The reaction of metals with gas mixtures such as CO/CO2 and SO2/O2 can lead to products in which the reaction of the oxygen potential in the gas mixture to form tire metal oxides is accompanied by the formation of carbon solutions or carbides in tire hrst case, and sulphide or sulphates in the second mixture. Since the most importairt aspects of this subject relate to tire performairce of materials in high temperature service, tire reactions are refeiTed to as hot corrosion reactions. These reactions frequendy result in the formation of a liquid as an intermediate phase, but are included here because dre solid products are usually rate-determining in dre coiTosion reactions. 

Aluminium Building materials Corrosion to aluminium sulphate (white)... 

Aqueous environments will range from very thin condensed films of moisture to bulk solutions, and will include natural environments such as the atmosphere, natural waters, soils, body fluids, etc. as well as chemicals and food products. However, since environments are dealt with fully in Chapter 2, this discussion will be confined to simple chemical solutions, whose behaviour can be more readily interpreted in terms of fundamental physicochemical principles, and additional factors will have to be considered in interpreting the behaviour of metals in more complex environments. For example, iron will corrode rapidly in oxygenated water, but only very slowly when oxygen is absent however, in an anaerobic water containing sulphate-reducing bacteria, rapid corrosion occurs, and the mechanism of the process clearly involves the specific action of the bacteria see Section 2.6). 

Soluble corrosion products may increase corrosion rates in two ways. Firstly, they may increase the conductivity of the electrolyte solution and thereby decrease internal resistance of the corrosion cells. Secondly, they may act hygroscopically to form solutions at humidities at and above that in equilibrium with the saturated solution (Table 2.7). The fogging of nickel in SO2-containing atmospheres, due to the formation of hygroscopic nickel sulphate, exemplifies this type of behaviour. However, whether the corrosion products are soluble or insoluble, protective or non-protective, the... 

Critical relative humidity The primary value of the critical relative humidity denotes that humidity below which no corrosion of the metal in question takes place. However, it is important to know whether this refers to a clean metal surface or one covered with corrosion products. In the latter case a secondary critical humidity is usually found at which the rate of corrosion increases markedly. This is attributed to the hygroscopic nature of the corrosion product (see later). In the case of iron and steel it appears that there may even be a tertiary critical humidity . Thus at about 60% r.h. rusting commences at a very slow rate (primary value) at 75-80% r.h. there is a sharp increase in corrosion rate probably attributable to capillary condensation of moisture within the rust . At 90% r.h. there is a further increase in rusting rate corresponding to the vapour pressure of saturated ferrous sulphate solution , ferrous sulphate being identifiable in rust as crystalline agglomerates. The primary critical r.h. for uncorroded metal surfaces seems to be virtually the same for all metals, but the secondary values vary quite widely. 

Rainfall, besides wetting the metal surface, can be beneficial in leaching otherwise deleterious soluble species and this can result in marked decreases in corrosion rate . A recent survey of rainfall analyses for Europe has shown that, with the exception of the UK, the acidity and sulphate content of rainfall markedly increased in the period 1956 to 1966, pH values having fallen by 0 05 to 0-10 units per ann. The exception of the UK may be due to anti-pollution measures introduced in this period. However, even in the UK a pH of 4 is not uncommon for rainfall in industrial areas. The significance of electrolyte solution pH will be discussed in the context of corrosion mechanisms. The remaining cases of electrolyte formation are those in which it exists in equilibrium with air at a relative humidity below 100%. 

Chemical condensation This occurs when soluble corrosion products or atmospheric contaminants are present on the metal surface. When the humidity exceeds that in equilibrium with a saturated solution of the soluble species, a solution, initially saturated, is formed until equilibrium is established with the ambient humidity. The contaminants have already been detailed and of the corrosion products, obviously sulphates, chlorides and carbonates are most important in this context. However, in some cases there is a lack of reliable data on the vapour pressure exerted by saturated solutions of likely corrosion products. The useful data was summarised in Table 2.7. 

For some non-ferrous metals (copper, lead, nickel) the attack by sulphuric acid is probably direct with the formation of sulphates. Lead sulphate is barely soluble and gives good protection. Nickel and copper sulphates are deliquescent but are gradually converted (if not leached away) into insoluble basic sulphates, e.g. Cu Cu(OH)2)3SO4, and the metals are thus protected after a period of active corrosion. For zinc and cadmium the sulphur acids probably act by dissolution of the protective basic carbonate film. This reforms, consuming metal in the process, redissolves, and so on. Zinc and cadmium sulphates are formed in polluted winter conditions whereas in the purer atmospheres of the summer the corrosion products include considerable amounts of oxide and basic carbonate. ... 

Thus for non-ferrous metals, SO is consumed in the corrosion reactions whereas in the rusting of iron and steel it is believed that ferrous sulphate is hydrolysed to form oxides and that the sulphuric acid is regenerated. Sulphur dioxide thus acts as a catalyst such that one SOj" ion can catalyse the dissolution of more than 100 atoms of iron before it is removed by leaching, spalling of rust or the formation of basic sulphate. These reactions can be summarised as follows ... 

Weather conditions at the time of initial exposure of zinc and steel have a large influence on the protective nature of the initial corrosion products This can still be detected some months after initial exposure. Finally, rust on steel contains a proportion of ferrous sulphate which increases with increase in SO2 pollution of the atmosphere. The effect of this on corrosion rate is so strong that mild steel transferred from an industrial atmosphere to a rural one corrodes for some months as though it was still exposed to the industrial environment. ... 

Dissolved mineral salts The principal ions found in water are calcium, magnesium, sodium, bicarbonate, sulphate, chloride and nitrate. A few parts per million of iron or manganese may sometimes be present and there may be traces of potassium salts, whose behaviour is very similar to that of sodium salts. From the corrosion point of view the small quantities of other acid radicals present, e.g. nitrite, phosphate, iodide, bromide and fluoride, have little significance. Larger concentrations of some of these ions, notably nitrite and phosphate, may act as corrosion inhibitors, but the small quantities present in natural waters will have little effect. Some of the minor constituents have other beneficial or harmful effects, e.g. there is an optimum concentration of fluoride for control of dental caries and very low iodide or high nitrate concentrations are objectionable on medical grounds. 

Sulphate in general appears to behave very similarly Hatch and Rice have shown that small concentrations in distilled water increase corrosion more than similar concentrations of chloride". In practice, high-sulphate waters may attack concrete, and the performance of some inhibitors appears to be adversely affected by the presence of sulphate. Sulphates have also a special role in bacterial corrosion under anaerobic conditions. Both sulphates and nitrates are acceptable in low-pressure boiler feed water as they are believed to be of value in controlling caustic cracking. 

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