Layers corroded

The interfacial layer is anodic to aluminum and to any metals present in the solder with the exception of zinc. Figure 5 illustrates the difference in electrode potential across a low-temperature soldered joint. In such joints, the interfacial layer corrodes preferentially to protect both the aluminum and the solder. Because the cross section and the total amount of interfacial layer are very small in comparison to the remainder of the assembly, this area can corrode rapidly, and the corrosion resistance of low-temperature soldered joints is relatively poor. 

Rusting can be prevented by painting or coating with a continuous layer of another metal which does not itself corrode rapidly, for example zinc or tin. More recently, steel has been coated with plastics by electrophonetic decomposition from an emulsion of the plastic. 

The resistance to corrosion of some alloy sheet is improved by cladding the sheet with a thin layer of aluminum or aluminum alloy that is anodic to the base alloy. These anodic layers are typically 5—10% of the sheet thickness. Under corrosive conditions, the cladding provides electrochemical protection to the core at cut edges, abrasions, and fastener holes by corroding preferentially. Aircraft skin sheet is an example of such a clad product. 

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. 

Tantalum is not resistant to substances that can react with the protective oxide layer. The most aggressive chemicals are hydrofluoric acid and acidic solutions containing fluoride. Fuming sulfuric acid, concentrated sulfuric acid above 175°C, and hot concentrated aLkaU solutions destroy the oxide layer and, therefore, cause the metal to corrode. In these cases, the corrosion process occurs because the passivating oxide layer is destroyed and the underlying tantalum reacts with even mild oxidising agents present in the system. 

The corroded floor usually is covered with porous friable corrosion product containing ferrous hydroxide, which may form in place by conversion of the steel surface. If acidity is significant, the thickness of this corrosion product layer is slight. 

Copper is not ordinarily corroded in water unless dissolved oxygen is present. In nearly pure aerated water, a thin, protective layer of cuprous oxide and cupric hydroxide forms. Oxygen must diffuse through the film for corrosion to occur. 

Zinc is susceptible to attack from oiQ gen concentration cells. Shielded areas or areas depleted in oxygen concentration tend to corrode, forming voluminous, white, friable corrosion products. Once the zinc layer is breached, the underlying steel becomes susceptible to attack and is severely wasted locally (Figs. 5.12 and 5.13). 

Figure 6.14 A generally corroded carbon steel surface after the slime layer was removed.

Fresh acid attack is recognized by the absence of corrosion product in wasted areas and the sharpness of attack. Oxide layers are usually easily stripped by a test drop of hydrochloric acid in freshly corroded areas. Deposits are almost always absent. Edges of attacked areas are sharp and angular, as intervening corrosion has not recently occurred. In stainless steels such distinctions blur, as corrosion in intervening periods is usually slight. 

At a pH above about 9, in the presence of sodium carbonate or sodium hydroxide, for example, the protective oxide layer is rapidly dissolved and corrosion becomes severe (Fig. 8.1). Aluminum in the presence of sodium hydroxide corrodes as in Reaction 8.2 ... 

Figure 13.1 Layer-type dezincification on a brass casting. The red layers are uniformly corroded regions. The original yellow of the brass is visible in between.

A pump impeller and a shaft bushing from a small cooling water pump assembly were generally corroded. Reddish surface discoloration revealed layer-type dezincification (Figs. 13.14 and 13.15). 

Most of the surface is covered with a black corrosion product that is thicker in relatively low-flow areas near the hub. This layer of soft corrosion product can be shaved from corroded surfaces. Microstructural examinations revealed flakes of graphite embedded in iron oxide near the surfaces. 

Metal loss in these areas had produced a smooth surface, free of deposits and corrosion products. The rest of the internal surface was covered by a thin, uniform layer of soft, black corrosion product. The graphitically corroded surfaces of the pump casing provided soft, friable corrosion products that were relatively easily dislodged by the abrasive effects of high-velocity or turbulent water (erosion-corrosion). 

How does galvanising work As Fig. 24.4 shows, the galvanising process leaves a thin layer of zinc on the surface of the steel. This acts as a barrier between the steel and the atmosphere and although the driving voltage for the corrosion of zinc is greater than that for steel (see Fig. 23.3) in fact zinc corrodes quite slowly in a normal urban atmosphere because of the barrier effect of its oxide film. The loss in thickness is typically 0.1 mm in 20 years. 

At first sight, the answer would seem to be to increase the thickness of the zinc layer. This is not easily done, however, because the hot dipping process used for galvanising is not sufficiently adjustable and electroplating the zinc onto the steel sheet increases the production cost considerably. Painting the sheet (for example, with a bituminous paint) helps to reduce the loss of zinc considerably, but at the same time should vastly decrease the area available for the cathodic protection of the steel and if a scratch penetrates both the paint and the zinc, the exposed steel may corrode through much more quickly than before. 

Under aggressive corrosion conditions it is estimated that the maximum corrosion current density in a galvanised steel sheet will be 6 X 10 A m . Estimate the thickness of the galvanised layer needed to give a rust-free life of at least 5 years. The density of zinc is 7.13 Mg m , and its atomic weight is 65.4. Assume that the zinc corrodes to give Zn " ions. 

Sodium and potassium are restricted because they react with sulfur at elevated temperatures to corrode metals by hot corrosion or sulfurization. The hot-corrision mechanism is not fully understood however, it can be discussed in general terms. It is believed that the deposition of alkali sulfates (Na2S04) on the blade reduces the protective oxide layer. Corrosion results from the continual forming and removing of the oxide layer. Also, oxidation of the blades occurs when liquid vanadium is deposited on the blade. Fortunately, lead is not encountered very often. Its presence is primarily from contamination by leaded fuel or as a result of some refinery practice. Presently, there is no fuel treatment to counteract the presence of lead. 

Corrosion products formed as thin layers on metal surfaces in either aqueous or gaseous environments, and the nature and stability of passive and protective films on metals and alloys, have also been major areas of XPS application. XPS has been used in two ways, one in which materials corroded or passivated in the natural environment are analyzed, and another in which well-characterized, usually pure metal surfaces are studied after exposure to controlled conditions. 

The equilibrium potentials and E, can be calculated from the standard electrode potentials of the H /Hj and M/M " " equilibria taking into account the pH and although the pH may be determined an arbitrary value must be used for the activity of metal ions, and 0 1 = 1 is not unreasonable when the metal is corroding actively, since it is the activity in the diffusion layer rather than that in the bulk solution that is significant. From these data it is possible to construct an Evans diagram for the corrosion of a single metal in an acid solution, and a similar approach may be adopted when dissolved O2 or another oxidant is the cathode reactant. 

One of the outstanding properties of the austenitic irons is their resistance to graphitic corrosion or graphitisation . In some environments ferritic cast irons corrode in such a manner that the surface becomes covered with a layer of graphite. This compact graphite layer, being more noble than the matrix, markedly increases the rate of attack. The austenitic irons rarely form this... 

With a single-phase brass the whole of the metal in the corroded areas is affected. Dezincification may proceed fairly uniformly over the surface, and this layer type takes much longer to cause perforation than the localised plug type that more often occurs . With a two-phase brass the zinc-rich 8 phase is preferentially attacked as shown in Fig. 4.12. Eventually the a phase may be attacked as well. The zinc corrosion products that accompany dezincification may be swept away, or in some conditions may form voluminous deposits on the surface which may lead to blockages, e.g. in fittings. 

Feitknecht has examined the corrosion products of zinc in sodium chloride solutions in detail. The compound on the inactive areas was found to be mainly zinc oxide. When the concentration of sodium chloride was greater than 0-1 M, basic zinc chlorides were found on the corroded parts. At lower concentrations a loose powdery form of a crystalline zinc hydroxide appeared. A close examination of the corroded areas revealed craters which appeared to contain alternate layers and concentric rings of basic chlorides and hydroxides. Two basic zinc chlorides were identified, namely 6Zn(OH)2 -ZnClj and 4Zn(OH)2 ZnCl. These basic salts, and the crystalline zinc hydroxides, were found to have layer structures similar in general to the layer structure attributed to the basic zinc carbonate which forms dense adherent films and appears to play such an important role in the corrosion resistance of zinc against the atmosphere. The presence of different reaction products in the actual corroded areas leads to the view that, in addition to action between the major anodic and cathodic areas as a whole, there is also a local interaction between smaller anodic and cathodic elements. 

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