Passivation concentration effect

Passivation phenomena on the whole are highly multifarious and complex. One must distinguish between the primal onset of the passive state and the secondary phenomena that arise when passivation has already occurred (i.e., as a result of passivation). It has been demonstrated for many systems by now that passivation is caused by adsorbed layers, and that the phase layers are formed when passivation has already been initiated. In other cases, passivation may be produced by the formation of thin phase layers on the electrode surface. Relatively thick porous layers can form both before and after the start of passivation. Their effects, as a rule, amount to an increase in true current density and to higher concentration gradients in the solution layer next to the electrode. Therefore, they do not themselves passivate the electrode but are conducive to the onset of a passive state having different origins. 

Chromium passivates very effectively down to very negative potentials even in strongly acidic electrolytes (Fig. 5). The cathodic current density of hydrogen evolution is followed by a small potential range of E = —0.4 to O V of anodic metal dissolution where Cr dissolves as Cr2+. At E > 0 V Cr passivates with a drop of the current density to less than 0.1 pA cm 2. In this potential range Cr3+ is the corrosion product. RRD studies have been applied to determine quantitatively the formation of Cr3+ ions. In principle the dissolution of Cr3+ at a Cr disc may be studied with two concentric analytical rings with their reduction to Cr2+ at the inner ring and its... 

FIGURE 7.3 A schematic illustration of hydrogen peroxide concentration effect on material removal rate of copper with the addition of complexing agent such as glycine and passivating agent such as BTA (from Ref. 11). 

Figure 17.1. Polarization curves that show effect of passivator concentration on corrosion of iron. An oxidizing substance that reduces sluggishly does not induce passivity (dotted cathodic polarization curve) (schematic).

Activation-controlled processes. For purely activation-controlled processes, each reaction can be described by a straight line on an versus log i plot, with positive Tafel slopes for anodic processes and negative Tafel slopes for cathodic processes. The corrosion anodic processes are never limited by concentration effects, but they can be limited by the passivation or formation of a protective film. 

From an electrochemical viewpoint, stable pit growtli is maintained as long as tire local environment witliin tire pit keeps tire pit under active conditions. Thus, tire effective potential at tire pit base must be less anodic tlian tire passivation potential (U ) of tire metal in tire pit electrolyte. This may require tire presence of voltage-drop (IR-drop) elements. In tliis respect the most important factor appears to be tire fonnation of a salt film at tire pit base. (The salt film fonns because tire solubility limit of e.g. FeCl2 is exceeded in tire vicinity of tire dissolving surface in tlie highly Cl -concentrated electrolyte.)... 

Pits occur as small areas of localized corrosion and vary in size, frequency of occurrence, and depth. Rapid penetration of the metal may occur, leading to metal perforation. Pits are often initiated because of inhomogeneity of the metal surface, deposits on the surface, or breaks in a passive film. The intensity of attack is related to the ratio of cathode area to anode ai ea (pit site), as well as the effect of the environment. Halide ions such as chlorides often stimulate pitting corrosion. Once a pit starts, a concentration-cell is developed since the base of the pit is less accessible to oxygen. 

The effects of concentration, velocity and temperature are complex and it will become evident that these factors can frequently outweigh the thermodynamic and kinetic considerations detailed in Section 1.4. Thus it has been demonstrated in Chapter 1 that an increase in hydrogen ion concentration will raise the redox potential of the aqueous solution with a consequent increase in rate. On the other hand, an increase in the rate of the cathodic process may cause a decrease in rate when the metal shows an active/passive transition. However, in complex environmental situations these considerations do not always apply, particularly when the metals are subjected to certain conditions of high velocity and temperature. 

For many metals and alloys the determination of /p is complex, and its magnitude is governed by many factors such as surface finish, rate of formation, alloying constituents, and the presence of those anions, such as halides, that promote localised breakdown. In many instances the attack on passive films by halide ions shows a temperature and concentration dependence similar to the effect of hydrogen ions, i.e. the rate of film dissolution increases with concentration in accordance with a Freundlich adsorption relationship... 

In the main there exists, for each system of a chemical in contact with those metals and alloys that rely on a passive film, the possibility of an increase in corrosion rate with increasing concentration but reaching a maximum and followed by a decrease in rate. If the concentration when this maximum is reached is low, then the chemical is inhibitive . The effect of temperature on corrosion is dependent on the position of the maximum concentration. For many chemical/metal systems this maximum may be at a temperature... 

The arbitrary division of behaviour has been made because of the extreme behaviour of some chemicals that initiate small areas of attack on a well-passivated metal surface. The form of attack may manifest itself as stress-corrosion cracking, crevice attack or pitting. At certain temperatures and pressures, minute quantities of certain chemicals can result in this form of attack. Chloride ions, in particular, are responsible for many of the failures observed, and it can be present as an impurity in a large number of raw materials. This has led to the development of metals and alloys that can withstand pitting and crevice corrosion, but on the whole these are comparatively expensive. It has become important, therefore, to be able to predict the conditions where more conventional materials may be used. The effect of an increase in concentration on pitting corrosion follows a similar relationship to the Freundlich equation where... 

The corrosion behaviour of amorphous alloys has received particular attention since the extraordinarily high corrosion resistance of amorphous iron-chromium-metalloid alloys was reported. The majority of amorphous ferrous alloys contain large amounts of metalloids. The corrosion rate of amorphous iron-metalloid alloys decreases with the addition of most second metallic elements such as titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel, copper, ruthenium, rhodium, palladium, iridium and platinum . The addition of chromium is particularly effective. For instance amorphous Fe-8Cr-13P-7C alloy passivates spontaneously even in 2 N HCl at ambient temperature ". (The number denoting the concentration of an alloy element in the amorphous alloy formulae is the atomic percent unless otherwise stated.)... 

Amorphous Fe-3Cr-13P-7C alloys containing 2 at% molybdenum, tungsten or other metallic elements are passivated by anodic polarisation in 1 N HCl at ambient temperature". Chromium addition is also effective in improving the corrosion resistance of amorphous cobalt-metalloid and nickel-metalloid alloys (Fig. 3.67). The combined addition of chromium and molybdenum is further effective. Some amorphous Fe-Cr-Mo-metalloid alloys passivate spontaneously even in 12 N HCl at 60° C. Critical concentrations of chromium and molybdenum necessary for spontaneous passivation of amorphous Fe-Cr-Mo-13P-7C and Fe-Cr-Mo-18C alloys in hydrochloric acids of various concentrations and different temperatures are shown in Fig. 3.68 ... 

As with most other metals, the anodic behaviour of nickel is influenced by the composition of the solution in which measurements are made, particularly if the solution is acidic. Acidic solutions containing d ions or certain sulphur compounds in particular have a pronounced influence both in increasing the rate of anodic dissolution in the active range and in preventing passivation, and in stimulating localised corrosion . Thiourea and some of its derivatives have a complex effect, acting either as anodic stimulators or inhibitors, depending on their concentration . 

In addition to impurities, other factors such as fluid flow and heat transfer often exert an important influence in practice. Fluid flow accentuates the effects of impurities by increasing their rate of transport to the corroding surface and may in some cases hinder the formation of (or even remove) protective films, e.g. nickel in HF. In conditions of heat transfer the rate of corrosion is more likely to be governed by the effective temperature of the metal surface than by that of the solution. When the metal is hotter than the acidic solution corrosion is likely to be greater than that experienced by a similar combination under isothermal conditions. The increase in corrosion that may arise through the heat transfer effect can be particularly serious with any metal or alloy that owes its corrosion resistance to passivity, since it appears that passivity breaks down rather suddenly above a critical temperature, which, however, in turn depends on the composition and concentration of the acid. If the breakdown of passivity is only partial, pitting may develop or corrosion may become localised at hot spots if, however, passivity fails completely, more or less uniform corrosion is likely to occur. 

Niobium like tantalum relies for its corrosion resistance on a highly adherent passive oxide film it is however not as resistant as tantalum in the more aggressive media. In no case reported in the literature is niobium inert to corrosives that attack tantalum. Niobium has not therefore been used extensively for corrosion resistant applications and little information is available on its performance in service conditions. It is more susceptible than tantalum to embrittlement by hydrogen and to corrosion by many aqueous corrodants. Although it is possible to prevent hydrogen embrittlement of niobium under some conditions by contacting it with platinum the method does not seem to be broadly effective. Niobium is attacked at room temperature by hydrofluoric acid and at 100°C by concentrated hydrochloric, sulphuric and phosphoric acids. It is embrittled by sodium hydroxide presumably as the result of hydrogen absorption and it is not suited for use with sodium sulphide. 

In hydrochloric acid at temperatures up to 100°C, the corrosion rate decreases with time and ferric iron concentration . The presence of air does not affect the general corrosion rate but in IOn acid it promotes pitting attack, which also arises in chloride-containing methanolic solutions in the absence of sufficient water to effect passivation . Alloying niobium with 2.5% or more of tantalum significantly decreases corrosion rates in hydrochloric acid . 

Fig. IS.S Effect of sulphuric acid concentration on chromate passivation of zinc. Solution 182g/1 of Na2Cr207 -2H20 + H2SO4 as indicated temp. I8°C I 0 x 10 mg Zn/cm =...

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