Passivity metal oxidation

Environmental tests have been combined with conventional electrochemical measurements by Smallen et al. [131] and by Novotny and Staud [132], The first electrochemical tests on CoCr thin-film alloys were published by Wang et al. [133]. Kobayashi et al. [134] reported electrochemical data coupled with surface analysis of anodically oxidized amorphous CoX alloys, with X = Ta, Nb, Ti or Zr. Brusic et al. [125] presented potentiodynamic polarization curves obtained on electroless CoP and sputtered Co, CoNi, CoTi, and CoCr in distilled water. The results indicate that the thin-film alloys behave similarly to the bulk materials [133], The protective film is less than 5 nm thick [127] and rich in a passivating metal oxide, such as chromium oxide [133, 134], Such an oxide forms preferentially if the Cr content in the alloy is, depending on the author, above 10% [130], 14% [131], 16% [127], or 17% [133], It is thought to stabilize the non-passivating cobalt oxides [123], Once covered by stable oxide, the alloy surface shows much higher corrosion potential and lower corrosion rate than Co, i.e. it shows more noble behavior [125]. 

In 1985 David DeBerry [107], reported for the first time a change in corrosion behaviour of stainless steel with an electroactive polyaniline coating. He deposited polyaniline electrochemically from a pHl.O perchloric acid solution onto stainless steel and concluded that the coating was deposited over the passive metal oxide film (present on the metal surface in an acid environment). 

The formation of a passive metal oxide layer, which prevents the metal from being corroded, does proceed without any electrochemical step. For this purpose, polyaniline is deposited on metal surfaces using dispersions. 

During EMM, oxide layer is formed on the workpiece due to anodic reaction. For some material this oxide layer is passive in nature which minimize the rate of current flow and thus lower the machining rate. Laser beam can also minimize the formation of oxide layer by increasing the temperature of the upper surface of the workpiece which restricts the chemical reaction responsible for the formation of passive metal oxide layer especially in the case of passivating electrolytes. Hence, the combination of laser beam with EMM will prove to be beneficial for higher material removal. 

A second attempt to explain the corrosion protection of polyanUine was the formulation of a mechanism with a catalytic reduction of oxygen and a simultaneous formation of a passivating metal oxide film on the substrate. Later it was shown that this mechanism is not supported by experimental investigations. ... 

F. Passivating Metal Oxide Layers and Electronic Structures of Conductive Polymers... 

Visual observation of passivation oxide layers revealed the deposition of a grayish oxide layer film over the CRS surface (Wessling, 1994, 1996) under an EPCN coating on a CRS electrode. SEM image studies revealed that oxide layers were formed at the interface of an EPCN (i.e. EPCN03) coating and a CRS surface (Fig. 13.19(b)). However, the bare CRS surface was smooth and clear we could not observe the passive metal oxide layer on the bare CRS surface (Fig. 13.19(a)). 

Corrosion protection of metals can take many fonns, one of which is passivation. As mentioned above, passivation is the fonnation of a thin protective film (most commonly oxide or hydrated oxide) on a metallic surface. Certain metals that are prone to passivation will fonn a thin oxide film that displaces the electrode potential of the metal by +0.5-2.0 V. The film severely hinders the difflision rate of metal ions from the electrode to tire solid-gas or solid-liquid interface, thus providing corrosion resistance. This decreased corrosion rate is best illustrated by anodic polarization curves, which are constructed by measuring the net current from an electrode into solution (the corrosion current) under an applied voltage. For passivable metals, the current will increase steadily with increasing voltage in the so-called active region until the passivating film fonns, at which point the current will rapidly decrease. This behaviour is characteristic of metals that are susceptible to passivation. 

For example,copper has relatively good corrosion resistance under non-oxidizing conditions. It can be alloyed with zinc to yield a stronger material (brass), but with lowered corrosion resistance. Flowever, by alloying copper with a passivating metal such as nickel, both mechanical and corrosion properties are improved. Another important alloy is steel, which is an alloy between iron (>50%) and other alloying elements such as carbon. 

Highly protective layers can also fonn in gaseous environments at ambient temperatures by a redox reaction similar to that in an aqueous electrolyte, i.e. by oxygen reduction combined with metal oxidation. The thickness of spontaneously fonned oxide films is typically in the range of 1-3 nm, i.e., of similar thickness to electrochemical passive films. Substantially thicker anodic films can be fonned on so-called valve metals (Ti, Ta, Zr,. ..), which allow the application of anodizing potentials (high electric fields) without dielectric breakdown. 

The passive state of a metal can, under certain circumstances, be prone to localized instabilities. Most investigated is the case of localized dissolution events on oxide-passivated surfaces [51, 106, 107, 108, 109, 110, ill, 112, 113, 114, 115, 116, 117 and 118]. The essence of localized corrosion is that distinct anodic sites on the surface can be identified where the metal oxidation reaction (e.g. Fe —> Fe + 2e ) dominates, surrounded by a cathodic zone where the reduction reaction takes place (e.g. 2Fi + 2e —> Fi2). The result is the fonnation of an active pit in the metal, an example of which is illustrated in figure C2.8.6(a) and (b). 

Nitric acid reacts with all metals except gold, iridium, platinum, rhodium, tantalum, titanium, and certain alloys. It reacts violentiy with sodium and potassium to produce nitrogen. Most metals are converted iato nitrates arsenic, antimony, and tin form oxides. Chrome, iron, and aluminum readily dissolve ia dilute nitric acid but with concentrated acid form a metal oxide layer that passivates the metal, ie, prevents further reaction. 

Metal Cleaning. Citric acid, partially neutralized to - pH 3.5 with ammonia or triethanolamine, is used to clean metal oxides from the water side of steam boilers and nuclear reactors with a two-step single fill operation (104—122). The resulting surface is clean and passivated. This process has a low corrosion rate and is used for both pre-operational mill scale removal and operational cleaning to restore heat-transfer efficiency. 

For example, chloride and duoride ions, even in trace amounts (ppm), could cause the dissolution of aluminum metallization of complimentary metal oxide semiconductor (CMOS) devices. CMOS is likely to be the trend of VLSI technology and sodium chloride is a common contaminant. The protection of these devices from the effects of these mobile ions is an absolute requirement. The use of an ultrahigh purity encapsulant to encapsulate the passivated IC is the answer to some mobile ion contaminant problems. 

There is often a period before corrosion starts in a crevice in passivating metals. This so-called incubation period corresponds to the time necessary to establish a crevice environment aggressive enough to dissolve the passive oxide layer. The incubation period is well known in stainless steels exposed to waters containing chloride. After a time period in which crevice corrosion is negligible, attack begins, and the rate of metal loss increases (Fig. 2.8). 

Ox and Red are general symbols for oxidation and reduction media respectively, and n and (n-z) indicate their numerical charge (see Section 2.2.2). Where there is no electrochemical redox reaction [Eq. (2-9)], the corrosion rate according to Eq. (2-4) is zero because of Eq. (2-8). This is roughly the case with passive metals whose surface films are electrical insulators (e.g., A1 and Ti). Equation (2-8) does not take into account the possibility of electrons being diverted through a conductor. In this case the equilibrium... 

Figure 4-421. Corrosion characteristics of an active passive metal as a function of solution oxidizing power (eiectrode potential). (From Ref. [183].)...

There are various theories on how passive films are formed however, there are two commonly accepted theories. One theory is called the oxide film theory and states that the passive film is a diffusion-barrier layer of reaction products (i.e., metal oxides or other compounds). The barriers separate the metal from the hostile environment and thereby slow the rate of reaction. Another theory is the adsorption theory of passivity. This states that the film is simply adsorbed gas that forms a barrier to diffusion of metal ions from the substrata. 

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