Cathode surface

The most favorable conditions for equation 9 are temperature from 60—75°C and pH 5.8—7.0. The optimum pH depends on temperature. This reaction is quite slow and takes place in the bulk electrolyte rather than at or near the anode surface (44—46). Usually 2—5 g/L of sodium dichromate is added to the electrolysis solution. The dichromate forms a protective Cr202 film or diaphragm on the cathode surface, creating an adverse potential gradient that prevents the reduction of OCU to CU ion (44). Dichromate also serves as a buffering agent, which tends to stabilize the pH of the solution (45,46). Chromate also suppresses corrosion of steel cathodes and inhibits O2 evolution at the anode (47—51). 

The low current efficiency of this process results from the evolution of hydrogen at the cathode. This occurs because the hydrogen deposition overvoltage on chromium is significantly more positive than that at which chromous ion deposition would be expected to commence. Hydrogen evolution at the cathode surface also increases the pH of the catholyte beyond 4, which may result in the precipitation of Cr(OH)2 and Cr(OH)2, causing a partial passivation of the cathode and a reduction in current efficiency. The latter is also inherently low, as six electrons are required to reduce hexavalent ions to chromium metal. 

Current density can be increased without impairing the quaUty of the copper by polishing the cathode surface by brief periodic current reversals (PCR). Reversed current electrolysis, first developed for electroplating, was tested in 1952 for copper refining. Although good results were obtained, no suitable electrical equipment for current reversal was available. The thyristor-controUed siUcon rectifier, introduced in the 1960s, provided a means for... 

Asahi also reports an undivided cell process employing a lead alloy cathode, a nickel—steel anode, and an electrolyte composed of an emulsion of 20 wt % of an oil phase and 80 wt % of an aqueous phase (125). The aqueous phase is 10 wt % K HPO, 3 wt % K B O, and 2 wt % (C2H (C4H )2N)2HP04. The oil phase is about 28 wt % acrylonitrile and 50 wt % adiponitrile. The balance of the oil phase consists of by-products and water. The cell operates at a current density of 20 A/dm at 50°C. Circulated across the cathode surface at a superficial velocity of 1.5 m/s is the electrolyte. A 91% selectivity to adiponitrile is claimed at a current efficiency of 90%. The respective anode and cathode corrosion rates are about mg/(Ah). Asahi s improved EHD process is reported to have been commercialized in 1987. 

The crevice shape markedly affects corrosion. Crevices so tight that water may not enter are entirely immune to attack. In misting environments or alternately wet-diy environments, the crevice holds water and may allow continued attack even when neeu by surfaces eire dry. In sea water, the severity of attack in stainless steel crevices depends on the ratio of the crevice area to the cathodic surface area outside the crevice. If the cathodic area is large relative to crevice eirea, corrosion is promoted. 

Stainless steels tend to pit in acid solutions. Pits form local areas of metal loss associated with breakdown of a protective oxide layer. Breakdown is stimulated by low pH as well as by the decrease of dissolved oxygen in occluded regions. Small, active pit sites form and remain stable because of the large ratio of cathodic surface area (unattacked metal surface) to the pit area. Active corrosion in the pit cathodically protects immediately adjacent areas. If conditions become very severe, pitting will give way to general attack as more and more of the surface becomes actively involved in corrosion. 

Different microstructural regions in a material which has an almost uniform composition can also lead to the formation of corrosion cells (e.g., in the vicinity of welds). Basically, corrosion cells can be successfully overcome by cathodic protection. However, in practice, care has to be taken to avoid electrical shielding by large current-consuming cathode surfaces by keeping the area as small as possible. In general, with mixed installations of different metals, it must be remembered that the protection potentials and the protection range depend on the materials (Section 2.4). This can restrict the use of cathodic protection or make special potential control necessary. 

In practice, the current densities for protecting concrete structures are generally lower than the values in Table 19-1. The reason is that the cathode surfaces are not well aerated and areas of the anodes are dry. Practical experience and still-incomplete investigations [43] indicate that at even more positive potentials than those given in Table 19-1 with U = -0.35 V, noticeable protection can be achieved so that = -0.4 V can be regarded as the protection potential. In DIN 30676, t/jj5 = -0.43 V is given [44] (see also Section 2.4). 

Passivating inhibitors act in two ways. First they can reduce the passivating current density by encouraging passive film formation, and second they raise the cathodic partial current density by their reduction. Inhibitors can have either both or only one of these properties. Passivating inhibitors belong to the group of so-called dangerous inhibitors because with incomplete inhibition, severe local active corrosion occurs. In this case, passivated cathodic surfaces are close to noninhibited anodic surfaces. 

Fig. 3.55. LEIS spectra obtained from an Os/Ru top layer dispenser cathode with 3 keV He, Ne, and Ar projectiles, respectively. The He spectrum demonstrates the absence ofO on an undamaged cathode surface, the insert in the He spectrum was obtained for a cathode exposed to 20 Langmuir oxygen at room temperature [3.141].

Kathoden-dichte, /. cathode density, -fiache, /. cathode surface, -licht, n. cathode glow, -niederschlag, m. cathode deposit, -raum, m. cathode space, space aroimd the cathode, -rdhre, /. cathode-ray tube, -strahl, m. cathode ray. -strahlenbiindel. n. cathode beam, -strahlrbhre, /. cathode-ray tube, -strahlimg. /. cathode radiation, -strom, m. cathode current, -zerstaubimg, /. cathode sputtering. 

From these two examples, which as will be seen subsequently, present a very oversimplified picture of the actual situation, it is evident that macroheterogeneities can lead to localised attack by forming a large cathode/small anode corrosion cell. For localised attack to proceed, an ample and continuous supply of the electron acceptor (dissolved oxygen in the example, but other species such as the ion and Cu can act in a similar manner) must be present at the cathode surface, and the anodic reaction must not be stifled by the formation of protective films of corrosion products. In general, localised attack is more prevalent in near-neutral solutions in which dissolved oxygen is the cathode reactant thus in a strongly acid solution the millscale would be removed by reductive dissolution see Section 11.2) and attack would become uniform. 

A simple calculation based on the solubility product of ferrous hydroxide and assuming an interfacial pH of 9 (due to the alkalisation of the cathodic surface by reaction ) shows that, according to the Nernst equation, at -0-85 V (vs. CU/CUSO4) the ferrous ion concentration then present is sufficient to permit deposition hydroxide ion. It appears that the ferrous hydroxide formed may be protective and that the practical protection potential ( —0-85 V), as opposed to the theoretical protection potential (E, = -0-93 V), is governed by the thermodynamics of precipitation and not those of dissolution. 

Attention must be paid to field end effects, particularly on cantilever anodes, e.g. on long anodes that extend away from the cathode surface. Under these circumstances the anode surface close to the cathode may be operating at a considerably higher current density than the mean value, with the exact values dependent upon the system geometry. The life of the platinising in this region would then be reduced in inverse proportion to the current density. 

Some investigatorshave advocated a type of accelerated test in which the specimens are coupled in turn to a noble metal such as platinum in the corrosive environment and the currents generated in these galvanic couples are used as a measure of the relative corrosion resistance of the metals studied. This method has the defects of other electrolytic means of stimulating anodic corrosion, and, in addition, there is a further distortion of the normal corrosion reactions and processes by reason of the differences between the cathodic polarisation characteristics of the noble metal used as an artificial cathode and those of the cathodic surfaces of the metal in question when it is corroding normally. 

The chemical mechanism rests on the effect of intervening redox systems (see Section 13.6). Here intermediate reactants such as species on a cathode surface, species on an anode surface, or reducing and oxidizing agents in the solution layer next to the electrode are first produced electrochemicaUy from solution components. The further interaction of these reactants with the organic substance is purely chemical in character, for example, following a reaction... 

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