Transition anodes

The porous electrodes in PEFCs are bonded to the surface of the ion-exchange membranes which are 0.12- to 0.25-mm thick by pressure and at a temperature usually between the glass-transition temperature and the thermal degradation temperature of the membrane. These conditions provide the necessary environment to produce an intimate contact between the electrocatalyst and the membrane surface. The early PEFCs contained Nafton membranes and about 4 mg/cm of Pt black in both the cathode and anode. Such electrode/membrane combinations, using the appropriate current coUectors and supporting stmcture in PEFCs and water electrolysis ceUs, are capable of operating at pressures up to 20.7 MPa (3000 psi), differential pressures up to 3.5 MPa (500 psi), and current densities of 2000 m A/cm. ... 

Iron carbide (3 1), Fe C mol wt 179.56 carbon 6.69 wt % density 7.64 g/cm mp 1650°C is obtained from high carbon iron melts as a dark gray air-sensitive powder by anodic isolation with hydrochloric acid. In the microstmcture of steels, cementite appears in the form of etch-resistant grain borders, needles, or lamellae. Fe C powder cannot be sintered with binder metals to produce cemented carbides because Fe C reacts with the binder phase. The hard components in alloy steels, such as chromium steels, are double carbides of the formulas (Cr,Fe)23Cg, (Fe,Cr)2C3, or (Fe,Cr)3C2, that derive from the binary chromium carbides, and can also contain tungsten or molybdenum. These double carbides are related to Tj-carbides, ternary compounds of the general formula M M C where M = iron metal M = refractory transition metal. 

Spontaneous Passivation The anodic nose of the first curve describes the primary passive potential Epp and critical anodic current density (the transition from active to passive corrosion), if the initial active/passive transition is 10 lA/cm or less, the alloy will spontaneously passivate in the presence of oxygen or any strong oxidizing agent. 

Stress corrosion can arise in plain carbon and low-alloy steels if critical conditions of temperature, concentration and potential in hot alkali solutions are present (see Section 2.3.3). The critical potential range for stress corrosion is shown in Fig. 2-18. This potential range corresponds to the active/passive transition. Theoretically, anodic protection as well as cathodic protection would be possible (see Section 2.4) however, in the active condition, noticeable negligible dissolution of the steel occurs due to the formation of FeO ions. Therefore, the anodic protection method was chosen for protecting a water electrolysis plant operating with caustic potash solution against stress corrosion [30]. The protection current was provided by the electrolytic cells of the plant. 

The transition resistance between the surface of the metal and the electrolyte with uncoated iron anodes in coke backfill, the transition resistance is usually low. With metals in soil, it can be increased by films of grease, paint, rust or deposits. It contains in addition an electrochemical polarization resistance that depends on the current [see Eq. (2-35)]. 

The typical features of a metal/solution system that exhibits an active to passive transition is shown in Fig. 1.33, which represents diagrammatically the potentiostatically determined anodic / curve for iron in HjS04. ... 

Fig. 1.39 Schematic anodic polarisation curve for a metal. Region AB describes active dissolution of the metal. BC is the active/passive transition, with passivation commencing at B. Passivation is complete only at potentials higher than C. The metal is passive over the range CD...

Fig. 1.41 Schematic anodic polarisation curves for a passivatable metal showing the effect of a passivating agent that has no specific cathodic action, but forms a sparingly soluble salt with the metal cation, a without the passivating agent, b with the passivating agent. The passive current density, the active/passive transition and the critical current density are all lowered in b. The effect of the cathodic reaction c, is to render the metal active in case a, and passive...

Note that Reference" draws attention to the possibility of an increase of anodic polarisation of the more negative member of a couple leading to a decrease in galvanic corrosion rate. There can also be a risk of increased corrosion of the more positive member of a couple. Both these features can arise as a result of active/passive transition effects on certain metals in certain environments. 

It is convenient to consider three stages of anode polarisation with regard to temperature effects, (a) under film-free conditions, (b) under film-forming conditions and (c) at the active-passive transition. 

The influence of temperature on the anodic behaviour of nickel has been studied, and in acidic and neutral solutions the active-passive transition is not observed at temperatures greater than about 100°C (Fig. 4.21). 

The use of the potentiostatic method has helped to show that the process of self-passivation is practically identical to that which occurs when the metal is made anodically passive by the application of an external current" . The polarisation curve usually observed is shown schematically in Fig. 19.37a. Without the use of a potentiostat, the active portion of the curve AB would make a sudden transition to the curve DE, e.g. along curve AFE or AFD, and observation of the part of the curve BCDE during anodic polarisation was not common until the potentiostat was used. 

Active Loop the region of an anodic polarisation curve of a metal comprising the active region and the active-passive transition. 

Critical Anode Current Density anodic current density that must be exceeded in order to produce an active to passive transition (for a given metal it varies with the nature of the solution, temperature, velocity, etc.). 

A thin layer deposited between the electrode and the charge transport material can be used to modify the injection process. Some of these arc (relatively poor) conductors and should be viewed as electrode materials in their own right, for example the polymers polyaniline (PAni) [81-83] and polyethylenedioxythiophene (PEDT or PEDOT) [83, 841 heavily doped with anions to be intrinsically conducting. They have work functions of approximately 5.0 cV [75] and therefore are used as anode materials, typically on top of 1TO, which is present to provide lateral conductivity. Thin layers of transition metal oxide on ITO have also been shown [74J to have better injection properties than ITO itself. Again these materials (oxides of ruthenium, molybdenum or vanadium) have high work functions, but because of their low conductivity cannot be used alone as the electrode. 

Examples of such situations are very numerous perhaps the best known example is the transition of the performance of an electronic circuit from regenerative amplification to the generation of oscillations. The parameter A in this case is the coefficient of mutual inductance between the anode and the grid circuits. As long as A < A0, the circuit functions as amplifier whose coefficient of amplification gradually... 

Figure 50. Semilogarithmic plot of cathodic (Ec) and anodic (E) potentials against values of 1 IQ [cPQityd ] extracted from Figs. 52 and 53. Following Eq. (48), values of the coefficient of electrochemical relaxation (zr) and the coefficient of cathodic polarization (ze) can be deduced from the slopes. (Reprinted from T. F. Otero and H.-J. Grande, Reversible 2D to 3D electrode transition in polypyrrole films. ColloidSurf. A. 134,85, 1998, Figs. 4-9. Copyright 1998. Reproduced with kind permission of Elsevier Science-NL, Sara Burgerhartstraat 25, 1055 Amsterdam, The Netherlands.)...

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