Stabilization cathodic

Organic electroluminescent device with stabilizing cathode capping layer... 

Organic electroluminescent device with stabilized cathode... 

Another approach to having a milder cell environment is to increase the fraction of Li in the baseline electrolyte or change the electrolyte to Li/Na rather than the baseline 62/38 Li/K melt (23,39,40). Within the past 10 years, a lower cost stabilized cathode was developed with a base material cost comparable to the unstabilized cathode (41). A 100 cm cell test of the lower cost stabilized cathode with a Li/Na electrolyte system completed 10,000 hours of operation. 

The dotted lines represent the cases when the above cathodic reactions, (a) or (b), drive the reaction. The solid lines indicate the stability ranges for Fe and its corrosion products (Fe, Fe, Fe O, Fc202, tthcOT). 

The following mechanisms in corrosion behavior have been affected by implantation and have been reviewed (119) (/) expansion of the passive range of potential, (2) enhancement of resistance to localized breakdown of passive film, (J) formation of amorphous surface alloy to eliminate grain boundaries and stabilize an amorphous passive film, (4) shift open circuit (corrosion) potential into passive range of potential, (5) reduce/eliminate attack at second-phase particles, and (6) inhibit cathodic kinetics. 

Copper Corrosion Inhibitors. The most effective corrosion inhibitors for copper and its alloys are the aromatic triazoles, such as benzotriazole (BZT) and tolyltriazole (TTA). These compounds bond direcdy with cuprous oxide (CU2O) at the metal surface, forming a "chemisorbed" film. The plane of the triazole Hes parallel to the metal surface, thus each molecule covers a relatively large surface area. The exact mechanism of inhibition is unknown. Various studies indicate anodic inhibition, cathodic inhibition, or a combination of the two. Other studies indicate the formation of an insulating layer between the water surface and the metal surface. A recent study supports the idea of an electronic stabilization mechanism. The protective cuprous oxide layer is prevented from oxidizing to the nonprotective cupric oxide. This is an anodic mechanism. However, the triazole film exhibits some cathodic properties as well. 

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). 

Surface films are formed by corrosion on practically all commercial metals and consist of solid corrosion products (see area II in Fig. 2-2). It is essential for the protective action of these surface films that they be sufficiently thick and homogeneous to sustain the transport of the reaction products between metal and medium. With ferrous materials and many other metals, the surface films have a considerably higher conductivity for electrons than for ions. Thus the cathodic redox reaction according to Eq. (2-9) is considerably less restricted than it is by the transport of metal ions. The location of the cathodic partial reaction is not only the interface between the metal and the medium but also the interface between the film and medium, in which the reaction product OH is formed on the surface film and raises the pH. With most metals this reduces the solubility of the surface film (i.e., the passive state is stabilized). 

Enamel coatings usually consist of several layers in which the prime coating is applied for adhesion but does not have the chemical stability of the outer layers. With cathodic polarization at holidays, attack on the exposed prime coating is possible as the cathodically produced alkali causes the defects to increase in size. This particularly cannot be excluded in salt-rich media. 

Enamels have very varied properties where their chemical stability is concerned. Relevant stability testing must be carried out for the different areas of application. Enamel coatings for hot water heaters, their requirements and combination with cathodic protection are described in Section 20.4.1. 

In the tidal zone and the spray zone (known as the splash zone), cathodic protection is generally not very effective. Here thick coatings or sheathing with corrosion-resistance materials (e.g., based on NiCu) are necessary to prevent corrosion attack [4]. The coatings are severely mechanically stressed and must be so formed that repair is possible even under spray conditions. Their stability against cathodic polarization (see Section 17.2), marine growths, UV rays and seawater must be ensured [4,5]. 

Cathodic protection cannot work with prestressed concrete structures that have electrically insulated, coated pipes. There is positive experience in the case of a direct connection without coated pipes this is protection of buried prestressed concrete pipelines by zinc anodes [38], Stability against H-induced stress corrosion in high-strength steels with impressed current has to be tested (see Section 2.3.4). 

As the measurements show, the small heater without an electrical separation (from the boiler) is not detrimental to cathodic protection. However, with the uninsulated built-in Cu heat exchanger without an electrical separation, cathodic protection was not achieved. As expected, the polarization increased with increasing conductivity of the water. It should be pointed out that the Cu tube was tinned and that the tin could act as a weak cathodic component. Apart from the unknown long-term stability of such a coating, the apparent raising of the cathodic polarization resistance of tin is not sufficient to provide cathodic protection with such a large fixture. This applies also to other metal coatings (e.g., nickel). 

Fig. 1. The rotating-cathode DC arc method [6a]. The cathode deposit is immediately taken out of the discharge by rotation and cropped within one turn. This method offers high stability and reliability of the handling and makes the continuous mass production possible.

A key criterion for selection of a solvent for electrochemical studies is the electrochemical stability of the solvent [12]. This is most clearly manifested by the range of voltages over which the solvent is electrochemically inert. This useful electrochemical potential window depends on the oxidative and reductive stability of the solvent. In the case of ionic liquids, the potential window depends primarily on the resistance of the cation to reduction and the resistance of the anion to oxidation. (A notable exception to this is in the acidic chloroaluminate ionic liquids, where the reduction of the heptachloroaluminate species [Al2Cl7] is the limiting cathodic process). In addition, the presence of impurities can play an important role in limiting the potential windows of ionic liquids. 

Conceptually elegant, the SOFC nonetheless contains inherently expensive materials, such as an electrolyte made from zirconium dioxide stabilized with yttrium oxide, a strontium-doped lanthanum man-gaiiite cathode, and a nickel-doped stabilized zirconia anode. Moreover, no low-cost fabrication methods have yet been devised. 

Before considering the principles of this method, it is useful to distinguish between anodic protection and cathodic protection (when the latter is produced by an external e.m.f.). Both these techniques, which may be used to reduce the corrosion of metals in contact with electrolytes, depend upon the electrochemical mechanisms that result from changing the potential of a metal. The appropriate potential-pH diagram for the Fe-H20 system (Section 1.4) indicates the magnitude and direction of the changes in the potential of iron immersed in water (pH about 7) necessary to make it either passive or immune in the former case the stability of the metal depends on the formation of a protective film of metal oxide (passivation), whereas in the latter the metal itself is thermodynamically stable and egress of metal ions from the lattice into the solution is thus prevented. 

Similar considerations apply to oxidation. An anion which is considerably more stable than water will be unaffected in the neighbourhood of the anode. With a soluble anode, in principle, an anion only needs be more stable than the dissolution potential of the anode metal, but with an insoluble anode it must be stable at the potential for water oxidation (equation 12.4 or 12.5) plus any margin of polarisation. The metal salts, other than those of the metal being deposited, used for electroplating are chosen to combine solubility, cheapness and stability to anode oxidation and cathode reduction. The anions most widely used are SOj", Cl", F and complex fluorides BF4, SiFj , Br , CN and complex cyanides. The nitrate ion is usually avoided because it is too easily reduced at the cathode. Sulphite,... 

The current-voltage and luminance-voltage characteristics of a state of the art polymer LED [3] are shown in Figure 11-2. The luminance of this device is roughly 650 cd/m2 at 4 V and the luminous efficiency can reach 2 lm/W. This luminance is more than adequate for display purposes. For comparison, the luminance of the white display on a color cathode ray tube is about 500 cd/m2l5J. The luminous efficiency, 2 lm/W, is comparable to other emissive electronic display technologies [5], The device structure of this state of the art LED is similar to the first device although a modified polymer and different metallic contacts are used to improve the efficiency and stability of the diode. Reference [2] provides a review of the history of the development of polymer LEDs. 

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