Coatings continued cathodic

Usually, M02C and WjC coatings are applied onto non-oriented metal substrates by electrolysis of Na2W04-based oxide melts [10, 11]. However, in many instances, it is necessary to obtain continuous cathode deposits with preset properties (structure, orientation, and crystallite size). Therefore, an important role in electrolysis is played by the initial stages of crystal nucleation. In Refs [12-14], the results of such a study for electrodeposited Mo and W are presented. The initial stages of nucleation of Mo and W carbides have not been yet studied. The only known investigation was performed for platinum and glassy carbon electrodes [15]. 

The reaction mixture is filtered. The soHds containing K MnO are leached, filtered, and the filtrate composition adjusted for electrolysis. The soHds are gangue. The Cams Chemical Co. electrolyzes a solution containing 120—150 g/L KOH and 50—60 g/L K MnO. The cells are bipolar (68). The anode side is monel and the cathode mild steel. The cathode consists of small protmsions from the bipolar unit. The base of the cathode is coated with a corrosion-resistant plastic such that the ratio of active cathode area to anode area is about 1 to 140. Cells operate at 1.2—1.4 kA. Anode and cathode current densities are about 85—100 A/m and 13—15 kA/m, respectively. The small cathode areas and large anode areas are used to minimize the reduction of permanganate at the cathode (69). Potassium permanganate is continuously crystallized from cell Hquors. The caustic mother Hquors are evaporated and returned to the cell feed preparation system. 

The cost and economics of cathodic protection depend on a variety of parameters so that general statements on costs are not really possible. In particular, the protection current requirement and the specific electrical resistance of the electrolyte in the surroundings of the object to be protected and the anodes can vary considerably and thus affect the costs. Usually electrochemical protection is particularly economical if the structure can be ensured a long service life, maintained in continuous operation, and if repair costs are very high. As a rough estimate, the installation costs of cathodic protection of uncoated metal structures are about 1 to 2% of the construction costs of the structure, and are 0.1 to 0.2% for coated surfaces. 

Thermionic Emission - Because of. the nonzero temperature of the cathode, free electrons are continuously bouncing inside. Some of these have sufficient energy to overcome the work function of the material and can be found in the vicinity of the surface. The cathode may be heated to increase this emission. Also to enhance this effect, cathodes are usually made of, or coated with, a low work-function material such as thorium. 

General corrosion damage was the cause of failure of an A1 alloy welded pipe assembly in an aircraft bowser which was attacked by a deicing-fluid — water mixture at small weld defects . Selective attack has been reported in welded cupro-nickel subjected to estuarine and seawater environments . It was the consequence of the combination of alloy element segregation in the weld metal and the action of sulphate reducing bacteria (SRB). Sulphide-coated Cu-enriched areas were cathodic relative to the adjacent Ni-rich areas where, in the latter, the sulphides were being continuously removed by the turbulence. Sulphite ions seemed to act as a mild inhibitor. 

At the start the cathode is invariably a metal different from that to be deposited. Frequently, the aim is to coat a base metal with a more noble one, but it may not be possible to do this in one step. When a metal is immersed in a plating bath it will corrode unless its potential is sufficiently low to suppress its ionisation. Fortunately, a low rate of corrosion is tolerable for a brief initial period. There are cases where even when a cathode is being plated at a high cathodic (nett) current density, the substrate continues to corrode rapidly because the potential (determined by the metal deposited) is too high. No satisfactory coating forms if the substrate dissolves at a high rate concurrently with electrodeposition. This problem can be overcome by one or more of the following procedures ... 

A continuous intact film of water-resistant paint forms an effective electrical resistance to the flow of a corrosion current (a resistance of over lO flcm through the film is easily achieved). Underfilm corrosion can then only occur if a channel of electrolyte connecting anode and cathode can be established by local adhesion failure between the coating and the metal substrate. 

The primary function of a coating is to act as a barrier which isolates the underlying metal from the environment, and in certain circumstances such as an impervious continuous vitreous enamel on steel, this could be regarded as thermodynamic control. However, whereas a thick bituminous coating will act in the same way as n vitreous enamel, paint coatings are normally permeable to oxygen and water and in the case of an inhibitive primer (red lead, zinc chromate) anodic control will be significant, whilst the converse applies to a zinc-rich primer that will provide cathodic control to the substrate. 

In plain tinplate cans for acid foods, tin provides cathodic protection to steel (3,4). The slow dissolution of tin prevents steel corrosion. Many investigators (5-1I) have defined this mechanism in detail and have shown that the tin dissolution rate is a function of the cathodic activity of the base steel, the steel area exposed through the tin and the tin-iron alloy layers, and the stannous ion concentration. Kamm et al. showed that control of the growth of the tin—iron alloy layer provides a nearly continuous tin-iron alloy layer and improves the corrosion resistance of heavily coated (over 45 X 10"6 in. tin) ETP for mildly acid food products in which tin provides cathodic protection to steel (12). The controlled tin-iron alloy layer reduces the area of steel exposed to the product. ETP with the controlled alloy is designated type K, and since 1964, 75 type K ETP has been used to provide the same protection as 100 ETP provided previously (13). 

Electroless deposition should not be confused with metal displacement reactions, which are often known as cementation or immersion plating processes. In the latter, the less noble metal dissolves and eventually becomes coated with a more noble metal, and the deposition process ceases. Coating thicknesses are usually < 1 pm, and tend to be less continuous than coatings obtained by other methods. A well-known example of an immersion plating process that has technological applications is the deposition of Sn on Cu [17] here a strong complexant for Cu(I), such as thiourea, forces the Cu(I)/Cu couple cathodic with respect to the Sn(II)/Sn couple, thereby increasing the thermodynamic stability in solution of thiourea-complexed Cu(I) relative to Sn(II). 

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