Cathodic deposition process

Since in many cases, electrodeposition in the presence of an additive does not use up the additive (no incorporation of the additive in the deposit), one can conclude that the adsorption equilibrium is a dynamic one. In a dynamic adsorption equilibrium state, the adsorbed molecules continually desorb at a rate equal to the rate at which dissolved molecules from the solution become adsorbed. If the rates of the adsorption and desorption processes are high and of the same order of magnitude as that of the cathodic deposition process, then no incorporation, entrapment, of additives in the deposit will occur. However, if they are much smaller, additive molecules will be entrapped in the deposit via propagating steps... 

A chief advantage claimed for coatings applied by the cathodic ED is their superior corrosion resistance, and this has been the main incentive for our work in this area. Initially, we tried to establish whether the cathodic deposition process as such would lead to improved corrosion resistance of the coatings. To this end... 

Manganese metal made by this process is 99.9% pure. It is in the form of irregular flakes (broken cathode deposits) about 3-mm thick, and because of its brittleness, has Httle use alone. Most of the electrolytic manganese that is used in the aluminum industry is ground to a fine size and compacted with granulated aluminum to form briquettes that typically contain 75% Mn and 25% Al. 

Electrorefining. Electrolytic refining is a purification process in which an impure metal anode is dissolved electrochemicaHy in a solution of a salt of the metal to be refined, and then recovered as a pure cathodic deposit. Electrorefining is a more efficient purification process than other chemical methods because of its selectivity. In particular, for metals such as copper, silver, gold, and lead, which exhibit Htfle irreversibHity, the operating electrode potential is close to the reversible potential, and a sharp separation can be accompHshed, both at the anode where more noble metals do not dissolve and at the cathode where more active metals do not deposit. 

An electrolytic process for purifying cmde vanadium has been developed at the U.S. Bureau of Mines (16). It involves the cathodic deposition of vanadium from an electrolyte consisting of a solution of VCI2 in a fused KCl—LiCl eutectic. The vanadium content of the mixture is 2—5 wt % and the operating temperature of the cell is 650—675°C. Metal crystals or flakes of up to 99.995% purity have been obtained by this method. 

The use of an extractant depends on loading capacity, extraction rate, pH range, and the cost of the reagent and the diluent. Loss of the extractant must be minimised because of its high cost. Organic losses to the aqueous phase are also undesirable because of the deleterious effect on cathode deposits. Advances in SX—EW processes are described in Reference 38. 

The CNT cavity is not directly accessible for experiments for CNTs obtained from the cathode deposit because, their tips are almost always closed by multishell hemispherical or polyhedral domes. The first step of any capillaryfilling procedure consists of an opening process, that will be discussed in detail in the following section. 

The principles of electrolysis with controlled cathode potential have been discussed in Section 12.6, and the details given below serve to illustrate the procedure. In this case the amounts of copper and antimony (which are deposited simultaneously) are small, and so the cathode potential can be set immediately to the limiting value, but with the higher proportion of tin it can be set initially to a value which is more positive than the limiting value so as to speed up the deposition process. 

The isomerization of 1-butene to cis- and trans- 2-butene onPd/C/Nafion and Pd-Ru/Nafion electrodes is one of the most remarkable and astonishing electrochemical promotion studies which has appeared in the literature.39,40 Smotkin and coworkers39,40 were investigating the electrocatalytic reduction of 1-butene to butane on high surface area Pd/C and Pd-Ru cathodes deposited on Nafion 117 when, to their great surprise, they observed at slightly negative overpotentials (Fig. 9.31) the massive production of 1-butene isomerization, rather than reduction, products, i.e. cis- and trans-2-butenes. This is extremely important as it shows that electrochemical promotion can be used also to enhance nonredox catalytic reactions such as isomerization processes. 

Cathodic deposition (electrocrystallization) of metals is the basic process in electrometallurgy and electroplating. 

If the electrolyte components can react chemically, it often occurs that, in the absence of current flow, they are in chemical equilibrium, while their formation or consumption during the electrode process results in a chemical reaction leading to renewal of equilibrium. Electroactive substances mostly enter the charge transfer reaction when they approach the electrode to a distance roughly equal to that of the outer Helmholtz plane (Section 5.3.1). It is, however, sometimes necessary that they first be adsorbed. Similarly, adsorption of the products of the electrode reaction affects the electrode reaction and often retards it. Sometimes, the electroinactive components of the solution are also adsorbed, leading to a change in the structure of the electrical double layer which makes the approach of the electroactive substances to the electrode easier or more difficult. Electroactive substances can also be formed through surface reactions of the adsorbed substances. Crystallization processes can also play a role in processes connected with the formation of the solid phase, e.g. in the cathodic deposition of metals. 

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). 

Paunovic [23] and Saito [24] first advanced the notion that an electroless deposition process could be modeled using a simple electrochemical approach. They reasoned that the potential of a surface undergoing electroless deposition could be regarded as a mixed potential intermediate in value between the potentials of its constituent anodic and cathodic partial reactions. These authors employed the mixed potential concept of corrosion reactions first outlined in a systematic manner by Wagner and... 

Figure 1 shows a generalized representation of an electroless deposition process obeying MPT [28]. Polarization curves are shown for the two partial reactions (full lines), and the curve expected for the full electroless solution (dashed curve). The polarization curve for anodic and cathodic partial reactions intersect the potential axis at their respective equilibrium potential values, denoted by / j]cd and respectively. At Emp, the anodic and cathodic partial current densities are equal, a... 

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