Deposit formation mechanism

The explicit aims of boiler and feed-water treatment are to minimise corrosion, deposit formation, and carryover of boiler water solutes in steam. Corrosion control is sought primarily by adjustment of the pH and dissolved oxygen concentrations. Thus, the cathodic half-cell reactions of the two common corrosion processes are hindered. The pH is brought to a compromise value, usually just above 9 (at 25°C), so that the tendency for metal dissolution is at a practical minimum for both steel and copper alloys. Similarly, by the removal of dissolved oxygen, by a combination of mechanical and chemical means, the scope for the reduction of oxygen to hydroxyl is severely constrained. 

Deposit formation, due either to crud (suspended matter-mostly metallic oxides) transported into the boiler or to the products of corrosion in situ, is undesirable as, in many parts of the system, quite apart from the risk of overheating which they present, deposits are able to participate in a mechanism for concentrating solutes to unacceptably high corrosive levels, and are particularly dangerous in high-pressure plant (see Section 4.5). 

A further example is the effect of tube failure resulting from longterm overheating. Here it is likely that the principle contributing causes are a combination of deposit formation and stresses resulting from mechanical operation of the boiler in excess of design limits. To minimize or eliminate the risks of deposits and the subsequent effects they produce within the boiler, control again requires a twofold approach ... 

Ferrous bicarbonate may be transported to a point where little or no amine is available, which then provides the source for various secondary corrosion reactions. Corrosion mechanisms and deposition formation often take place at points in the system well downstream of the original points of steam condensation and initiation of corrosion. 

In the case of electrochemical deposition, several mechanisms have been proposed to account for the formation of the end-product film, the difference among them consisting in the assumed electrochemical step. This may be the reduction of selenosulfate (3.3), inducing deposition of the metal (3.4) ... 

The different growth modes discussed above have been exemplified also from structural studies. Froment and Lincot [247] used structural characterization methods, such as TEM and HRTEM, to determine the formation mechanisms and habits of chemically deposited CdS, ZnS, and CdSe thin film at the atomic level. These authors formulated reaction schemes for the different deposition mechanisms and considered that these should be distinguished to (a) atom-by-atom process, providing autoregulation in normal systems (b) aggregation of colloids (precipitation) ... 

In section 2.3 and in Chapter 3, it is shown that the formation of back-arc basins take important role for the mineralization (back-arc deposits (Kuroko deposits), epithermal Au veins) and global geochemical cycle. Thus, it must be worth considering the formation mechanism of back-arc basins. 

Recently, chimney-like ores have been described from Kuroko deposits (Matsuku-ma, 1989 Shimazaki and Horikoshi, 1990 Shikazono and Kusakabe, 1999). The formation mechanism of chimney from the hydrothermal ore deposits at midoceanic ridges was clarified. Thus, these studies constrain the formation mechanism of Kuroko ore deposits. 

Based on these summaries, the formation mechanism of ore deposits and origin of ore fluids were considered. Mixing of ascending hydrothermal solution and ambient cold water (seawater, groundwater) is considered to be an important depositional mechanism. 

An additional mechanism affects the deposits formation from the H-Oil reactor, rejection of vanadium and nickel sulfides from the catalyst. In the vacuum tower, asphaltene precipitation was found to be the prevalent fouling mechanism. In asphaltene... 

Bannayan, M. A., Fouling Mechanisms and Effect of Process Conditions on Deposit Formation in H-Oil Equipment, in Catalysts in Petroleum Refining and Petrochemical Industries, 1996. Kuwait, Studies in Surface Science and Catalysis, Elsevier. 100 pp. 273-281. 

It is noteworthy to mention that employment of silver(i) trifluoroacetate in place of silver(i) acetate, as in the case of A-confused porphyrin, did not give the desired products. This has been attributed to the better basicity of the acetate anion than the trifluoroacetate, which aided the deprotonation of the three interior GH/NH protons at the carbaporphyrin ligand. Besides, it has been noticed that an excessive amount of silver acetate was required for the synthesis. The mechanism of the silver insertion reaction for this type of ligands was proposed, according to what Bruckner had proposed for the synthesis of silver(m) w -triarylcorroles.218,236 The reaction was suggested to occur via a disproportionation reaction, with the supportive observation of silver deposit formation after the reaction.237... 

Many theories on the formation mechanisms of PS emerged since then. Beale et al.12 proposed that the material in the PS is depleted of carriers and the presence of a depletion layer is responsible for current localization at pore tips where the field is intensified. Smith et al.13-15 described the morphology of PS based on the hypothesis that the rate of pore growth is limited by diffusion of holes to the growing pore tip. Unagami16 postulated that the formation of PS is promoted by the deposition of a passive silicic acid on the pore walls resulting in the preferential dissolution at the pore tips. Alternatively, Parkhutik et al.17 suggested that a passive film composed of silicon fluoride and silicon oxide is between PS and silicon substrate and that the formation of PS is similar to that of porous alumina. 

The observation that nodules grow at widely varying rates provides further support for the existence of multiple formation mechanisms. The nodules that accrete most slowly (1 mm per million years) appear to have formed primarily by the process of hydrogenous precipitation. This accretion rate is equivalent to the annual deposition of a layer that is only one atom deep. These slow rates cause a significant amount of metal-rich seawater to become occluded between the Fe-Mn oxide layers. 

Deposit formation within the combustion chamber can also lead to knock. Knock is explained by the following mechanisms ... 

It is no wonder that the particles are spherical but crystalline, if one considers the formation mechanism. The rather smooth surface of the spherical magnetite may be due to the rapid contact recrystallization of the constituent primary particles (5), forming the rigid polycrystalline structure. Flowever, it must be noted that polycrystalline spheres are also prepared by normal deposition of monomeric solute, as shown in the formation of the uniform spherical polycrystalline particles of metal sulfides in Chapters 3.1-3.3. Thus, while we may be able to predict the final particle shape and structure from the formation mechanism, it is risky to conclude the formation mechanism only from characterization of the product. As a rule, scrupulous analyses are needed for concluding the growth mechanism in a particle system. 

The insoluble corrosion product Fe(OH)2 can help bacterial film to control the diffusion of oxygen to the anodic sites in the pit. This forms a typical tubercle. If chlorides are present in the aqueous solution, the pH of the solution trapped in the tubercle can become very acid due to the autocatalytic propagation mechanism of localized corrosion due to deposit formation and generation of hydrochloric acid. 

Ash deposition in biomass combustion systems has been the focus of numerous research efforts.559,659 The basic mechanism for deposit formation in biomass combustion systems starts with the vaporization of alkali metals, usually chlorides, in the combustor. Fly ash particles, which are predominantly silica, impact and stick to boiler tube surfaces. As the flue cools the alkali metal vapors and aerosols quench on the tube surfaces. When the ash chemistry approaches equilibrium on the surface and the deposit becomes molten, the likelihood increases that additional fly ash particles will stick, and deposits grow rapidly. Ash deposits can also accelerate the corrosion or erosion of the heat transfer surfaces. This greatly increases the maintenance requirements of the power plant often causing unscheduled plant interruptions and shutdown. 

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