Diffusion and corrosion

Page el al. (P52) determined the CP/OH" ratios in the pore solutions, CP diffusivities and corrosion rates of embedded steel in pastes of cements of several types. With Portland cements, the CP/OH" ratios decreased... 

Using AW devices to monitor dynamic processes such as diffusion and corrosion can dramatically reduce the time required to quantify these processes. For example, as discussed in Section 4.2.2, diffusion equilibration times typically increase with the square of the diffusional length. For a thin film, this length scale, the film thickness (h), is very small. This enables the quantification of diffusion coefficients as low as 10 cm /sec in less than one day, whereas months would be required using many conventional techniques that use thick films or bulk samples. For corrosion monitoring, the dramatic decrease in mass detection limits obtainable using coated AW devices, as compared with conventional balances and sample coupons, allows detectable mass changes to be achieved in minutes or hours rather than days or months (Section 4.4.3). 

In conclusion, the results presented in this chapter demonstrate the extreme versatility of AW devices for the characterization of materials. The inherent sensitivity of AW properties to the mechanical and electrical properties of thin films can be used to advantage to directly monitor a wide variety of film properties. Since the properties and behavior of thin-film materials can be very different from those of similar bulk materials, this ability to directly measure thin film properties can be a significant advantage in materials research and development. The ability to use thin films instead of bulk samples has the added advantage that the time required to perform an evaluation of dynamic processes such as diffusion and corrosion can be greatly decreased. The number of applications of AW devices to thin-film characterization continues to increase, and is limited only by the ingenuity of AW device researchers and developers. 

N.S. Berke, M.C. Hicks, Estimating the life cycle of reinforced concrete decks and marine piles using laboratory diffusion and corrosion data, in V. Chaker (Ed.), Corrosion Forms and Control for Infrastructure ASTM STP2137, ASTM International, Philadelphia, PA, 1992, pp. 207-230. 

Metallic coatings should be selected for their suitability for the application involved, attention being given to the problems of ageing, diffusion, and corrosion and selected as follows ... 

Growth of the deposited material so as to minimize residual stresses and develop a film morphology resistant to diffusion and corrosion. 

Materials made of siHcon nitride, siHcon oxynitride, or sialon-bonded siHcon carbide have high thermal shock and corrosion resistance and may be used for pump parts, acid spray nozzles, and in aluminum reduction ceUs (156—159). A very porous siHcon carbide foam has been considered for surface combustion burner plates and filter media. It can also be used as a substrate carrying materials such as boron nitride as planar diffusion source for semiconductor doping appHcations. 

Water injection, or steam injection systems, are being used extensively to augment power. Corrosion problems in the compressor diffuser and combustor have not been found to be major problems. The increase in work and efficiency with a reduction in NO makes the process very attractive. Split-shaft cycles are attractive for use in variable-speed mechanical drives. The off-design characteristics of such an engine are high efficiency and high torque at low speeds. 

The use of equipment close to the temperature at wliich the material was diffusion treated will result in continuing diffusion of chromium, aluminum etc., into the substrate, thus depleting chromium with consequent loss in oxidation and corrosion resistance. For aluminum, this effect is noticeable above 700°C in steels, and above 900°C in nickel alloys. For chromium, the effect is pronounced above 850°C for steels and above 950°C for nickel alloys. 

Change in viscosity may affect the circulation, diffusion and other properties pertinent to the corrosion process. 

For diffusion controlled corrosion reactions e.g. dissolved oxygen reduction, and the effect of temperature which increases diffusion rates, then by substituting viscosity and the diffusion coefficients at appropriate temperatures into the Reynolds No. and Schmidt No., changes in corrosion rate can be calculated. 

This represents a special case of high-level turbulence at a surface by the formation of steam and the possibility of the concentration of ions as water evaporates into the steam bubbles . For those metals and alloys in a particular environment that allow diffusion-controlled corrosion processes, rates will be very high except in the case where dissolved gases such as oxygen are the main cathodic reactant. Under these circumstances gases will be expelled into the steam and are not available for reaction. However, under conditions of sub-cooled forced circulation, when cool solution is continually approaching the hot metal surface, the dissolved oxygen... 

Under certain conditions, it will be impossible for the metal and the melt to come to equilibrium and continuous corrosion will occur (case 2) this is often the case when metals are in contact with molten salts in practice. There are two main possibilities first, the redox potential of the melt may be prevented from falling, either because it is in contact with an external oxidising environment (such as an air atmosphere) or because the conditions cause the products of its reduction to be continually removed (e.g. distillation of metallic sodium and condensation on to a colder part of the system) second, the electrode potential of the metal may be prevented from rising (for instance, if the corrosion product of the metal is volatile). In addition, equilibrium may not be possible when there is a temperature gradient in the system or when alloys are involved, but these cases will be considered in detail later. Rates of corrosion under conditions where equilibrium cannot be reached are controlled by diffusion and interphase mass transfer of oxidising species and/or corrosion products geometry of the system will be a determining factor. 

Some disadvantages stem from the same phenomena impeded diffusion reduces the maximum practical rate of plating to well below that possible with aquocation baths. The cyanide ion is not entirely stable both oxidation and reduction products accumulate, including carbonate. Carbonate is also formed in the alkaline cyanide baths (all cyanide baths are alkaline except some based on aurocyanides) by absorption of COj from the air, and it is necessary either to replace or purify baths periodically. Much has been made of the toxicity of cyanides, but the other process solutions used in plating are generally extremely toxic and corrosive or caustic, and it is necessary to treat them all with respect. 

Tin will protect copper from corrosion by neutral water. Pure tin is anodic to copper, and protects discontinuities by sacrificial corrosion. Both intermetallic phases are strongly cathodic to copper, and corrosion is stimulated at gaps in wholly alloyed coatings. An adequate thickness of tin is needed for long service, e.g. 25-50 xm. Another diffusion problem occurs with tin-plated brass. Zinc passes very quickly to the tin surface, where under conditions of damp storage zinc corrosion products produce a film... 

Phase transition occurs at a state of thermodynamic equilibrium, inducing a change in the microstructure of atoms. However, corrosion is a typical nonequilibrium phenomenon accompanied by diffusion and reaction processes. We can also observe that this phenomenon is characterized by much larger scales of length than an atomic order (i.e., masses of a lot of atoms), which is obvious if we can see the morphological change in the pitted surface. 

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