Solid metals interface

Coriell et al. [92] solved the transient one-dimensional heat and solute diffusion equation without considering convective effect. The situation considered was similar to a diffusion-controlled problem of Coates and Kirkaldy [93] and Maugis et al. [90], which has multiple similarity solutions. Assuming local equilibrium at the solid/metal interface Coriell et al. [92] obtained the equation for the parabolic growth rate which was solved numerically. Using a lead-tin alloy as an example to examine phase stability, it was found that the diffusion path begins at the composition and temperature of one phase, crosses the two-phase region between the liquidus and solidus lines, and terminates at the composition and temperature of the other phase. 

The equations of electrocapillarity become complicated in the case of the solid metal-electrolyte interface. The problem is that the work spent in a differential stretching of the interface is not equal to that in forming an infinitesimal amount of new surface, if the surface is under elastic strain. Couchman and co-workers [142, 143] and Mobliner and Beck [144] have, among others, discussed the thermodynamics of the situation, including some of the problems of terminology. 

Corrosion protection of metals can take many fonns, one of which is passivation. As mentioned above, passivation is the fonnation of a thin protective film (most commonly oxide or hydrated oxide) on a metallic surface. Certain metals that are prone to passivation will fonn a thin oxide film that displaces the electrode potential of the metal by +0.5-2.0 V. The film severely hinders the difflision rate of metal ions from the electrode to tire solid-gas or solid-liquid interface, thus providing corrosion resistance. This decreased corrosion rate is best illustrated by anodic polarization curves, which are constructed by measuring the net current from an electrode into solution (the corrosion current) under an applied voltage. For passivable metals, the current will increase steadily with increasing voltage in the so-called active region until the passivating film fonns, at which point the current will rapidly decrease. This behaviour is characteristic of metals that are susceptible to passivation. 

Cavitation damage is a fonn of deterioration associated with materials in rapidly moving liquid environments, due to collapse of cavities (or vapour bubbles) in the liquid at a solid-liquid interface, in the high-pressure regions of high flow. If the liquid in movement is corrosive towards the metal, the damage of the metal may be greatly increased (cavitation corrosion). 

Interface The common boundary layer between two substances such as between water and a solid (metal) or between water and a gas (air) or between a liquid (water) and another liquid (oil). 

Thus in all corrosion reactions one (or more) of the reaction products will be an oxidised form of the metal, aquo cations (e.g. Fe (aq.), Fe (aq.)), aquo anions (e.g. HFeO aq.), Fe04"(aq.)), or solid compounds (e.g. Fe(OH)2, Fej04, Fe3 04-H2 0, Fe203-H20), while the other reaction product (or products) will be the reduced form of the non-metal. Corrosion may be regarded, therefore, as a heterogeneous redox reaction at a metal/non-metal interface in which the metal is oxidised and the non-metal is reduced. In the interaction of a metal with a specific non-metal (or non-metals) under specific environmental conditions, the chemical nature of the non-metal, the chemical and physical properties of the reaction products, and the environmental conditions (temperature, pressure, velocity, viscosity, etc.) will clearly be important in determining the form, extent and rate of the reaction. 

Concave surfaces are of industrial importance, in relation to the internal surface of bores, holes and pipes, but are not found on typical solid testpieces and have received much less discussion. The stress patterns will tend to be the opposite of those found on convex surfaces for example, an oxide growing by cation diffusion should be in tension at the metal interface. Bruce and Hancock have discussed the oxidation of curved surfaces and show how the time to adhesive failure of the oxide can be predicted if its mechanical properties are known. 

Chemical reaction This involves the formation of distinct compounds by reaction between the solid metal and the fused metal or salt. If such compounds form an adherent, continuous layer at the interface they tend to inhibit continuation of the reaction. If, however, they are non-adherent or soluble in the molten phase, no protection will be offered. In some instances, the compounds form in the matrix of the alloy, for example as grain-boundary intermetallic compound, and result in harmful liquid metal embrittlement (LME) although no corrosion loss can be observed. 

The majority of work on the electrified interface has been carried out using a mercury electrode, which has the advantage that it has a well-defined and reproducible surface and a highly polarisable interface when immersed in a solution. In the case of solid metals the concepts outlined are equally applicable, but modifications are necessary to allow for the following ... 

Some emphasis has been placed inthis Section on the nature of theel trified interface since it is apparent that adsorption at the interface between the metal and solution is a precursor to the electrochemical reactions that constitute corrosion in aqueous solution. The majority of studies of adsorption have been carried out using a mercury electrode (determination of surface tension us. potential, impedance us. potential, etc.) and this has lead to a grater understanding of the nature of the electrihed interface and of the forces that are responsible for adsorption of anions and cations from solution. Unfortunately, it is more difficult to study adsorption on clean solid metal surfaces (e.g. platinum), and the situation is even more complicated when the surface of the metal is filmed with solid oxide. Nevertheless, information obtained with the mercury electrode can be used to provide a qualitative interpretation of adsorption phenomenon in the corrosion of metals, and in order to emphasise the importance of adsorption phenomena some examples are outlined below. 

Again the extent to which such parallel reactions contribute to the measured current is not very easy to quantify. However, fortunately, such a quantification is not necessary for the description of NEMCA. What is needed is only a measure of the overall electrocatalytic activity of the metal-solid electrolyte interface or, equivalently, of the tpb, and this can be obtained by determining the value of a single electrochemical parameter, the exchange current I0, which is related to the exchange current density i0 via ... 

We start by considering a schematic representation of a porous metal film deposited on a solid electrolyte, e.g., on Y203-stabilized-Zr02 (Fig. 5.17). The catalyst surface is divided in two distinct parts One part, with a surface area AE is in contact with the electrolyte. The other with a surface area Aq is not in contact with the electrolyte. It constitutes the gas-exposed, i.e., catalytically active film surface area. Catalytic reactions take place on this surface only. In the subsequent discussion we will use the subscripts E (for electrolyte) and G (for gas), respectively, to denote these two distinct parts of the catalyst film surface. Regions E and G are separated by the three-phase-boundaries (tpb) where electrocatalytic reactions take place. Since, as previously discussed, electrocatalytic reactions can also take place to, usually,a minor extent on region E, one may consider the tpb to be part of region E as well. It will become apparent below that the essence of NEMCA is the following One uses electrochemistry (i.e. a slow electrocatalytic reaction) to alter the electronic properties of the metal-solid electrolyte interface E. 

Figure 5.17. Schematic representation of a metal crystallite deposited on YSZ and of the changes induced in its electronic properties upon polarizing the catalyst-solid electrolyte interface and changing the Fermi level (or electrochemical potential of electrons) from an initial value p to a new value p -eri30 31 Reprinted with permission from Elsevier Science.

The non-zero value of e Fw-e FR in Eq. (5.35) implies that there are net surface charges on the gas exposed electrode surfaces. These charges (q+,q.) have to be opposite and equal as the cell is overall electrically neutral and all other charges are located at the metal-solid electrolyte interfaces to maintain their electroneutrality. The charges q+ = -q. are quite small in relation to the charges, Q, stored at the metal-electrolyte interface but nevertheless the... 

Figures 5.29a and 5.29b show the Bode and Nyquist plot for a resistor, Ro, connected in series with a resistor, Rt, and capacitor, Ci, connected in parallel. This is the simplest model which can be used for a metal-solid electrolyte interface. Note in figure 5.29b how the first intersect of the semicircle with the real axis gives Ro and how the second intersect gives Ro+Rj. Also note how the capacitance, Ct, can be computed from the frequency value, fm, at the top of the semicircle (summit frequency), via C l JifmR .

Figure 5.29. Bode (a) and corresponding Nyquist plot (b) of the circuit shown in inset which is frequently used to model a metal/solid electrolyte interface. Effect (c) of capacitance C2 on the Nyquist plot at fixed R0, R( and R2.

Electrochemically induced and controlled Na backspillover is the origin of electrochemical promotion on metals interfaced with p"-Al203 solid electrolytes. 

It is thus clear from the previous discussion that the absolute electrode potential is not a property of the electrode material (as it does not depend on electrode material) but is a property of the solid electrolyte and of the gas composition. To the extent that equilibrium is established at the metal-solid electrolyte interface the Fermi levels in the two materials are equal (Fig. 7.10) and thus eU 2 (abs) also expresses the energy of transfering an electron from the Fermi level of the YSZ solid electrolyte, in equilibrium with po2=l atm, to a point outside the electrolyte surface. It thus also expresses the energy of solvation of an electron from vacuum to the Fermi level of the solid electrolyte. 

Chemists use a special notation to specify the structure of electrode compartments in a galvanic cell. The two electrodes in the Daniell cell, for instance, are denoted Zn(s) Zn2+(aq) and Cu2+(aq) Cu(s). Each vertical line represents an interface between phases—in this case, between solid metal and ions in solution in the order reactant product. 

Ina similarmarmerto surface-enhanced Raman scattering, surface-enhancement of hyper-Raman scattering is a promising method to study adsorbed molecules on metal surfaces [24]. Based on recent developments in plasmonics, design and fabrication of metal substrates with high enhancement activities is now becoming possible [21]. Combination of the surface enhancement with the electronic resonances would also be helpful for the practical use of hyper-Raman spectroscopy. Development of enhanced hyper-Raman spectroscopy is awaited for the study of solid/liquid interfaces. 

Fig. 15. Schematic energy diagram of the n-type semiconductor electronic bands at the solid/liquid interface modulated by discontinuous metal coating ...

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