The Metallic Surface

Once a metal is unmersed in a solvent, a second dipolar layer will fomi at the metal surface due to the... 

Figure Bl.6.10 Energy-loss spectrum of 3.5 eV electrons specularly reflected from benzene absorbed on the rheniiun(l 11) surface [H]. Excitation of C-H vibrational modes appears at 100, 140 and 372 meV. Only modes with a changing electric dipole perpendicular to the surface are allowed for excitation in specular reflection. The great intensity of the out-of-plane C-H bending mode at 100 meV confimis that the plane of the molecule is parallel to the metal surface. Transitions at 43, 68 and 176 meV are associated with Rli-C and C-C vibrations.

If a compact film growing at a parabolic rate breaks down in some way, which results in a non-protective oxide layer, then the rate of reaction dramatically increases to one which is linear. This combination of parabolic and linear oxidation can be tenned paralinear oxidation. If a non-protective, e.g. porous oxide, is fonned from the start of oxidation, then the rate of oxidation will again be linear, as rapid transport of oxygen tlirough the porous oxide layer to the metal surface occurs. Figure C2.8.7 shows the various growth laws. Parabolic behaviour is desirable whereas linear or breakaway oxidation is often catastrophic for high-temperature materials. 

Atmospheric corrosion results from a metal s ambient-temperature reaction, with the earth s atmosphere as the corrosive environment. Atmospheric corrosion is electrochemical in nature, but differs from corrosion in aqueous solutions in that the electrochemical reactions occur under very thin layers of electrolyte on the metal surface. This influences the amount of oxygen present on the metal surface, since diffusion of oxygen from the atmosphere/electrolyte solution interface to the solution/metal interface is rapid. Atmospheric corrosion rates of metals are strongly influenced by moisture, temperature and presence of contaminants (e.g., NaCl, SO2,. ..). Hence, significantly different resistances to atmospheric corrosion are observed depending on the geographical location, whether mral, urban or marine. 

Corrosion associated with the action of micro-organisms present in the corrosion system. The biological action of organisms which is responsible for the enliancement of corrosion can be, for instance, to produce aggressive metabolites to render the environment corrosive, or they may be able to participate directly in the electrochemical reactions. In many cases microbial corrosion is closely associated with biofouling, which is caused by the activity of organisms that produce deposits on the metal surface. 

The electrode potential of aluminium would lead us to expect attack by water. The inertness to water is due to the formation of an unreactive layer of oxide on the metal surface. In the presence of mercury, aluminium readily forms an amalgam (destroying the original surface) which is. therefore, rapidly attacked by water. Since mercury can be readily displaced from its soluble salts by aluminium, contact with such salts must be avoided if rapid corrosion and weakening of aluminium structures is to be prevented. 

The commonly accepted mechanism of heterogeneously catalyzed hydrogenation involves activation of both the hydrogen and the C—C multiple bond adsorbed on the metal surface. First one hydrogen atom is transferred to the least hindered position of the multiple bond to give a half-hydrogenated adsorbed species. This reaction is fully reversible and ac-... 

Reaction with an alkyl halide takes place at the metal surface In the hist step an election is transfeiied from lithium to the alkyl halide... 

The work function (p is the energy necessary to just remove an electron from the metal surface in thermoelectric or photoelectric emission. Values are dependent upon the experimental technique (vacua of 10 or torr, clean surfaces, and surface conditions including the crystal face identification). 

It has been known for many years that strongly heating a metal wire in a vacuum causes emission of electrons from the metal surface. This effect is important for thermionic devices used to control or amplify electrical current, but this aspect of surface emission is not considered here. Rather, the discussion here focuses on the effect of heating a sample substance to a high temperature on a metal wire or ribbon. 

Schematic diagram showing how placing a thin layer of highly dispersed carbon onto the surface of a metal filament leads to an induced dipolar field having positive and negative image charges. The positive side is always on the metal, which is much less electronegative than carbon. This positive charge makes it much more difficult to remove electrons from the metal surface. The higher the value of a work function, the more difficult it is to remove an electron. Effectively, the layer of carbon increases the work function of the filament metal. Very finely divided silicon dioxide can be used in place of carbon.

Whereas ATR spectroscopy is most commonly applied in obtaining infrared absorption spectra of opaque materials, reflection-absorption infrared spectroscopy (RAIRS) is usually used to obtain the absorption spectrum of a thin layer of material adsorbed on an opaque metal surface. An example would be carbon monoxide adsorbed on copper. The metal surface may be either in the form of a film or, of greaf imporfance in fhe sfudy of cafalysfs, one of fhe parficular crysfal faces of fhe mefal. 

Seldom is the temperature difference across the wall thickness of an item of equipment known. Siace large temperature gradients may occur ia the boundary layers adjacent to the metal surfaces, the temperature difference across the wall should not be estimated from the temperatures of the fluids on each side of the wall, but from the heat flux usiag equation 27... 

Rust inhibitors usually are corrosion inhibitors that have a high polar attraction toward metal surfaces and that form a tenacious, continuous film which prevents water from reaching the metal surface. Typical mst inhibitors are amine succinates and alkaline-earth sulfonates. Rust inhibitors can be used in most types of lubricating oils, but factors of selection include possible corrosion of nonferrous metals or formation of emulsions with water. Because mst inhibitors are adsorbed on metal surfaces, an oil can be depleted of its mst inhibitor. In certain cases, it is possible to correct the depletion by adding more inhibitor. 

HCl gas reacts with metal oxides to form chlorides, oxychlorides, and water. Therefore, all the steel equipment should be pickled to remove the oxide scales before it is put in service. Because oxidi2ing agents in the HCl gas such as oxygen or chlorine significantly affect the corrosion rate, it is essential that the operating temperature of the steel equipment be kept below the temperature (316°C) at which ferric chloride is vapori2ed from the metal surface. 

The mechanism of the anionic polymerization of styrenes and 1,3-dienes initiated by alkaU metals has been described in detail (3,20) as shown in equations 3—5 where Mt represents an alkaU metal and M is a monomer molecule. Initiation is a heterogeneous process occurring on the metal surface. The... 

Sometimes the formation of oxide films on the metal surface binders efficient ECM, and leads to poor surface finish. Eor example, the ECM of titanium is rendered difficult in chloride and nitrate electrolytes because the oxide film formed is so passive. Even when higher (eg, ca 50 V) voltage is apphed, to break the oxide film, its dismption is so nonuniform that deep grain boundary attack of the metal surface occurs. 

Metal Preparation. Preparation of the metal surfaces to be bonded usually is required because most metals contain surface imperfections or contaminants that undesirably affect bond properties. The cladding faces usually are surface ground, using an abrasive machine, and then are degreased with a solvent to ensure consistent bond strength (26). In general, a surface finish that is >3.8 fim deep is needed to produce consistent, high quaUty bonds. 

Paint-base phosphate coatings could be appHed in two to five minutes. In 1934, this time constraint was shortened even further when phosphate solutions were sprayed onto the metal surface. Processing times as short as 60 seconds became possible. 

Hydrogenis prevented from forming a passivating layer on the surface by an oxidant additive which also oxidizes ferrous iron to ferric iron. Ferric phosphate then precipitates as sludge away from the metal surface. Depending on bath parameters, tertiary iron phosphate may also deposit and ferrous iron can be incorporated into the crystal lattice. When other metals are included in the bath, these are also incorporated at distinct levels to generate species that can be written as Zn2Me(P0 2> where Me can represent Ni, Mn, Ca, Mg, or Fe. 

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