Clean metal surfaces

For very clean metal surfaces, m should approach unity, and /t becomes very large, as observed with even a small decrease in m, y, falls to about unity, or to the type of value found for practically clean surfaces. And if a boundary film is present, making m < 0.2, Eq. XII-11 reduces to... 

The molten salts quickly dissolve the metal oxides at high temperatures to form a clean metal surface. Other uses are as catalysts and in fire-retardant formulations (see Flame retardants). 

Ion implantation (qv) direcdy inserts nitrogen into metal surfaces. A carefully poHshed and cleaned metal surface at room temperature in a vacuum (-- 0.133 mPa (l-) m Hg)) can be directly implanted with 80-keV nitrogen ions (10) (see Metal surface treatments, case hardening). In an alternative synthesis, argon ions (Ar ) of 8 keV can be used to ionize gas-phase nitrogen to obtain the same results (17). 

The fdr studies reveal that the alkyl chains in SAMs of thiolates on Au(lll) usually are tilted 26-28° from the surface normal, and display 52-55° rotation about the molecular axis. This tilt is a result of the chains reestabUshing VDW contact in an assembly with - 0.5 nm S—S distance, larger than the distance of - 0.46 nm, usually quoted for perpendicular alkyl chains in a close-packed layer. On the other hand, thiolate monolayers on Ag(lll) are more densely packed owing to the shorter S—S distance. There were a number of different reports on chain tilt in SAMs on Ag(lll), probably owing to different amounts of oxide, formed on the clean metallic surface (229,230,296,297). In carefully prepared SAMs of alkanethiolates on a clean Ag(lll) surface, the alkyl chains are practically perpendicular to the surface. 

Adhesion to Metals. For interaction between coating and substrate to occur, it is necessary for the coating to wet the substrate (107). Somewhat oversimplified, the surface tension of the coating must be lower than the surface tension of the substrate. In the case of metal substrates, clean metal surfaces have very high surface tensions and any coating wets a clean metal substrate. 

Electroless reactions must be autocatalytic. Some metals are autocatalytic, such as iron, in electroless nickel. The initial deposition site on other surfaces serves as a catalyst, usually palladium on noncatalytic metals or a palladium—tin mixture on dielectrics, which is a good hydrogenation catalyst (20,21). The catalyst is quickly covered by a monolayer of electroless metal film which as a fresh, continuously renewed clean metal surface continues to function as a dehydrogenation catalyst. Silver is a borderline material, being so weakly catalytic that only very thin films form unless the surface is repeatedly cataly2ed newly developed baths are truly autocatalytic (22). In contrast, electroless copper is relatively easy to maintain in an active state commercial film thicknesses vary from <0.25 to 35 p.m or more. 

Alter the environment to render it less eorrosive. This approach may be as simple as maintaining clean metal surfaces. It is well known that the chemistry of the environment beneath deposits can become substantially different than that of the bulk environment. This difference can lead to localized, underdeposit corrosion (see Chap. 4, Underdeposit Corrosion ). The pit sites produced may then induce corrosion fatigue when cyclic stresses are present. The specific steps taken to reduce corrosivity vary with the metal under consideration. In general, appropriate adjustments to pH and reduction or elimination of aggressive ions should be considered. 

Separate the metal from the environment with a physical barrier. Many corrosion inhibitors make use of this principal to protect metals. Proper use of an appropriate inhibitor may reduce or eliminate pitting. Pits are frequently initiation sites for corrosion-fatigue cracks. The effectiveness of inhibitors depends upon their application to clean metal surfaces. An example of this method is the use of zinc coatings on steel to stifle pit formation. 

The gases that have been used most often are hydrogen, carbon monoxide, and oxygen. Hydrogen is by far the most useful, and it has the best established adsorption mechanism. It dissociates at room temperature on most clean metal surfaces of... 

Because LEED theory was initially developed for close packed clean metal surfaces, these are the most reliably determined surface structures, often leading to 7 p factors below 0.1, which is of the order of the agreement between two experimental sets of 7-V curves. In these circumstances the error bars for the atomic coordinates are as small as 0.01 A, when the total energy range of 7-V curves is large enough (>1500 eV). A good overview of state-of-the-art LEED determinations of the structures of clean metal surfaces, and further references, can be found in two recent articles by Heinz et al. [2.272, 2.273]. 

The above measurements all rely on force and displacement data to evaluate adhesion and mechanical properties. As mentioned in the introduction, a very useful piece of information to have about a nanoscale contact would be its area (or radius). Since the scale of the contacts is below the optical limit, the techniques available are somewhat limited. Electrical resistance has been used in early contact studies on clean metal surfaces [62], but is limited to conducting interfaces. Recently, Enachescu et al. [63] used conductance measurements to examine adhesion in an ideally hard contact (diamond vs. tungsten carbide). In the limit of contact size below the electronic mean free path, but above that of quantized conductance, the contact area scales linearly with contact conductance. They used these measurements to demonstrate that friction was proportional to contact area, and the area vs. load data were best-fit to a DMT model. 

The very new techniques of scanning tunnelling microscopy (STM) and atomic force microscopy (AFM) have yet to establish themselves in the field of corrosion science. These techniques are capable of revealing surface structure to atomic resolution, and are totally undamaging to the surface. They can be used in principle in any environment in situ, even under polarization within an electrolyte. Their application to date has been chiefly to clean metal surfaces and surfaces carrying single monolayers of adsorbed material, rendering examination of the adsorption of inhibitors possible. They will indubitably find use in passive film analysis. 

Critical relative humidity The primary value of the critical relative humidity denotes that humidity below which no corrosion of the metal in question takes place. However, it is important to know whether this refers to a clean metal surface or one covered with corrosion products. In the latter case a secondary critical humidity is usually found at which the rate of corrosion increases markedly. This is attributed to the hygroscopic nature of the corrosion product (see later). In the case of iron and steel it appears that there may even be a tertiary critical humidity . Thus at about 60% r.h. rusting commences at a very slow rate (primary value) at 75-80% r.h. there is a sharp increase in corrosion rate probably attributable to capillary condensation of moisture within the rust . At 90% r.h. there is a further increase in rusting rate corresponding to the vapour pressure of saturated ferrous sulphate solution , ferrous sulphate being identifiable in rust as crystalline agglomerates. The primary critical r.h. for uncorroded metal surfaces seems to be virtually the same for all metals, but the secondary values vary quite widely. 

Ensure a clean metal surface free from cathodic contaminants. 

The self-adhesive tape coatings are thin and the adhesive itself does not necessarily come into contact with the valleys in the cleaned metal surface. Under these circumstances, the transmission of water vapour through the film to the metal may be possible. Moisture-transmission characteristics and other properties of p.v.c. and polyethylene tapes, as given by major manufacturers, are provided in Table 14.6. 

On an atomic scale, metal surfaces are usually described in terms of the terrace-ledge-kink model shown in Fig. 20.36Z>. Essentially, it is suggested that clean metal surfaces consist of low-energy low-index terraces separated by ledges of monatomic height which occasionally contain monatomic kinks. 

At least as important, however, is the need to ensure clean metal surfaces because, as stated earlier, concentration cell corrosion mechanisms commonly occur under boiler section sludges and deposits. 

Inadequate acid cleaning procedures also may introduce traces of copper into the boiler (typically originally present as copper-containing deposits), which can plate out onto clean metal surfaces and cause localized, anodic area pitting corrosion. 

Once a filmer program starts, feeding of amine must be continuous because with the gradual removal of old iron oxide debris, the clean metal surface is subject to rapid corrosion should the continuous film cease to be maintained. 

The alkali promotion of CO dissociation is substrate-specific, in the sense that it has been observed only for a restricted number of substrates where CO does not dissociate on the clean surface, specifically on Na, K, Cs/Ni( 100),38,47,48 Na/Rh49 and K, Na/Al(100).43 This implies that the reactivity of the clean metal surface for CO dissociation plays a dominant role. The alkali induced increase in the heat of CO adsorption (not higher than 60 kJ/mol)50 and the decrease in the activation energy for dissociation of the molecular state (on the order of 30 kJ/mol)51 are usually not sufficient to induce dissociative adsorption of CO on surfaces which strongly favor molecular adsorption (e. g. Pd or Pt). 

The adsorption of C02 on metal surfaces is rather weak, with the exception of Fe, and no molecular or dissociative adsorption takes place at room temperature on clean metal surfaces. At low temperatures, lower than 180 to 300 K, a chemisorbed COf" species has been observed by UPS6 on Fe(lll) and Ni(110) surfaces, which acts as a precursor for further dissociation to CO and adsorbed atomic oxygen. A further step of CO dissociation takes place on Fe(l 11) above 300 to 390 K. 

It should be emphasized that is the actual, promoter modified, work function of the catalyst surface and not that of a clean metal surface for which we reserve the symbol o- It should also be clarified that the kinetic constant kR is also expected to vary with . Since, however, we have no rules on how it varies with we will attempt here to rationalize some classical promotional kinetics treating it as a constant. What is amazing is that this procedure works, which indicates that the promoter action effect on kD andkA, together with the 1-0P term, is dominant. 

The work function of clean metal surfaces, which we denote throughout this book by O0) varies between 2 eV for alkalis up to 5.5 eV for transition metals such as Pt. In general it increases as one moves to the right on the periodic table but deviations exist (Figure 4.19 in Chapter 4). 

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