Bare metal surface

SERS substrates with bare metal surfaces irreversibly adsorb thioorganics (Eig. 4.59) and other compounds and can thus serve for the detection and identification of very low gas or solution concentrations of these substances [4.303]. SERS is especially well suited for the analysis of traces of gases, because it combines measurement of surface concentration with extremely high sensitivity. A monolayer in a typical focus of a laser with a diameter of 10 pm has a mass in the range of 10 femtograms even smaller amounts of substance are easily detectable, because 1% of a monolayer in a region 1-pm in diameter results in SERS of sufficient intensity. 

Filiform corrosion is characterised by the formation of a network of threadlike filaments of corrosion products on the surface of a metal coated with a transparent lacquer or a paint him, as a result of exposure to a humid atmosphere. This phenomenon first attracted attention because of its formation on lacquered steel, and for this reason it is sometimes referred to as underfilm corrosion, but although it is most readily observed under a transparent lacquer it can also occur under an opaque paint film or on a bare metal surface. Filiform corrosion has been observed on steel, zinc, magnesium and aluminium coated with lacquers and paints, and with aluminium foil coated with paper. Surface treatment of the metal by phosphating or chromating lessens the tendency for filiform corrosion to occur, but it is not completely... 

In contrast chemical and electrolytic polishing enables a smooth level surface to be produced without any residual stress being developed in the surface because the surface is removed by dissolution at relatively low chemical potential and at relatively low rates is such a way that metallic surface asperities are preferentially removed. For this to be most effective the solution properties must be optimised and the pretreatment must leave an essentially bare metal surface for attack by the electrolyte. 

In acid conditions oxide films are not usually present on the metal surface and the cathodic reaction is primarily that of hydrogen discharge rather than oxygen reduction. Thus, inhibitors are required that will adsorb or bond directly onto the bare metal surfaces and/or raise the overpotential for hydrogen ion discharge. Inhibitors are usually organic compounds... 

Corrosion or mixed potentials (a) Active corrosion in acid solutions (b) Passive metal in acid solutions Potential dependent on the redox potential of the solution and the kinetics of the anodic and cathodic reactions. Potential dependent on the kinetics of the h.e.r. on the bare metal surface. Potential is that of an oxide-hlmed metal, and is dependent on the redox potential of the solution. Zn in HCI Stainless steel in oxygenated H2SO4... 

Additionally, the surfactant properties of filmers reduce the potential for stagnant, heat-transfer-resisting films, which typically develop in a filmwise condensation process, by promoting the formation of condensate drops (dropwise condensation process) that reach critical mass and fall away to leave a bare metal surface (see Figure 11.2). This function, together with the well-known scouring effect on unwanted deposits keeps internal surfaces clean and thus improves heat-transfer efficiencies (often by 5-10%). 

An aspect that is difficult to treat is the nature of the boundary between the adsorbate layer and the bulk of the solution. Solvent molecules are now in contact with an organic layer and the kind of interaction is expected to differ substantially from that with a bare metal surface. The layers of solvent molecules in the immediate proximity of the adsorbate might exhibit some preferential orientation, which is not explicitly accounted for in Eq. (36), and this adds some additional ambiguity to the physical interpretation of the results. 

As discussed in Section I.3(i), AX indicates the variation in the work function of a metal as an interface is created by bringing a solid and a liquid in contact. In principle, it should be possible to compare AX values with A values measured directly in gas phase experiments. This is the aim of UHV synthesis of the electrochemical double layer868 in which the electrode interface is created molecule by molecule, starting with the bare metal surface. It is thus possible to obtain evidence of ion-water interactions that can be envisaged from electrochemical measurements but that are not directly demonstrable. Wagner55 has given a recent comprehensive review of electrochemical UHV experiments. 

In the polarization curve for anodic dissolution of iron in a phosphoric acid solution without CP ions, as shown in Fig. 3, we can see three different states of metal dissolution. The first is the active state at the potential region of the less noble metal where the metal dissolves actively, and the second is the passive state at the more noble region where metal dissolution barely proceeds. In the passive state, an extremely thin oxide film called a passive film is formed on the metal surface, so that metal dissolution is restricted. In the active state, on the contrary, the absence of the passive film leads to the dissolution from the bare metal surface. The difference of the dissolution current between the active and passive states is quite large for a system of an iron electrode in 1 mol m"3 sulfuric acid, the latter value is about 1/10,000 of the former value.6... 

These species are adsorbed not only on the bare metal surface but also on surface sections already oxidized. They can undergo further reaction in a variety of steps, both purely chemical ones and steps of the electrochemical desorption type ... 

It is also interesting that if some of the simple models for the bare metal surface are used to calculate the metal s contribution to the capacitance, a fit to experimental results would require unreasonable values for the solution contribution. Thus, the simple Thomas-Fermi result88 of C(dip) = 47r/ATF (Atf = Thomas-Fermi screening length) is greater than C(experiment)-1, and the same is true for the improved Thomas-Fermi results of Newns40 and the model of free electrons at an infinitely repulsive wall [see Eq. (12)]. These models are thus considered to be less realistic than the model of this work.30... 

Modern theories of electronic structure at a metal surface, which have proved their accuracy for bare metal surfaces, have now been applied to the calculation of electron density profiles in the presence of adsorbed species or other external sources of potential. The spillover of the negative (electronic) charge density from the positive (ionic) background and the overlap of the former with the electrolyte are the crucial effects. Self-consistent calculations, in which the electronic kinetic energy is correctly taken into account, may have to replace the simpler density-functional treatments which have been used most often. The situation for liquid metals, for which the density profile for the positive (ionic) charge density is required, is not as satisfactory as for solid metals, for which the crystal structure is known. 

In general a polar bond is formed when an ion is specifically adsorbed on a metal electrode this results in an uneven distribution of charges between the adsorbate and the metal and hence in the formation of a surface dipole moment. So the adsorption of an ion gives rise to a dipole potential drop across the interface in addition to that which exists at the bare metal surface. 

Anodic passivation can be observed easily and clearly with iron group metals and alloys as shown in Fig. 11-10. In principal, anodic passivation occurs with most metals. For instance, even with noble metals such as platinum, which is resistant to anodic dissolution in sulfuric acid solutions, a bare metal surface is realized in the active state and a superficial thin oxide film is formed in the passive state. For less noble metals of which the affinity for the oxide formation is high, the active state is not observed because the metal surface is alwa covered with an oxide film. 

As implied in the schemes of the mechanisms above, a surface oxide is formed during O2 evolution. Since M-0 is a much stronger bond than M-H, absorption of O is much more probable than that of H. Thus, whereas H2 evolution can be treated as occurring on bare metal surfaces, O2 evolution cannot. In the end, after O2 evolution, a metal surface turns out coated by an oxide layer electrolytically... 

Low-viscosity primers can also easily fill the irregularities on the substrate surface and displace air and fill hollows. This can improve the wetting properties of the adhesive system. For example, if the adhesive is a hot melt and it is applied to a bare metallic surface, the adhesive will gel before it gets a chance to efficiently wet the surface and mechanically interact with any surface roughness. However, if a dilute primer were first applied to the substrate and dried, the hot-melt adhesive could bond directly to the primer that in turn has bonded to the interstices of the substrate, thus providing excellent adhesion. 

The surface films covering the active metals are formed by a gradually decreasing driving force. When the fresh, active metal is exposed either to reactive gases or to solution species, its reactivity is maximal, and, thus, reduction of atmospheric or solutions components takes place under highly nonselective conditions. Any bare metal surface is readily... 

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