Film and adsorption theories

In this respect and regarding the discussion on the initial passivations, as pointed out by an increasing number of writers, the oxide-film and adsorption theories do not contradict but rather supplement one another. In looking at the primary act of passivation as the formation of a tightly held monolayer containing oxide or hydroxide anions and metal... 

Chapter 4 presents the fundamentals of passivity the film and adsorption theories of passivity criterion for passivation methods for spontaneous passivation factors affecting passivation, such as the effect of solution velocity and acid concentration alloy evaluation anodic protection systems and design requirements. A fuU discussion on stainless steel composition and crystalline structure, oxidizer concentration, and alloy evaluation is included. The chapter also considers anodic protection to establish a basis for anodic... 

There are various theories on how passive films are formed however, there are two commonly accepted theories. One theory is called the oxide film theory and states that the passive film is a diffusion-barrier layer of reaction products (i.e., metal oxides or other compounds). The barriers separate the metal from the hostile environment and thereby slow the rate of reaction. Another theory is the adsorption theory of passivity. This states that the film is simply adsorbed gas that forms a barrier to diffusion of metal ions from the substrata. 

In view of the fact that there are two opposing views on the mechanism of passivity it is not surprising that a similar situation prevails concerning the mechanism of breakdown of passivity. The solid film theory of passivity and breakdown of passivity is dealt with in some detail in Section 1.5, so that it is appropriate here to discuss briefly the views based on the adsorption theory. 

Figures 11(a) and 11(b) [112] show the variation of Ni-Ge-P deposition rate and Ge content as a function of aspartic acid and Ge(IV) concentration, respectively. A relatively low P content, ca. 1-2 at%, was observed in the case of films exhibiting a high concentration of Ge (> 18 at%). Like other members of its class, which includes molybdate and tungstate, Ge(IY) behaves a soft base according to the hard and soft acids and bases theory (HSAB) originated by Pearson [113, 114], capable of strong adsorption, or displaying inhibitor-like behavior, on soft acid metal surfaces. In weakly acidic solution, uncomplexed Ge(IV) most probably exists as the hydrated oxide, or Ge(OH)4, which, due to acid-base reactions, may be more accurately represented as [Gc(OH)4 nO ] ".

Before 1916, adsorption theories postulated either a condensed liquid film or a compressed gaseous layer which decreases in density as the distance from the surface increases. Langmuir (1916) was of the opinion that, because of the rapidity with which intermolecular forces fall off with distance, adsorbed layers are not likely to be more than one molecular layer in thickness. This view is generally accepted for chemisorption and for physical adsorption at low pressures and moderately high temperatures. 

In recent years the electrochemistry of the enzyme membrane has been a subject of great interest due to its significance in both theories and practical applications to biosensors (i-5). Since the enzyme electrode was first proposed and prepared by Clark et al. (6) and Updike et al. (7), enzyme-based biosensors have become a widely interested research field. Research efforts have been directed toward improved designs of the electrode and the necessary membrane materials required for the proper operation of sensors. Different methods have been developed for immobilizing the enzyme on the electrode surface, such as covalent and adsorptive couplings (8-12) of the enzymes to the electrode surface, entrapment of the enzymes in the carbon paste mixture (13 etc. The entrapment of the enzyme into a conducting polymer has become an attractive method (14-22) because of the conducting nature of the polymer matrix and of the easy preparation procedure of the enzyme electrode. The entrapment of enzymes in the polypyrrole film provides a simple way of enzyme immobilization for the construction of a biosensor. It is known that the PPy-... 

Formation and stability studies of black foam films can be summarised as follows 1) surface forces in black foam films direct measurement of disjoining pressure isotherm DLVO- and non-DLVO-forces 2) thin foam film/black foam film transition establishing the conditions for the stability of both types of black films and CBF/NBF transition 3) formation of black foam films in relation to the state of the adsorption layers at the solution/air interface 4) stability of bilayer films (NBF) theory and experimental data. 

Let us summarise the conditions of formation of a microscopic foam film in order to serve the in vivo situation. These are film radius r from 100 to 400 pm capillary pressure pa = 0.3 - 2.5-102 Pa electrolyte (NaCl) concentration Ce 0.1 mol dm 3, ensuring formation of black films (see Section 3.4) and close to the physiological electrolyte concentration sufficient time for surfactant adsorption at both film surfaces. Under such conditions it is possible also to study the suitable dependences for foam films and to use parameters related to formation and stability of black foam films, including bilayer films (see Section 3.4.4). For example, the threshold concentration C, is a very important parameter to characterise stability and is based on the hole-nucleation theory of bilayer stability of Kashchiev-Exerowa. As discussed in Section 3.4.4, the main reason for the stability of amphiphile bilayers are the short-range interactions between the first neighbour molecules in lateral and normal direction with respect to the film plane. The binding energy Q of a lipid molecule in the foam bilayer has been estimated in Section 11.2. 

Another theory of the reason for increased friction in the presence of moisture was proposed by Gao et al . They found that in a humid environment molybdenum disulphide films were more readily thinned by sliding contact, due to increased ease of interlamellar slip. They suggested that adsorption of water softened the films, and that resulting increased deformation by plowing in sliding contact led to a poorly oriented film and thus to increased friction. However, they considered that this was a short-term reversible effect which was not in conflict with theories of chemical breakdown. Gao et al also poiinted out the possibility that an increase In friction is caused by capillary pressure effects of moisture at asperity contacts. 

The reaction is conceived to occur with the adsorption of CO on the cluster and the adsorption of oxygen on the particle periphery as shown in Fig. 16.5 [6]. The production of CO was greatly enhanced for Au clusters supported on defect-rich films as compared to clusters supported on defect-poor films. Density functional theory (DFT) calculations indicated the reaction barrier was lowered from 0.8 to... 

The electrostatic components of disjoining pressure and free energy of interaction in the film, given by eqs. (VII.21) and (VII.22), are positive, i.e. represent repulsion. These quantities may be compared with corresponding molecular components that are negative and describe attraction. This allows one to analyze according to the DLVO theory the stability of thin films, and consequently of disperse systems stabilized by adsorption layers. Carrying out summation of eqs. (VII.21) and (VII.22) with expressions (VII.9) and (VII. 10) one obtains ... 

In coating processes the problem of controlling the flow of liquids down an inclined plate is a key question (Scriven 1960, Kretzschmar 1974). Therefore, the hydrodynamic flow of such films in combination with surface rheological and adsorption kinetics models were described. As the principle of a flowing film can be used also as a separate method to study adsorption processes in the range of milliseconds, the theory is presented here, while the experimental details are given in the next chapter. 

A different antifoaming mechanism was suggested by Kulkarni et al. (96). They found that surfactants adsorb on the surface of hydrophobic particles during antifoaming, and this adsorption results in deactivation of the particles. On the basis of this observation, they postulated that the adsorption of surfactants onto the hydrophobic particles is so fast that it results in surfactant depletion around the particle in a foam film, and this effect breaks the film. However, no direct proof was presented on this theory. Moreover, depletion of surfactant would cause the film liquid to flow toward the particle because of the increased surface tension (Gibbs— Marangoni effect), and thus cause a stabilizing effect. 

The precise mechanism resppnsible for the passivity conferred on metals by anodic inhibitors, such as chromate, is not known. While some early workers thought that a protective salt film (e.g., chromate) was formed, this view is not generally applicable, since passivity can occur in a system where the salt film would be freely soluble (e.g., iron in nitric acid). It is, however, generally accepted that passivity is associated with the formation of a protective film, and current views ascribe the action of anodic inhibitors either to adsorption at anodic sites or to continuous repair of the protective film. The former view has received attention in recent publications by Cartledge ), while the latter is favored by Evans (2). However, work on aluminum has suggested that true passivity is associated with the crystal structure of the film, which in turn determines its stability. This principle has recently been introduced by one of the authors (3) and is developed below into a general theory of passivity. 

The Frenkel-Halsey-Hill (FHH) isotherm was originally developed to describe the growth of thick films and wetting phenomena on a flat surface and was later extended to studying adsorption on fractal surfaces [3, 55]. In contrast to BET theory, FHH theory applies to long-range adsorbate-absorbent interactions and its approach is closely related to the so-called potential theory of adsorption of Eucken and Polanyi (see Ref. [35]). 

The preceding discussion of hquid-fluid interfaces, adsorption, monolayer films, and so forth, was extremely limited and a great deal of interesting and useful information was excluded. Although the theories and techniques discussed may be considered to be old in comparison to much of modern science, one finds repeatedly that a great many modern technological problems can be understood and solved on the basis of a little understanding of the classical ideas of such interfaces. 

The adsorption theory emphasizes that the observed Flade potential of passive iron is too noble by about 0.6 V to be explained by any of the known iron oxides in equilibrium with iron. Observed values of the Flade potential are consistent with a chemisorbed film of oxygen on the surface of iron, the corresponding potential of which is calculated (see Problem 2 in Chapter 6) using the observed heat and estimated entropy of adsorption of oxygen on iron in accord with the reaction [21]... 

According to the adsorption theory, passivity of chromium and the stainless steels, because of their pronounced affinity for oxygen, can occur by direct chemisorption of oxygen from the air or from aqueous solutions, and the equivalents of oxygen so adsorbed were found [22] to be of the same order of magnitude as the equivalents of passive film formed on iron when passivated either anodically, by concentrated nitric acid, or by exposure to chromates. Similarly, oxygen in air can adsorb directly on iron and passivate it in aerated alkaline solutions, or also in near-neutral solutions if the partial pressure of oxygen is increased sufficiently. 

The structure of the passive film on alloys, as with passive films in general, has been described both by the oxide-film theory and by the adsorption theory. It has been suggested that protective oxide films form above the critical alloy composition for passivity, but nonprotective oxide films form below the critical composition. The preferential oxidation of passive constituents (e.g., chromium) may form protective oxides (e.g., Cr203) above a specific alloy content, but not below. No quantitative predictions have been offered based on this point of view, and the fact that the passive film on stainless steels can be reduced cathodically, but not stoichiometric Cr203 itself, remains unexplained. 

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