Films, oxide

The study of passive films on electrode surfaces is an area of great fundamental and practical relevance. Despite decades of intensive investigations, there still exists a great deal of controversy as to the exact structural nature of passive films, especially when they are formed in the presence or absence of glass-forming additives such as chromium. 

One of the main sources of controversy is that many of the structural studies performed have been on dried films and, as pointed out by O Grady,69 this results in the determination of the structure of dehydrated films whose structure can be significantly different from that of hydrated ones. 

The use of surface EXAFS in the study of passive films represents a natural application of the technique and, in fact, the studies by Kruger and co-workers70 73 on the passive film on iron represent the first reported. 

Upon Fourier transforming of the data, two peaks corresponding to Fe—O and Fe—Fe distances are obtained (Fig. 13). The 

These results point to the importance of hydration effects on the structure of passive films on iron. However, these results were obtained ex situ and therefore are subject to some uncertainty. 

Compared with XPS and AES, the higher surface specificity of SSIMS (1-2 mono-layers compared with 2-8 monolayers) can be useful for more precise determination of the chemistry of an outer surface. Although from details of the 01s spectrum, XPS could give the information that OH and oxide were present on a surface, and from the Cls spectrum that hydrocarbons and carbides were present, only SSIMS could be used to identify the particular hydroxide or hydrocarbons. In the growth of oxide films for different purposes (e.g. passivation or anodization), such information is valuable, because it provides a guide to the quality of the film and the nature of the growth process. 

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Studies have been made on the rate of growth of oxide films on different crystal faces of a metal using ellipsometric methods. The rate was indeed different for (100), (101), (110), and (311) faces of copper [162] moreover, the film on a (311) surface was anisotropic in that its apparent thickness varied with the angle of rotation about the film normal. 

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. 

Thin oxide films may be prepared by substrate oxidation or by vapour deposition onto a suitable substrate. An example of the fomrer method is the preparation of silicon oxide thin-films by oxidation of a silicon wafer. In general, however, the thickness and stoichiometry of a film prepared by this method are difficult to control. 

Shanthi E, Dutta V, Baneqee A and Chopra K L 1980 Electrical and optical properties of undoped and antimony-doped tin oxide films J. Appi. Rhys. 51 6243-51... 

Gundlach K H and Kadlech J 1974 The influence of the oxide film on the current in AI-AI oxide-fatty acid monolayer-metal functions Chem. Phys. Lett. 25 293-5... 

Considering the case of pH > 9, the fonnation of an oxide film is favoured compared with Fe dissolution. 

In tenns of an electrochemical treatment, passivation of a surface represents a significant deviation from ideal electrode behaviour. As mentioned above, for a metal immersed in an electrolyte, the conditions can be such as predicted by the Pourbaix diagram that fonnation of a second-phase film—usually an insoluble surface oxide film—is favoured compared with dissolution (solvation) of the oxidized anion. Depending on the quality of the oxide film, the fonnation of a surface layer can retard further dissolution and virtually stop it after some time. Such surface layers are called passive films. This type of film provides the comparably high chemical stability of many important constmction materials such as aluminium or stainless steels. 

Highly protective layers can also fonn in gaseous environments at ambient temperatures by a redox reaction similar to that in an aqueous electrolyte, i.e. by oxygen reduction combined with metal oxidation. The thickness of spontaneously fonned oxide films is typically in the range of 1-3 nm, i.e., of similar thickness to electrochemical passive films. Substantially thicker anodic films can be fonned on so-called valve metals (Ti, Ta, Zr,. ..), which allow the application of anodizing potentials (high electric fields) without dielectric breakdown. 

Figure C2.8.5. Growth of an oxide film on a metal surface, (a) In tire absence of an externally applied potential ...

The protective quality of the passive film is detennined by the ion transfer tlirough the film as well as the stability of the film with respect to dissolution. The dissolution of passive oxide films can occur either chemically or electrochemically. The latter case takes place if an oxidized or reduced component of the passive film is more soluble in the electrolyte than the original component. An example of this is the oxidative dissolution of CrjO ... 

To illustrate some of the different approaches, let us consider passive films grown on Fe-Cr alloys. It has been established since 1911 [72] that an increase of Cr in the alloy increases the stability of the oxide film against dissolution. 

The percolation argument is based on the idea that with an increasing Cr content an insoluble interlinked cliromium oxide network can fonn which is also protective by embedding the otherwise soluble iron oxide species. As the tlireshold composition for a high stability of the oxide film is strongly influenced by solution chemistry and is different for different dissolution reactions [73], a comprehensive model, however, cannot be based solely on geometrical considerations but has in addition to consider the dissolution chemistry in a concrete way. 

Other authors have attributed the improved corrosion resistance with increasing Cr content with the increasing tendency of the oxide to become more disordered [69]. This would then suggest that an amoriDhous oxide film is more protective than a crystalline one, due to a bond and stmctural flexibility in amoriDhous films. 

C2.8.6(c). This increase occurs far below eitlier transpassive dissolution (oxide film dissolution due to tire fonnation of soluble higher oxidation states (e.g. Cr,0., ... 

In the potential range catliodic to one frequently observes so-called metastable pitting. A number of pit growtli events are initiated, but tire pits immediately repassivate (an oxide film is fonned in tire pit) because the conditions witliin tire pit are such that no stable pit growtli can be maintained. This results in a polarization curve witli strong current oscillations iU [Pg.2728]

C2.18.4.2 DEPOSITION OF OXIDE FILMS BY ATOMIC LAYER PROCESSING... 

Sheet aluminium can be given a colour by a similar process. The aluminium is first made the anode in a bath of chromic acid (p. 377) when, instead of oxygen being evolved, the aluminium becomes coated with a very adherent film of aluminium oxide which is very adsorbent. If a dye is added to the bath the oxide film is coloured, this colour being incorporated in a film which also makes the remaining aluminium resistant to corrosion. This process is called anodising aluminium. 

Films, anodic oxide Films, passivating Films, plastic Film theory Film wrappers Filter Filter aid Filter aids Filter fabrics Filtering centrifuges Filter media Filters... 

Dry chlorine has a great affinity for absorbing moisture, and wet chlorine is extremely corrosive, attacking most common materials except HasteUoy C, titanium, and tantalum. These metals are protected from attack by the acids formed by chlorine hydrolysis because of surface oxide films on the metal. Tantalum is the preferred constmction material for service with wet and dry chlorine. Wet chlorine gas is handled under pressure using fiberglass-reinforced plastics. Rubber-lined steel is suitable for wet chlorine gas handling up to 100°C. At low pressures and low temperatures PVC, chlorinated PVC, and reinforced polyester resins are also used. Polytetrafluoroethylene (PTFE), poly(vinyhdene fluoride) (PVDE), and... 

Hafnium Acetate. Hafnium acetate [15978-87-7], Hf(OH)2(CH2COO)2, solutions are prepared by reacting the basic carbonate or freshly precipitated hydroxide with acetic acid. The acetate solution has been of interest in preparing oxide films free of chloride or sulfate anions. 

This is essentially a corrosion reaction involving anodic metal dissolution where the conjugate reaction is the hydrogen (qv) evolution process. Hence, the rate depends on temperature, concentration of acid, inhibiting agents, nature of the surface oxide film, etc. Unless the metal chloride is insoluble in aqueous solution eg, Ag or Hg ", the reaction products are removed from the metal or alloy surface by dissolution. The extent of removal is controUed by the local hydrodynamic conditions. 

A rapid method to determine the calcium content of lead alloys is a Hquid-metal titration using lead—antimony (1%) (9). The end point is indicated by a gray oxide film pattern on the surface of a sohdifted sample of the metal when observed at a 45° angle to a light source. The basis for the titration is the reaction between calcium and antimony. The percentage of calcium in the sample can be calculated from the amount of antimony used. If additional calcium is needed in the alloy, the melt is sweetened with a lead—calcium (1 wt %) master alloy. 

If the ECM of titanium is attempted in sodium chloride electrolyte, very low (10—20%) current efficiency is usually obtained. When this solution is replaced by some mixture of fluoride-based electrolytes, to achieve greater efficiencies (> 60%), a higher voltage (ca 60 V) is used. These conditions ate needed to break down the tenacious oxide film that forms on the surface of titanium. It is this film which accounts for the corrosion resistance of titanium, and together with its toughness and lightness, make this metal so useful in the aircraft engine industry. 

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. 

Inasmuch as friction conditions determine the flow characteristics of a powder, coarser powder particles of spherical shape flow fastest and powder particles of identical diameter but irregular shape flow more slowly. Finer particles may start to flow, but stop after a short time. Tapping is needed in order to start the flow again. Very fine powders (fine powder particles to coarser ones may increase the apparent density, but usually decreases the flow quality. Metal powders having a thin oxide film may flow well. When the oxide film is removed and the friction between the particles therefore increases, these powders may flow poorly. 

Probably the most important powder property governing the formation of atomic bonds is the surface condition of the particles, especially with respect to the presence of oxide films. If heavy oxide layers are present, they must be penetrated by projections on the particles. This results in only local rather than widespread bonding. A ductile metal such as iron which has a heavy oxide layer may not form as strong or as many bonds as a less ductile metal. 

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