Alloy films surface area

Copper Corrosion Inhibitors. The most effective corrosion inhibitors for copper and its alloys are the aromatic triazoles, such as benzotriazole (BZT) and tolyltriazole (TTA). These compounds bond direcdy with cuprous oxide (CU2O) at the metal surface, forming a "chemisorbed" film. The plane of the triazole Hes parallel to the metal surface, thus each molecule covers a relatively large surface area. The exact mechanism of inhibition is unknown. Various studies indicate anodic inhibition, cathodic inhibition, or a combination of the two. Other studies indicate the formation of an insulating layer between the water surface and the metal surface. A recent study supports the idea of an electronic stabilization mechanism. The protective cuprous oxide layer is prevented from oxidizing to the nonprotective cupric oxide. This is an anodic mechanism. However, the triazole film exhibits some cathodic properties as well. 

The pure metals are readily available to try out as catalysts, whereas the alloys are not, if a moderate surface area is required. Methods for preparing alloys as high-area powders, etc., raise questions about the unwanted introduction of promoters, e.g., chloride ions. Here, again, evaporated alloy films recommend themselves for the exploration of a whole new territory of alloy systems as catalysts in a variety of reactions. 

Vapor quenching provides a method of bridging the miscibility gap which exists in many alloy systems, and makes a range of novel alloys available for study. Such films, of course, would not be ideal for catalytic studies. They could not be used at high temperatures, and indeed the heat of reaction might be sufficient to induce a transformation to a more stable structure. In addition, characterization by X-ray diffraction would be difficult, even for the crystalline films, because of line broadening by the small crystallites. Nevertheless, alloy films which are metastable above room temperature can be prepared, and their high surface area would... 

The characterization of evaporated alloy films can be carried out at widely different levels of sophistication. At the very least, it is necessary to determine the bulk composition, probably after the film has been used for an adsorption or catalytic experiment. Then various techniques can be applied, e.g., X-ray diffraction, electron diffraction, and electron microscopy, to investigate the homogeneity or morphology of the film. The measurement of surface area by chemisorption presents special problems compared with the pure metals. Finally, there is the question of the surface composition (as distinct from the bulk or overall composition), and a brief account is given of techniques such as Auger electron spectroscopy which might be applied to alloy films. 

Alloy films are commonly sintered during preparation by deposition on substrates heated to, say, 400°C or by subsequent annealing at such temperatures, and, consequently, rather small surface areas have to be measured, perhaps in vessels of substantial volume. Krypton adsorption at liquid nitrogen temperature was used with induction-evaporated Cu-Ni, Fe-Ni, and Pd-Ni films, and BET surface areas of 1000-2000 cm2 were recorded (48), after correction for bare glass. The total area of Cu-Ni films was measured by the physical adsorption of xenon at — 196°C (70) in addition, the chemisorption of hydrogen on the same samples enabled the quantity a to be determined where... 

The observed ratio aaiioy/aNi agreed well with the Ni content predicted.) As discussed later, it was believed that hydrogen chemisorption was proportional to the surface nickel concentration (see Section IV). It is clear, however, that chemisorption as a method of surface area measurement must be used with discretion in the case of alloy films. 

In earlier work with pure metals, it was generally accepted that the area of films deposited at, say, 0°C was proportional to their weight (with the exception of group IB and low melting-point metals). Information was available on the surface areas of films of Ni, Pt, Pd, Rh, etc. (71), and hence absolute reaction rates could be calculated. It would be a considerable undertaking to establish similar data for alloy systems, bearing in mind that various compositions would have to be examined and also a method for preparing exact compositions would be required. However, for sintered alloy films, approximate methods can be proposed. 

Alternatively, it may be possible to demonstrate for the pure metals that the catalytic activity is independent of film weight in a certain weight range. For example, rates of ethylene oxidation were constant over pure palladium films, deposited and annealed at 400°C and weighing between 4 and 40 mg (73). Then, if electron micrographs show that the crystallite size is relatively independent of composition, a satisfactory comparison of catalytic activity can be made at the various alloy compositions. Finally, surface area measurements are less urgently needed when activity varies by orders of magnitude, or where the main interest lies outside the determination of absolute reaction rates. 

In one of the earliest reports of the use of clean evaporated alloy films in surface studies, Stephens described the preparation and characterization of Pd-Au films and presented some results for the adsorption of oxygen on them 46). Films of pure Pd and 60% Au were evaporated directly from wires, while films of 80% Au and pure Au were evaporated from a pre-outgassed tungsten support wire. The films were evaporated in a UHV system and the pressure was kept below PC8 Torr during evaporation. After evaporation, the films were stabilized by cycling between —195° and 30°C four times. They w ere characterized by X-ray diffraction and chemical analysis surface areas were measured by the BET method using krypton adsorption. 

There is now available a substantial amount of information on the principles and techniques involved in preparing evaporated alloy films suitable for adsorption or catalytic work, although some preparative methods, e.g., vapor quenching, used in other research fields have not yet been adopted. Alloy films have been characterized with respect to bulk properties, e.g., uniformity of composition, phase separation, crystallite orientation, and surface areas have been measured. Direct quantitative measurements of surface composition have not been made on alloy films prepared for catalytic studies, but techniques, e.g., Auger electron spectroscopy, are available. 

Here we will consider mainly the short-circuit current (SCC) output stability characteristics of both small grain, thin film CdSe and Cd(Se,Te)-based PEC s as well as those of single crystal CdSe-based cells, wh are different crystal faces are exposed to the solution, after they have undergone any of a series of surface treatments. These studies show a strong dependence of the output stability on solution composition, on real electrode surface area, on surface treatment, on crystal face and on crystal structure (for the Cd(Se,Te) alloys) (1,2 7). 

The development of new and improved electrocatalysts begins with the discovery of materials displaying improved intrinsic electrochemical activity. Intrinsic activity is best observed and compared in a well-controlled catalyst environment where variables that may disguise the intrinsic activity trends are minimized or absent. Particle size, particle size distribution, surface area, catalyst utilization and the distribution of crystallographic phases are parameters that are typically difficult to control. Vapor deposition of unsupported thin film electrocatalysts eliminates many of these variables. This method provides a controlled synthetic route to smooth, single-phase or multi-phase, ordered or disordered metal alloy phases depending on deposition and processing conditions. 

Li alloys may form a rigid host matrix to which Li is inserted upon charging. Hence, the surface area of the anode remains stable upon cycling, as do the surface films that cover the electrode, so exposure of fresh, reactive Li to the solution is avoided. 

There is an obvious overlap among various applications categories. An example of the overlap is alumina which is both a structural refractory ceramic as well as a catalyst support. The additives modify the interconversion of various AI2O3 phases and the high surface area of y-Al203 is maintained by the added 3 wt% ceria or lanthana. Additives like yttria stabilize zirconia with respect to inertness and mechanical stability. Addition of yttrium or lanthanide to Fe-Cr-Al alloys reduces the spallation of oxide film. 

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